The 100 most-cited articles in Advanced Materials, 2023

Abstract Flexible multifunctional polymer‐based electromagnetic interference (EMI) shielding composite films have important applications in the fields of 5G communication technology, wearable electronic devices, and artificial intelligence. Based on the design of a porous/multilayered structure and using polyimide (PI) as the matrix and polymethyl methacrylate (PMMA) microspheres as the template, flexible (Fe 3 O 4 /PI)–Ti 3 C 2 T x –(Fe 3 O 4 /PI) composite films with controllable pore sizes and distribution of Ti 3 C 2 T x hollow microspheres are successfully prepared by sacrificial template method. Owing to the porous/multilayered structure, when the pore size of the Ti 3 C 2 T x hollow microspheres is 10 µm and the mass ratio of PMMA/Ti 3 C 2 T x is 2:1, the (Fe 3 O 4 /PI)–Ti 3 C 2 T x –(Fe 3 O 4 /PI) composite film has the most excellent EMI shielding performance, with EMI shielding effectiveness (EMI SE) of 85 dB. It is further verified by finite element simulation that the composite film has an excellent shielding effect on electromagnetic waves. In addition, the composite…

Abstract Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N‐containing fertilizers induces the increase of nitrate level in surface and ground waters, and substantial emission of nitrogen oxides causes heavy air pollution. Nitrogen gas, as the main component of air, has been used for mass ammonia production for over a century, providing enough nutrition for agriculture to support world population increase. In the last decade, researchers have made great efforts to develop ammonia processes under ambient conditions to combat the intensive energy consumption and high carbon emission associated with the Haber–Bosch process. Among different techniques, electrochemical nitrate reduction reaction (NO 3 RR) can achieve nitrate removal and ammonia generation simultaneously using renewable electricity as the power, and there is an exponential growth of studies in this research direction. Here, a timely and comprehensive review on the important progresses of electrochemical NO 3 RR, covering the rational design of electrocatalysts, emerging CN…

"Nanozyme" is used to describe various catalysts from immobilized inorganic metal complexes, immobilized enzymes to inorganic nanoparticles. Here, the history of nanozymes is dvescribed in detail, and they can be largely separated into two types. Type 1 nanozymes refer to immobilized catalysts or enzymes on nanomaterials, which were dominant in the first decade since 2004. Type 2 nanozymes, which rely on the surface catalytic properties of inorganic nanomaterials, are the dominating type in the past decade. The definition of nanozymes is evolving, and a definition based on the same substrates and products as enzymes are able to cover most currently claimed nanozymes, although they may have different mechanisms compared to their enzyme counterparts. A broader definition can inspire application-based research to replace enzymes with nanomaterials for analytical, environmental, and biomedical applications. Comparison with enzymes also requires a clear definition of a nanozyme unit. Four ways of defining a nanozyme unit are described, with iron oxide and horseradish peroxidase activity…

Hard carbons, an important category of amorphous carbons, are non-graphitizable and are widely accepted as the most promising anode materials for emerging sodium-ion batteries (SIBs)， because of their changeable low-potential charge/discharge plateaus. However, their microstructures are not fixed and are difficult to accurately demonstrate as graphites do. The successful use of hard carbons in SIBs revives the interest to clearly picture their complicated microstructures that are in close relevance to sodium storage. In this review, the past definitions and structural models of hard carbons are revisited first, and a renewed understanding of their sodium storage is presented. Three critical structural features are highlighted for hard carbons, namely crystallites, defects, and nanopores, which are directly responsible for the presence of the low-potential plateaus and their reversible extension. The impact of these structural features upon the sodium storage is then deeply discussed and sieving carbons is finally proposed as an ideal configuration of carbon anode for superhigh…

Semiconductor photocatalytic technology holds immense promise for converting sustainable solar energy into chemically storable energy, with significant applications in the realms of energy and the environment. However, the inherent issue of rapid recombination of photogenerated electrons and holes hinders the performance of single photocatalysts. To overcome this challenge, the construction of 2D S-scheme heterojunction photocatalysts emerges as an effective strategy. The deliberate design of dimensionality ensures a substantial interfacial area; while, the S-scheme charge transfer mechanism facilitates efficient charge separation and maximizes redox capabilities. This review commences with a fresh perspective on the charge transfer mechanism in S-scheme heterojunctions, followed by a comprehensive exploration of preparation methods and characterization techniques. Subsequently, the recent advancements in 2D S-scheme heterojunction photocatalysts are summarized. Notably, the mechanism behind activity enhancement is elucidated. Finally, the prospects for the development of 2D…

Abstract Single‐atom catalysts (SACs) have attracted extensive interest to catalyze the oxygen reduction reaction (ORR) in fuel cells and metal–air batteries. However, the development of SACs with high selectivity and long‐term stability is a great challenge. In this work, carbon vacancy modified Fe–N–C SACs (Fe H –N–C) are practically designed and synthesized through microenvironment modulation, achieving high‐efficient utilization of active sites and optimization of electronic structures. The Fe H –N–C catalyst exhibits a half‐wave potential ( E 1/2 ) of 0.91 V and sufficient durability of 100 000 voltage cycles with 29 mV E 1/2 loss. Density functional theory (DFT) calculations confirm that the vacancies around metal–N 4 sites can reduce the adsorption free energy of OH*, and hinder the dissolution of metal center, significantly enhancing the ORR kinetics and stability. Accordingly, Fe H –N–C SACs presented a high‐power density and long‐term stability over 1200 h in rechargeable zinc–air batteries (ZABs). This work will not only guide for developing highly active and stable SACs…

Abstract Involving eight electron transfer process and multiple intermediates of nitrate (NO 3 − ) reduction reaction leads to a sluggish kinetic and low Faradaic efficiency, therefore, it is essential to get an insight into the reaction mechanism to develop highly efficient electrocatalyst. Herein, a series of reduced‐graphene‐oxide‐supported RuCu alloy catalysts (Ru x Cu x /rGO) are fabricated and used for the direct reduction of NO 3 − to NH 3 . It is found that the Ru 1 Cu 10 /rGO shows the ammonia formation rate of 0.38 mmol cm −2 h −1 (loading 1 mg cm −2 ) and the ammonia Faradaic efficiency of 98% under an ultralow potential of −0.05 V versus Reversible Hydrogen Electode (RHE), which is comparable to Ru catalyst. The highly efficient activity of Ru 1 Cu 10 /rGO can be attributed to the synergetic effect between Ru and Cu sites via a relay catalysis, in which the Cu shows the exclusively efficient activity for the reduction of NO 3 − to NO 2 − and Ru exhibits the superior activity for NO 2 − to NH 3 . In addition, the doping of Ru into Cu tunes the d‐band center of alloy and…

Messenger RNA (mRNA) has received great attention in the prevention and treatment of various diseases due to the success of coronavirus disease 2019 (COVID-19) mRNA vaccines (Comirnaty and Spikevax). To meet the therapeutic purpose, it is required that mRNA must enter the target cells and express sufficient proteins. Therefore, the development of effective delivery systems is necessary and crucial. Lipid nanoparticle (LNP) represents a remarkable vehicle that has indeed accelerated mRNA applications in humans, as several mRNA-based therapies have already been approved or are in clinical trials. In this review, the focus is on mRNA-LNP-mediated anticancer therapy. It summarizes the main development strategies of mRNA-LNP formulations, discusses representative therapeutic approaches in cancer, and points out current challenges and possible future directions of this research field. It is hoped that these delivered messages can help further improve the application of mRNA-LNP technology in cancer therapy.

Nanomaterials with more than one enzyme-like activity are termed multienzymic nanozymes, and they have received increasing attention in recent years and hold huge potential to be applied in diverse fields, especially for biosensing and therapeutics. Compared to single enzyme-like nanozymes, multienzymic nanozymes offer various unique advantages, including synergistic effects, cascaded reactions, and environmentally responsive selectivity. Nevertheless, along with these merits, the catalytic mechanism and rational design of multienzymic nanozymes are more complicated and elusive as compared to single-enzymic nanozymes. In this review, the multienzymic nanozymes classification scheme based on the numbers/types of activities, the internal and external factors regulating the multienzymatic activities, the rational design based on chemical, biomimetic, and computer-aided strategies, and recent progress in applications attributed to the advantages of multicatalytic activities are systematically discussed. Finally, current challenges and future perspectives regarding the development and…

Morphology optimization is critical for achieving high efficiency and stable bulk-heterojunction (BHJ) organic solar cells (OSCs). Herein, the use of 3,5-dichlorobromobenzene (DCBB) with high volatility and low cost to manipulate evolution of the BHJ morphology and improve the operability and photostability of OSCs is proposed. Systematic simulations reveal the charge distribution of DCBB and its non-covalent interaction with the active layer materials. The addition of DCBB can effectively tune the aggregation of PBQx-TF:eC9-2Cl during film formation, resulting in a favorable phase separation and a reinforced molecular packing. As a result, a power conversion efficiency of 19.2% (certified as 19.0% by the National Institute of Metrology) for DCBB-processed PBQx-TF:eC9-2Cl-based OSCs, which is the highest reported value for binary OSCs, is obtained. Importantly, the DCBB-processed devices exhibit superior photostability and have thus considerable application potential in the printing of large-area devices, demonstrating outstanding universality in various BHJ systems. The study…

Luminescence (nano)thermometry is a remote sensing technique that relies on the temperature dependency of the luminescence features (e.g., bandshape, peak energy or intensity, and excited state lifetimes and risetimes) of a phosphor to measure temperature. This technique provides precise thermal readouts with superior spatial resolution in short acquisition times. Although luminescence thermometry is just starting to become a more mature subject, it exhibits enormous potential in several areas, e.g., optoelectronics, photonics, micro- and nanofluidics, and nanomedicine. This work reviews the latest trends in the field, including the establishment of a comprehensive theoretical background and standardized practices. The reliability, repeatability, and reproducibility of the technique are also discussed, along with the use of multiparametric analysis and artificial-intelligence algorithms to enhance thermal readouts. In addition, examples are provided to underscore the challenges that luminescence thermometry faces, alongside the need for a continuous search and design of new…

Abstract Perovskite light‐emitting diodes (PeLEDs) are strong candidates for next‐generation display and lighting technologies due to their high color purity and low‐cost solution‐processed fabrication. However, PeLEDs are not superior to commercial organic light‐emitting diodes (OLEDs) in efficiency, as some key parameters affecting their efficiency, such as the charge carrier transport and light outcoupling efficiency, are usually overlooked and not well optimized. Here, ultrahigh‐efficiency green PeLEDs are reported with quantum efficiencies surpassing a milestone of 30% by regulating the charge carrier transport and near‐field light distribution to reduce electron leakage and achieve a high light outcoupling efficiency of 41.82%. Ni 0.9 Mg 0.1 O x films are applied with a high refractive index and increased hole carrier mobility as the hole injection layer to balance the charge carrier injection and insert the polyethylene glycol layer between the hole transport layer and the perovskite emissive layer to block the electron leakage and reduce the photon loss. Therefore, with the…

Abstract High‐entropy oxides (HEOs), which incorporate multiple‐principal cations into single‐phase crystals and interact with diverse metal ions, extend the border for available compositions and unprecedented properties. Herein, a high‐entropy‐stabilized (Ca 0.2 Sr 0.2 Ba 0.2 La 0.2 Pb 0.2 )TiO 3 perovskite is reported, and the effective absorption bandwidth (90% absorption) improves almost two times than that of BaTiO 3 . The results demonstrate that the regulation of entropy configuration can yield significant grain boundaries, oxygen defects, and an ultradense distorted lattice. These characteristics give rise to strong interfacial and defect‐induced polarizations, thus synergistically contributing to the dielectric attenuation performance. Moreover, the large strains derived from the strong lattice distortions in the high‐entropy perovskite offer varied transport for electron carriers. The high‐entropy‐enhanced positive/negative charges accumulation around grain boundaries and strain‐concentrated location, quantitatively validated by electron holography, results in unusual…

Growth factors play a crucial role in regulating a broad variety of biological processes and are regarded as powerful therapeutic agents in tissue engineering and regenerative medicine in the past decades. However, their application is limited by their short half-lives and potential side effects in physiological environments. Hydrogels are identified as having the promising potential to prolong the half-lives of growth factors and mitigate their adverse effects by restricting them within the matrix to reduce their rapid proteolysis, burst release, and unwanted diffusion. This review discusses recent progress in the development of growth factor-containing hydrogels for various biomedical applications, including wound healing, brain tissue repair, cartilage and bone regeneration, and spinal cord injury repair. In addition, the review introduces strategies for optimizing growth factor release including affinity-based delivery, carrier-assisted delivery, stimuli-responsive delivery, spatial structure-based delivery, and cellular system-based delivery. Finally, the review presents…

Abstract Rare‐earth (RE)‐based transition metal oxides (TMO) are emerging as a frontier toward the oxygen evolution reaction (OER), yet the knowledge regarding their electrocatalytic mechanism and active sites is very limited. In this work, atomically dispersed Ce on CoO is successfully designed and synthesized by an effective plasma (P)‐assisted strategy as a model (P‐Ce SAs@CoO) to investigate the origin of OER performance in RE–TMO systems. The P‐Ce SAs@CoO exhibits favorable performance with an overpotential of only 261 mV at 10 mA cm−2 and robust electrochemical stability, superior to individual CoO. X‐ray absorption spectroscopy and in situ electrochemical Raman spectroscopy reveal that the Ce‐induced electron redistribution inhibits CoO bond breakage in the CoOCe unit site. Theoretical analysis demonstrates that the gradient orbital coupling reinforces the CoO covalency of the Ce(4f)─O(2p)─Co(3d) unit active site with an optimized Co‐3d‐eg occupancy, which can balance the adsorption strength of intermediates and in turn reach the apex of the theoretical OER maximum, in…

Abstract As one of the most promising approaches to producing high‐purity hydrogen (H 2 ), electrochemical water splitting powered by the renewable energy sources such as solar, wind, and hydroelectric power has attracted considerable interest over the past decade. However, the water electrolysis process is seriously hampered by the sluggish electrode reaction kinetics, especially the four‐electron oxygen evolution reaction at the anode side, which induces a high reaction overpotential. Currently, the emerging hybrid electrochemical water splitting strategy is proposed by integrating thermodynamically favorable electro–oxidation reactions with hydrogen evolution reaction at the cathode, providing a new opportunity for energy–efficient H2 production. To achieve highly efficient and cost–effective hybrid water splitting toward large–scale practical H 2 production, much work has been continuously done to exploit the alternative anodic oxidation reactions and cutting–edge electrocatalysts. This review will focus on recent developments on electrochemical H 2 production coupled with…

Abstract The elastomers with the combination of high strength and high toughness have always been intensively pursued due to their diverse applications. Biomedical applications frequently require elastomers with biodegradability and biocompatibility properties. It remains a great challenge to prepare the biodegradable elastomers with extremely robust mechanical properties for in vivo use. In this report, we present a polyurethane elastomer with unprecedented mechanical properties for the in vivo application as hernia patches, which was obtained by the solvent‐free reaction of polycaprolactone (PCL) and isophorone diisocyanate (IPDI) with N , N ‐bis(2‐hydroxyethyl)oxamide (BHO) as the chain extender. Abundant and hierarchical hydrogen‐bonding interactions inside the elastomers hinder the crystallization of PCL segments and facilitate the formation of uniformly distributed hard phase microdomains, which miraculously realize the extremely high strength and toughness with the fracture strength of 92.2 MPa and true stress of 1.9 GPa, while maintaining the elongation‐at‐break of ≈1900%…

Cuproptosis is a new cell death that depends on copper (Cu) ionophores to transport Cu into cancer cells, which induces cell death. However, existing Cu ionophores are small molecules with a short blood half-life making it hard to transport enough Cu into cancer cells. Herein, a reactive oxygen species (ROS)-sensitive polymer (PHPM) is designed, which is used to co-encapsulate elesclomol (ES) and Cu to form nanoparticles (NP@ESCu). After entering cancer cells, ES and Cu, triggered by excessive intracellular ROS, are readily released. ES and Cu work in a concerted way to not only kill cancer cells by cuproptosis, but also induce immune responses. In vitro, the ability of NP@ESCu to efficiently transport Cu and induce cuproptosis is investigated. In addition, the change in the transcriptomes of cancer cells treated with NP@ESCu is explored by RNA-Seq. In vivo, NP@ESCu is found to induce cuproptosis in the mice model with subcutaneous bladder cancer, reprograming the tumor microenvironment. Additionally, NP@ESCu is further combined with anti-programmed cell death protein ligand-1…

Abstract Constructing a homogenous and inorganic‐rich solid electrolyte interface (SEI) can efficiently improve the overall sodium‐storage performance of hard carbon (HC) anodes. However, the thick and heterogenous SEI derived from conventional ester electrolytes fails to meet the above requirements. Herein, an innovative interfacial catalysis mechanism is proposed to design a favorable SEI in ester electrolytes by reconstructing the surface functionality of HC, of which abundant CO (carbonyl) bonds are accurately and homogenously implanted. The CO (carbonyl) bonds act as active centers that controllably catalyze the preferential reduction of salts and directionally guide SEI growth to form a homogenous, layered, and inorganic‐rich SEI. Therefore, excessive solvent decomposition is suppressed, and the interfacial Na + transfer and structural stability of SEI on HC anodes are greatly promoted, contributing to a comprehensive enhancement in sodium‐storage performance. The optimal anodes exhibit an outstanding reversible capacity (379.6 mAh g −1 ), an ultrahigh initial Coulombic…

Current therapeutic protocols for diabetic foot ulcers (DFUs), a severe and rapidly growing chronic complication in diabetic patients, remain nonspecific. Hyperglycemia-caused inflammation and excessive reactive oxygen species (ROS) are common obstacles encountered in DFU wound healing, often leading to impaired recovery. These two effects reinforce each other, forming an endless loop. However, adequate and inclusive methods are still lacking to target these two aspects and break the vicious cycle. This study proposes a novel approach for treating DFU wounds, utilizing an immunomodulatory hydrogel to achieve self-cascade glucose depletion and ROS scavenging to regulate the diabetic microenvironment. Specifically, AuPt@melanin-incorporated (GHM3) hydrogel dressing is developed to facilitate efficient hyperthermia-enhanced local glucose depletion and ROS scavenging. Mechanistically, in vitro/vivo experiments and RNA sequencing analysis demonstrate that GHM3 disrupts the ROS-inflammation cascade cycle and downregulates the ratio of M1/M2 macrophages, consequently improving the…

Abstract By providing dual active sites to synergistically accelerate H 2 O dissociation and H + reduction, ordered intermetallic alloys usually show extraordinary performance for pH‐universal hydrogen evolution reaction (HER). Herein, activated N‐doped mesoporous carbon spheres supported intermetallic Pt 3 Fe alloys (Pt 3 Fe/NMCS‐A), as a highly‐efficient electrocatalyst for pH‐universal HER, are reported. The Pt 3 Fe/NMCS‐A exhibits low overpotentials ( η 10 ) of 13, 29, and 48 mV to deliver 10 mA cm −2 in 0.5 m H 2 SO 4 , 1.0 m KOH, and 1.0 m phosphate buffered solution (PBS), respectively, as well as robust stability to maintain the overall catalytic performances. Theoretical studies reveal that the strong Pt 5d–Fe 3d orbital electronic interactions negatively shift the d‐band center ( ε d ) of Pt 5d orbital, resulting in reduced H* adsorption energy of Pt sites and enhanced acidic HER activity. With Pt and Fe acting as co‐adsorption sites for H* and *OH intermediates, respectively, a low energy barrier is required for Pt 3 Fe/NMCS‐A to dissociate H 2 O to afford H*…

Self-assembled monolayers (SAMs) are widely employed as effective hole-selective layers (HSLs) in inverted perovskite solar cells (PSCs). However, most SAM molecules are amphiphilic in nature and tend to form micelles in the commonly used alcoholic processing solvents. This introduces an extra energetic barrier to disassemble the micelles during the binding of SAM molecules on the substrate surface, limiting the formation of a compact SAM. To alleviate this problem for achieving optimal SAM growth, a co-solvent strategy to disassemble the micelles of carbazole-based SAM molecules in the processing solution is developed. This effectively increases the critical micelle concentration to be above the processing concentration and enhances the reactivity of the phosphonic acid anchoring group to allow densely packed SAMs to be formed on indium tin oxide. Consequently, the PSCs derived from using MeO-2PACz, 2PACz, and CbzNaph SAM HSLs show universally improved performance, with the CbzNaph SAM-derived device achieving a champion efficiency of 24.98% and improved stability.

Mechanical metamaterials are meticulously designed structures with exceptional mechanical properties determined by their microstructures and constituent materials. Tailoring their material and geometric distribution unlocks the potential to achieve unprecedented bulk properties and functions. However, current mechanical metamaterial design considerably relies on experienced designers' inspiration through trial and error, while investigating their mechanical properties and responses entails time-consuming mechanical testing or computationally expensive simulations. Nevertheless, recent advancements in deep learning have revolutionized the design process of mechanical metamaterials, enabling property prediction and geometry generation without prior knowledge. Furthermore, deep generative models can transform conventional forward design into inverse design. Many recent studies on the implementation of deep learning in mechanical metamaterials are highly specialized, and their pros and cons may not be immediately evident. This critical review provides a comprehensive overview of the…

Abstract Hard carbons, as one of the most commercializable anode materials for sodium‐ion batteries (SIBs), have to deal with the trade‐off between the rate capability and specific capacity or initial Columbic efficiency (ICE), and the fast performance decline at low temperature (LT) remains poorly understood. Here, a comprehensive regulation on the interfacial/bulk electrochemistry of hard carbons through atomic Zn doping is reported, which demonstrates a record‐high reversible capacity (546 mAh g −1 ), decent ICE (84%), remarkable rate capability (140 mAh g −1 @ 50 A g −1 ), and excellent LT capacity (443 mAh g −1 @ −40 °C), outperforming the state‐of‐the‐art literature. This work reveals that the Zn doping can generally induce a local electric field to enable fast bulk Na + transportation, and meanwhile catalyze the decomposition of NaPF 6 to form a robust inorganic‐rich solid‐electrolyte interphase, which elaborates the underlying origin of the boosted electrochemical performance. Importantly, distinguished from room temperature, the intrinsic Na + migration/desolvation ability…

Abstract This topical review focuses on the distinct role of carbon support coordination environment of single‐atom catalysts (SACs) for electrocatalysis. The article begins with an overview of atomic coordination configurations in SACs, including a discussion of the advanced characterization techniques and simulation used for understanding the active sites. A summary of key electrocatalysis applications is then provided. These processes are oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), and carbon dioxide reduction reaction (CO 2 RR). The review then shifts to modulation of the metal atom‐carbon coordination environments, focusing on nitrogen and other non‐metal coordination through modulation at the first coordination shell and modulation in the second and higher coordination shells. Representative case studies are provided, starting with the classic four‐nitrogen‐coordinated single metal atom (MN 4 ) based SACs. Bimetallic coordination models including homo‐paired and hetero‐paired active…

Abstract Diabetic wound (DW) therapy is currently a big challenge in medicine and strategies to enhance neurogenesis and angiogenesis have appeared to be a promising direction. However, the current treatments have failed to coordinate neurogenesis and angiogenesis simultaneously, leading to an increased disability rate caused by DWs. Herein, a whole‐course‐repair system is introduced by a hydrogel to concurrently achieve a mutually supportive cycle of neurogenesis‐angiogenesis under a favorable immune‐microenvironment. This hydrogel can first be one‐step packaged in a syringe for later in situ local injections to cover wounds long‐termly for accelerated wound healing via the synergistic effect of magnesium ions (Mg 2+ ) and engineered small extracellular vesicles (sEVs). The self‐healing and bio‐adhesive properties of the hydrogel make it an ideal physical barrier for DWs. At the inflammation stage, the formulation can recruit bone marrow‐derived mesenchymal stem cells to the wound sites and stimulate them toward neurogenic differentiation, while providing a favorable immune…

Abstract Electrocatalytic CN coupling between carbon dioxide and nitrate has emerged to meet the comprehensive demands of carbon footprint closing, valorization of waste, and sustainable manufacture of urea. However, the identification of catalytic active sites and the design of efficient electrocatalysts remain a challenge. Herein, the synthesis of urea catalyzed by copper single atoms decorated on a CeO 2 support (denoted as Cu 1 –CeO 2 ) is reported. The catalyst exhibits an average urea yield rate of 52.84 mmol h −1 g cat. −1 at −1.6 V versus reversible hydrogen electrode. Operando X‐ray absorption spectra demonstrate the reconstitution of copper single atoms (Cu 1 ) to clusters (Cu 4 ) during electrolysis. These electrochemically reconstituted Cu 4 clusters are real active sites for electrocatalytic urea synthesis. Favorable CN coupling reactions and urea formation on Cu 4 are validated using operando synchrotron‐radiation Fourier transform infrared spectroscopy and theoretical calculations. Dynamic and reversible transformations of clusters to single‐atom configurations…

Emerging piezocatalysts have demonstrated their remarkable application potential in diverse medical fields. In addition to their ultrahigh catalytic activities, their inherent and unique charge-carrier-releasing properties can be used to initiate various redox catalytic reactions, displaying bright prospects for future medical applications. Triggered by mechanical energy, piezocatalytic materials can release electrons/holes, catalyze redox reactions of substrates, or intervene in biological processes to promote the production of effector molecules for medical purposes, such as decontamination, sterilization, and therapy. Such a medical application of piezocatalysis is termed as piezocatalytic medicine (PCM) herein. To pioneer novel medical technologies, especially therapeutic modalities, this review provides an overview of the state-of-the-art research progress in piezocatalytic medicine. First, the principle of piezocatalysis and the preparation methodologies of piezoelectric materials are introduced. Then, a comprehensive summary of the medical applications of piezocatalytic…

The energy efficiency of metal-air batteries and water-splitting techniques is severely constrained by multiple electronic transfers in the heterogenous oxygen evolution reaction (OER), and the high overpotential induced by the sluggish kinetics has become an uppermost scientific challenge. Numerous attempts are devoted to enabling high activity, selectivity, and stability via tailoring the surface physicochemical properties of nanocatalysts. Lattice-strain engineering as a cutting-edge method for tuning the electronic and geometric configuration of metal sites plays a pivotal role in regulating the interaction of catalytic surfaces with adsorbate molecules. By defining the d-band center as a descriptor of the structure-activity relationship, the individual contribution of strain effects within state-of-the-art electrocatalysts can be systematically elucidated in the OER optimization mechanism. In this review, the fundamentals of the OER and the advancements of strain-catalysts are showcased and the innovative trigger strategies are enumerated, with particular emphasis on the…

reduction, reversible fuel cells, and metal-air batteries. However, OER catalysis in acids suffers from extra sluggish kinetics due to the additional step of water dissociation along with its multiple electron transfer processes. Furthermore, OER catalysts often suffer from poor stability in harsh acidic electrolytes due to the severe dissolution/corrosion processes. The development of active and stable OER catalysts in acids is highly demanded. Here, the recent advances in OER electrocatalysis in acids are reviewed and the key strategies are summarized to overcome the bottlenecks of activity and stability for both noble-metal-based and noble metal-free catalysts, including i) morphology engineering, ii) composition engineering, and iii) defect engineering. Recent achievements in operando characterization and theoretical calculations are summarized which provide an unprecedented understanding of the OER mechanisms regarding active site identification, surface reconstruction, and degradation/dissolution pathways. Finally, views are offered on the current challenges and opportunities…

Sluggish reaction kinetics and severe shuttling effect of lithium polysulfides seriously hinder the development of lithium-sulfur batteries. Heterostructures, due to unique properties, have congenital advantages that are difficult to be achieved by single-component materials in regulating lithium polysulfides by efficient catalysis and strong adsorption to solve the problems of poor reaction kinetics and serious shuttling effect of lithium-sulfur batteries. In this review, the principles of heterostructures expediting lithium polysulfides conversion and anchoring lithium polysulfides are detailedly analyzed, and the application of heterostructures as sulfur host, interlayer, and separator modifier to improve the performance of lithium-sulfur batteries is systematically reviewed. Finally, the problems that need to be solved in the future study and application of heterostructures in lithium-sulfur batteries are prospected. This review will provide a valuable reference for the development of heterostructures in advanced lithium-sulfur batteries.

Nanozymes, a class of nanomaterials mimicking the function of enzymes, have aroused much attention as the candidate in diverse fields with the arbitrarily tunable features owing to the diversity of crystalline nanostructures, composition, and surface configurations. However, the uncertainty of their active sites and the lower intrinsic deficiencies of nanomaterial-initiated catalysis compared with the natural enzymes promote the pursuing of alternatives by imitating the biological active centers. Single-atom nanozymes (SAzymes) maximize the atom utilization with the well-defined structure, providing an important bridge to investigate mechanism and the relationship between structure and catalytic activity. They have risen as the new burgeoning alternative to the natural enzyme from in vitro bioanalytical tool to in vivo therapy owing to the flexible atomic engineering structure. Here, focus is mainly on the three parts. First, a detailed overview of single-atom catalyst synthesis strategies including bottom-up and top-down approaches is given. Then, according to the structural…

Shape memory alloys (SMAs) are smart materials that are widely used to create intelligent devices because of their high energy density, actuation strain, and biocompatibility characteristics. Given their unique properties, SMAs are found to have significant potential for implementation in many emerging applications in mobile robots, robotic hands, wearable devices, aerospace/automotive components, and biomedical devices. Here, the state-of-the-art of thermal and magnetic SMA actuators in terms of their constituent materials, form, and scaling effects are summarized, including their surface treatments and functionalities. The motion performance of various SMA architectures (wires, springs, smart soft composites, and knitted/woven actuators) is also analyzed. Based on the assessment, current challenges of SMAs that need to be addressed for their practical application are emphasized. Finally, how to advance SMAs by synergistically considering the effects of material, form, and scale is suggested.

Abstract Poor thermodynamic stability and sluggish electrochemical kinetics of metallic Zn anode in aqueous solution greatly hamper its practical application. To solve such problems, to date, various zincophilic surface modification strategies are developed, which can facilitate reversible Zn plating/stripping behavior. However, there is still a lack of systematic and fundamental understanding regarding the metrics of thermodynamics inertia and kinetics zincophilia in selecting zincophilic sites. Herein, hetero‐metallic interfaces are prioritized for the first time via optimizing different hetero metals (Fe, Co, Ni, Sn, Bi, Cu, Zn, etc.) and synthetic solvents (ethanol, ethylene glycol, n ‐propanol, etc.). Specifically, both theoretical simulations and experimental results suggest that this Bi@Zn interface can exhibit high efficiency owing to the thermodynamics inertia and kinetics zincophilia. A best practice for prioritizing zincophilic sites in a more practical metric is also proposed. As a proof of concept, the Bi@Zn anode delivers ultralow overpotential of ≈55 mV at a high rate…

The study of direct methanol fuel cells (DMFCs) has lasted around 70 years, since the first investigation in the early 1950s. Though enormous effort has been devoted in this field, it is still far from commercialization. The methanol oxidation reaction (MOR), as a semi-reaction of DMFCs, is the bottleneck reaction that restricts the overall performance of DMFCs. To date, there has been intense debate on the complex six-electron reaction, but barely any reviews have systematically discussed this topic. To this end, the controversies and progress regarding the electrocatalytic mechanisms, performance evaluations as well as the design science toward MOR electrocatalysts are summarized. This review also provides a comprehensive introduction on the recent development of emerging MOR electrocatalysts with a focus on the innovation of the alloy, core-shell structure, heterostructure, and single-atom catalysts. Finally, perspectives on the future outlook toward study of the mechanisms and design of electrocatalysts are provided.

Abstract Regulating the electronic states of single atomic sites around the Fermi level remains a major concern for boosting the electrocatalytic oxygen reduction reaction (ORR). Herein, a Fe d‐orbital splitting manner modulation strategy by constructing axial coordination on FeN 4 sites is presented. Experimental investigations and theoretical calculations reveal that the axial tractions induce the distortion of square‐planar field (FeN 4 SP ), up to the quasi‐octahedral coordination (FeN 4 O 1 OC quasi ), thus leading to the electron rearrangement with a diluted spin polarization. The declined population of unpaired electrons in d z 2 , d x z and d yz states engenders a moderate adsorption of ORR intermediates, thereby reinforcing the intrinsic reaction activity. In situ infrared spectroscopy further demonstrates that the reordering of d‐orbital splitting and occupation facilitates the desorption of *OH. The FeN 4 O 1 OC quasi exhibits a dramatic improvement of kinetic current density and turnover frequency, which are fivefold and tenfold higher than those of FeN 4 SP . This…

Since 2004, the design of high entropy alloys (HEAs) has generated significant interest within the materials science community due to their exceptional structural and functional properties. By incorporating multiple principal elements into a common lattice, it is possible to create a single-phase crystal with a highly distorted lattice. This unique feature enables HEAs to offer a promising combination of mechanical and physical properties that are not typically observed in conventional alloys. In this article, an extensive overview of multifunctional HEAs that exhibit severe lattice distortion is provided, covering the theoretical models that are developed to understand lattice distortion, the experimental and computational methods employ to characterize lattice distortion, and most importantly, the impact of severe lattice distortion on the mechanical, physical and electrochemical properties of HEAs. Through this review, it is hoped to stimulate further research into the study of distorted lattices in crystalline solids.

Abstract As promising hydrogen energy carrier, formic acid (HCOOH) plays an indispensable role in building a complete industry chain of a hydrogen economy. Currently, the biomass upgrading assisted water electrolysis has emerged as an attractive alternative for co‐producing green HCOOH and H 2 in a cost‐effective manner, yet simultaneously affording high current density and Faradaic efficiency (FE) still remains a big challenge. Here, the ternary NiVRu‐layered double hydroxides (LDHs) nanosheet arrays for selective glycerol oxidation and hydrogen evolution catalysis are reported, which yield an industry‐level 1 A cm −2 at voltage of 1.933 V, meanwhile showing considerable HCOOH and H 2 productivities of 12.5 and 17.9 mmol cm −2 h −1 , with FEs of almost 80% and 96%, respectively. Experimental and theoretical results reveal that the introduced Ru atoms can tune the local electronic structure of Ni‐based LDHs, which not only optimizes hydrogen adsorption kinetics for HER, but also reduces the reaction energy barriers for both the conversion of Ni II into GOR‐active Ni III and…

Organic solar cells (OSCs) have made dramatic advancements during the past decades owing to the innovative material design and device structure optimization, with power conversion efficiencies surpassing 19% and 20% for single-junction and tandem devices, respectively. Interface engineering, by modifying interface properties between different layers for OSCs, has become a vital part to promote the device efficiency. It is essential to elucidate the intrinsic working mechanism of interface layers, as well as the related physical and chemical processes that manipulate device performance and long-term stability. In this article, the advances in interface engineering aimed to pursue high-performance OSCs are reviewed. The specific functions and corresponding design principles of interface layers are summarized first. Then, the anode interface layer, cathode interface layer in single-junction OSCs, and interconnecting layer of tandem devices are discussed in separate categories, and the interface engineering-related improvements on device efficiency and stability are analyzed. Finally,…

Solar-powered vapor evaporation (SVG), based on the liquid-gas phase conversion concept using solar energy, has been given close attention as a promising technology to address the global water shortage. At molecular level, water molecules escaping from liquid water should overcome the attraction of the molecules on the liquid surface layer to evaporate. For this reason, it is better to reduce the energy required for evaporation by breaking a smaller number of hydrogen bonds or forming weak hydrogen bonds to ensure efficient and convenient vapor production. Many novel evaporator materials and effective water activation strategies have been proposed to stimulate rapid steam production and surpass the theoretical thermal limit. However, an in-depth understanding of the phase/enthalpy change process of water evaporation is unclear. In this review, a summary of theoretical analyses of vaporization enthalpy, general calculations, and characterization methods is provided. Various water activation mechanisms are also outlined to reduce evaporation enthalpy in evaporators. Moreover, unsolved…

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric and electronic structure and uncovering the structure-property relationships of single/dual-metal atoms confront with grand challenges. Herein, this review summarizes the latest progress in microenvironment engineering of single/dual-atom active sites via a comprehensive comparison of single-atom catalyst (SACs) and dual-atom catalysts (DACs) in term of design principles, modulation strategy, and theoretical understanding of structure-performance correlations. Subsequently, recent advances in several typical electrocatalysis process are discussed to get general understanding of the reaction mechanisms on finely-tuned SACs and DACs. Finally, full-scaled summaries of the challenges and prospects are given for microenvironment engineering of SACs and DACs. This review will provide new inspiration on the development of atomically dispersed catalysts for electrocatalytic application.

Abstract Aqueous zinc‐metal batteries are considered to have the potential for energy storage due to their high safety and low cost. However, the practical applications of zinc batteries are limited by dendrite growth and side reactions. Epitaxial growth is considered an effective method for stabilizing Zn anode, especially for manipulating the (002) plane of deposited zinc. However, (002) texture zinc is difficult to achieve stable cycle at high capacity due to its large lattice distortion and uneven electric field distribution. Here, a novel zinc anode with highly (101) texture (denoted as (101)‐Zn) is constructed. Due to unique directional guidance and strong bonding effect, (101)‐Zn can achieve dense vertical electroepitaxy in near‐neutral electrolytes. In addition, the low grain boundary area inhibits the occurrence of side reactions. The resultant (101)‐Zn symmetric cells exhibit excellent stability over 5300 h (4 mA cm −2 for 2 mAh cm −2 ) and 330 h (15 mA cm −2 for 10 mAh cm −2 ). Meanwhile, the cycle life of Zn//MnO 2 full cell is meaningfully improved over 1000 cycles.

Abstract Proton‐exchange‐membrane water electrolysis (PEMWE) requires an efficient and durable bifunctional electrocatalyst for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, Ir‐based electrocatalyst is designed using the high entropy alloy (HEA) platform of ZnNiCoIrX with two elements (X: Fe and Mn). A facile dealloying in the vacuum system enables the construction of a nanoporous structure with high crystallinity using Zn as a sacrificial element. Especially, Mn incorporation into HEAs tailors the electronic structure of the Ir site, resulting in the d‐band center being far away from the Fermi level. Downshifting of the d‐band center weakens the adsorption energy with reaction intermediates, which is beneficial for catalytic reactions. Despite low Ir content, ZnNiCoIrMn delivers only 50 mV overpotential for HER at −50 mA cm −2 and 237 mV overpotential for the OER at 10 mA cm −2 . Furthermore, ZnNiCoIrMn shows almost constant voltage for the HER and OER for 100 h and a high stability number of 3.4 × 10 5 n hydrogen n Ir −1 and 2.4 × 10 5 n oxygen…

), cost-effectiveness, and environmental friendliness. Nevertheless, their practical applications are seriously impeded by the shuttle effect of soluble lithium polysulfides (LiPSs), and the uncontrolled dendrite growth of metallic Li, which result in rapid capacity fading and battery safety problems. A systematic and comprehensive review of the cooperative combination effect and tackling the fundamental problems in terms of cathode and anode synchronously is still lacking. Herein, for the first time, the strategies for inhibiting shuttle behavior and dendrite-free Li-S batteries simultaneously are summarized and classified into three parts, including "two-in-one" S-cathode and Li-anode host materials toward Li-S full cell, "two birds with one stone" modified functional separators, and tailoring electrolyte for stabilizing sulfur and lithium electrodes. This review also emphasizes the fundamental Li-S chemistry mechanism and catalyst principles for improving electrochemical performance; advanced characterization technologies to monitor real-time LiPS evolution are also discussed in…

Abstract The ternary blend is demonstrated as an effective strategy to promote the device performance of organic photovoltaics (OPVs) due to the dilution effect. While the compromise between the charge generation and recombination remains a challenge. Here, a mixed diluent strategy for further improving the device efficiency of OPV is proposed. Specifically, the high‐performance OPV system with a polymer donor, i.e., PM6, and a nonfullerene acceptor (NFA), i.e., BTP‐eC9, is diluted by the mixed diluents, which involve a high bandgap NFA of BTP‐S17 and a low bandgap NFA of BTP‐S16 (similar with that of the BTP‐eC9). The BTP‐S17 of better miscibility with BTP‐eC9 can dramatically enhance the open‐circuit voltage (VOC), while the BTP‐S16 maximizes the charge generation or the short‐circuit current density (JSC). The interplay of BTP‐17 and BTP‐S16 enables better compromise between charge generation and recombination, thus leading to a high device performance of 19.76% (certified 19.41%), which is the best among single‐junction OPVs. Further analysis on carrier dynamics validates the…

Microwave absorption materials (MAMs) are originally developed for military purposes, but have since evolved into versatile materials with promising applications in modern technologies, including household use. Despite significant progress in bench-side research over the past decade, MAMs remain limited in their scope and have yet to be widely adopted. This review explores the history of MAMs from first-generation coatings to second-generation functional absorbers, identifies bottlenecks hindering their maturation. It also presents potential solutions such as exploring broader spatial scales, advanced characterization, introducing liquid media, utilizing novel toolbox (machine learning, ML), and proximity of lab to end-user. Additionally, it meticulously presents compelling applications of MAMs in medicine, mechanics, energy, optics, and sensing, which go beyond absorption efficiency, along with their current development status and prospects. This interdisciplinary research direction differs from previous research which primarily focused on meeting traditional requirements (i.e.,…

Abstract It is essential and of great significance to impart high mechanical performance, environmental stability, and high sensitivity to emerging flexible temperature sensors. In this work, polymerizable deep eutectic solvents are designed and prepared by simply mixing N‐cyanomethyl acrylamide (NCMA) containing an amide group and a cyano group in the same side chain with lithium bis(trifluoromethane) sulfonimide (LiTFSI), and obtain supramolecular deep eutectic polyNCMA/LiTFSI gels after polymerization. These supramolecular gels exhibit excellent mechanical performance (tensile strength of 12.9 MPa and fracture energy of 45.3 kJ m −2 ), strong adhesion force, high‐temperature responsiveness, self‐healing ability, and shape memory behavior due to the reversible reconstruction ability of amide hydrogen bonds and cyano‐cyano dipole‐dipole interactions in the gel network. In addition, the gels also demonstrate good environmental stability and 3D printability. To verify its application potential as a flexible temperature sensor, the polyNCMA/LiTFSI gel‐based wireless temperature…

Abstract The continuous oxidation and leachability of active sites in Ru‐based catalysts hinder practical application in proton‐exchange membrane water electrolyzers (PEMWE). Herein, robust inter‐doped tungsten–ruthenium oxide heterostructures [(Ru–W)Ox] fabricated by sequential rapid oxidation and metal thermomigration processes are proposed to enhance the activity and stability of acidic oxygen evolution reaction (OER). The introduction of high‐valent W species induces the valence oscillation of the Ru sites during OER, facilitating the cyclic transition of the active metal oxidation states and maintaining the continuous operation of the active sites. The preferential oxidation of W species and electronic gain of Ru sites in the inter‐doped heterostructure significantly stabilize RuOx on WOx substrates beyond the Pourbaix stability limit of bare RuO2. Furthermore, the asymmetric Ru–O–W active units are generated around the heterostructure interface to adsorb the oxygen intermediates synergistically, enhancing the intrinsic OER activity. Consequently, the inter‐doped (Ru–W)Ox…

Colloidal quantum dots (QDs) exhibit tremendous potential in display technologies owing to their unique optical properties, such as size-tunable emission wavelength, narrow spectral linewidth, and near-unity photoluminescence quantum yield. Significant efforts in academia and industry have achieved dramatic improvements in the performance of quantum dot light-emitting diodes (QLEDs) over the past decade, primarily owing to the development of high-quality QDs and optimized device architectures. Moreover, sophisticated patterning processes have also been developed for QDs, which is an essential technique for their commercialization. As a result of these achievements, some QD-based display technologies, such as QD enhancement films and QD-organic light-emitting diodes, have been successfully commercialized, confirming the superiority of QDs in display technologies. However, despite these developments, the commercialization of QLEDs is yet to reach a threshold, requiring a leap forward in addressing challenges and related problems. Thus, representative research trends, progress, and…

Extracellular vesicles (EVs) are heterogeneous, phospholipid bilayer-enclosed biological particles that regulate cell communication by molecular cargo delivery and surface signaling. EVs are secreted by almost all living cells, including plant cells. Plant-derived vesicle-like nanoparticles (PDVLNs) is a generic term referring to vesicle-like nanostructure particles isolated from plants. Their low immunogenicity and wide availability make PDVLNs safer and more economical to be developed as therapeutic agents and drug carriers. Accumulating evidence indicates the key roles of PDVLNs in regulating interkingdom crosstalk between humans and plants. PDVLNs are capable of entering the human-body systemand delivering effector molecules to cells that modulate cell-signaling pathways. PDVLNs released by or obtained from plants thus have great influenceon human health and diseases. In this review, the biogenesis, detailed preparation methods, various physical and biochemical characteristics, biosafety, and preservation of PDVLNs are introduced, along with how these characteristics pertain to…

Nanozymes with intrinsic enzyme-mimicking activities have shown great potential to become surrogates of natural enzymes in many fields by virtue of their advantages of high catalytic stability, ease of functionalization, and low cost. However, due to the lack of predictable descriptors, most of the nanozymes reported in the past have been obtained mainly through trial-and-error strategies, and the catalytic efficacy, substrate specificity, as well as practical application effect under physiological conditions, are far inferior to that of natural enzymes. To optimize the catalytic efficacies and functions of nanozymes in biomedical settings, recent studies have introduced biosystem-inspired strategies into nanozyme design. In this review, recent advances in the engineering of biosystem-inspired nanozymes by leveraging the refined catalytic structure of natural enzymes, simulating the behavior changes of natural enzymes in the catalytic process, and mimicking the specific biological processes or living organisms, are introduced. Furthermore, the currently involved biomedical…

Traditional honeycomb-like structural electromagnetic (EM)-wave-absorbing materials have been widely used in various equipment as multifunctional materials. However, current EM-wave-absorbing materials are limited by narrow absorption bandwidths and incidence angles because of their anisotropic structural morphology. The work presented here proposes a novel EM-wave-absorbing metastructure with an isotropic morphology inspired by the gyroid microstructures seen in Parides sesostris butterfly wings. A matching redesign methodology between the material and subwavelength scale properties of the gyroid microstructure is proposed, inspired by the interaction mechanism between the microstructure and the material properties on the EM-wave-absorption performance of the prepared metastructure. The bioinspired metastructure is fabricated by additive manufacturing (AM) and subsequent coating through dipping processes, filled with dielectric lossy materials. Based on simulations and experiments, the metastructure designed in this work exhibits an ultrawide absorption bandwidth covering the…

Human-machine interaction (HMI) technology shows an important application prospect in rehabilitation medicine, but it is greatly limited by the unsatisfactory recognition accuracy and wearing comfort. Here, this work develops a fully flexible, conformable, and functionalized multimodal HMI interface consisting of hydrogel-based sensors and a self-designed flexible printed circuit board. Thanks to the component regulation and structural design of the hydrogel, both electromyogram (EMG) and forcemyography (FMG) signals can be collected accurately and stably, so that they are later decoded with the assistance of artificial intelligence (AI). Compared with traditional multichannel EMG signals, the multimodal human-machine interaction method based on the combination of EMG and FMG signals significantly improves the efficiency of human-machine interaction by increasing the information entropy of the interaction signals. The decoding accuracy of the interaction signals from only two channels for different gestures reaches 91.28%. The resulting AI-powered active rehabilitation system can…

Abstract Ultrathin separators are indispensable to high‐energy‐density zinc‐ion batteries (ZIBs), but their easy failure caused by zinc dendrites poses a great challenge. Herein, 23 µm‐thick functional ultrathin separators (FUSs), realizing superb electrochemical stability of zinc anodes and outstanding long‐term durability of ultrathin separators, are reported. In the FUSs, an ultrathin but mechanically strong nanoporous membrane substrate benefits fast and flux‐homogenized Zn 2+ transport, while a metal–organic framework (MOF)‐derived C/Cu nanocomposite decoration layer provides rich low‐barrier zinc nucleation sites, thereby synergistically stabilizing zinc anodes to inhibit zinc dendrites and dendrite‐caused separator failure. Investigation of the zinc affinity of the MOF‐derived C/Cu nanocomposites unravels the high zincophilicity of heteroatom‐containing C/Cu interfaces. Zinc anodes coupled with the FUSs present superior electrochemical stability, whose operation lifetime exceeds 2000 h at 1 mA cm −2 and 600 h at 10 mA cm −2 , 40–50 times longer than that of the zinc anodes…

The field of flexible electronics is a crucial driver of technological advancement, with a strong connection to human life and a unique role in various areas such as wearable devices and healthcare. Consequently, there is an urgent demand for flexible energy storage devices (FESDs) to cater to the energy storage needs of various forms of flexible products. FESDs can be classified into three categories based on spatial dimension, all of which share the features of excellent electrochemical performance, reliable safety, and superb flexibility. In this review, the application scenarios of FESDs are introduced and the main representative devices applied in disparate fields are summarized first. More specifically, it focuses on three types of FESDs in matched application scenarios from both structural and material aspects. Finally, the challenges that hinder the practical application of FESDs and the views on current barriers are presented.

Abstract Hard carbon anodes with all‐plateau capacities below 0.1 V are prerequisites to achieve high‐energy‐density sodium‐ion storage, which holds promise for future sustainable energy technologies. However, challenges in removing defects and improving the insertion of sodium ions head off the development of hard carbon to achieve this goal. Herein, a highly cross‐linked topological graphitized carbon using biomass corn cobs through a two‐step rapid thermal‐annealing strategy is reported. The topological graphitized carbon constructed with long‐range graphene nanoribbons and cavities/tunnels provides a multidirectional insertion of sodium ions whilst eliminating defects to absorb sodium ions at the high voltage region. Evidence from advanced techniques including in situ XRD, in situ Raman, and in situ/ex situ transmission electron microscopy (TEM) indicates that the sodium ions' insertion and Na cluster formation occurred between curved topological graphite layers and in the topological cavity of adjacent graphite band entanglements. The reported topological insertion mechanism…

The emergence of plastic electronics satisfies the increasing demand for flexible electronics. However, it has caused severe ecological problems. Flexible electronics based on natural materials are increasing to hopefully realize the "green" and eco-friendly concept. Herein, recent advances in the design and fabrication of green flexible electronics are reviewed. First, this review comprehensively introduces various natural materials and derivatives, focusing particularly on fibroin and silk, wood and paper, plants, and biomass. Second, fabrication techniques for modifying natural materials, including physical and chemical methods, are presented, after which their merits and demerits are thoroughly discussed. Green flexible electronics based on natural materials, comprising electrical wires/electrodes, antennas, thermal management devices, transistors, memristors, sensors, energy-harvesting devices, energy-storage devices, displays, actuators, electromagnetic shielding, and integration systems, are described in detail. Finally, perspectives on the existing challenges and…

Abstract Bifunctional catalysts can facilitate two different electrochemical reactions with conflicting characteristics. Here, a highly reversible bifunctional electrocatalyst for rechargeable zinc–air batteries (ZABs) is reported featuring a “core–shell structure” in which N‐doped graphene sheets wrap around vanadium molybdenum oxynitride nanoparticles. Single Mo atoms are released from the particle core during synthesis and anchored to electronegative N‐dopant species in the graphitic shell. The resultant Mo single‐atom catalysts excel as active oxygen evolution reaction (OER) sites in pyrrolic‐N and as active oxygen reduction reaction (ORR) sites in pyridinic‐N environments. ZABs with such bifunctional and multicomponent single‐atom catalysts deliver high power density (≈376.4 mW cm −2 ) and long cycle life of over 630 h, outperforming noble‐metal‐based benchmarks. Flexible ZABs that can tolerate a wide range of temperatures (−20 to 80 °C) under severe mechanical deformation are also demonstrated

As the soaring demand for energy storage continues to grow, batteries that can cope with extreme conditions are highly desired. Yet, existing battery materials are limited by weak mechanical properties and freeze-vulnerability, prohibiting safe energy storage in devices that are exposed to low temperature and unusual mechanical impacts. Herein, a fabrication method harnessing the synergistic effect of co-nonsolvency and "salting-out" that can produce poly(vinyl alcohol) hydrogel electrolytes with unique open-cell porous structures, composed of strongly aggregated polymer chains, and containing disrupted hydrogen bonds among free water molecules, is introduced. The hydrogel electrolyte simultaneously combines high strength (tensile strength 15.6 MPa), freeze-tolerance (< -77 °C), high mass transport (10× lower overpotential), and dendrite and parasitic reactions suppression for stable performance (30 000 cycles). The high generality of this method is further demonstrated with poly(N-isopropylacrylamide) and poly(N-tertbutylacrylamide-co-acrylamide) hydrogels. This work takes a…

Abstract Water electrolysis has been expected to assimilate the renewable yet intermediate energy‐derived electricity for green H2 production. However, current benchmark anodic catalysts of Ir/Ru‐based compounds suffer severely from poor dissolution resistance. Herein, an effective modification strategy is proposed by arming a sub‐nanometer RuO2 skin with abundant oxygen vacancies to the interconnected Ru clusters/carbon hybrid microsheet (denoted as Ru@V‐RuO2/C HMS), which can not only inherit the high hydrogen evolution reaction (HER) activity of the Ru, but more importantly, activate the superior activity toward the oxygen evolution reaction (OER) in both acid and alkaline conditions. Outstandingly, it can achieve an ultralow overpotential of 176/201 mV for OER and 46/6 mV for the HER to reach 10 mA cm−2 in acidic and alkaline solution, respectively. Inspiringly, the overall water splitting can be driven with an ultrasmall cell voltage of 1.467/1.437 V for 10 mA cm−2 in 0.5 m H2SO4/1.0 m KOH, respectively. Density functional theory calculations reveal that armoring the…

Abstract Nontoxic and safe aqueous Zn batteries are largely restricted by the detrimental dendrite growth and hydrogen evolution of Zn metal anode. The (002)‐textured Zn electrodeposition, demonstrated as an effective approach for solving these issues, is nevertheless achieved mainly by epitaxial or hetero‐epitaxial deposition of Zn on pre‐textured substrates. Herein, the electrodeposition of (002)‐textured and compact Zn on textureless substrates (commercial Zn, Cu, and Ti foils) at a medium‐high galvanostatic current density is reported. According to the systematic investigations on Zn nucleation and growth behaviors, this is ascribed to two reasons: i) the promoted nonepitaxial nucleation of fine horizontal (002) nuclei at increased overpotential and ii) the competitive growth advantages of (002)‐orientated nuclei. The resulting freestanding (002)‐textured Zn film exhibits significantly suppressed hydrogen evolution and prolonged Zn plating–stripping cycling life, achieving over 2100 mAh cm −2 cumulative capacity under a current density of 10 mA cm −2 and a high depth of…

Abstract Wearable blood‐pressure sensors have recently attracted attention as healthcare devices for continuous non‐invasive arterial pressure (CNAP) monitoring. However, the accuracy of wearable blood‐pressure (BP) monitoring devices has been controversial due to the low signal quality of sensors, the absence of an accurate transfer function to convert the sensor signals into BP values, and the lack of clinical validation regarding measurement precision. Here, a wearable piezoelectric blood‐pressure sensor (WPBPS) is reported, which achieves a high normalized sensitivity (0.062 kPa −1 ), and fast response time (23 ms) for CNAP monitoring. The transfer function of a linear regression model is designed, offering a simple solution to convert the flexible piezoelectric sensor signals into BP values. In order to verify the measurement accuracy of WPBPS, clinical trials are performed on 35 subjects aged from 20 to 80 s after screening. The mean difference between the WPBPS and a commercial sphygmomanometer of 175 BP data pairs is −0.89 ± 6.19 and −0.32 ± 5.28 mmHg for systolic blood…

Abstract Bacterial biofilm‐associated infections (BAIs) are the leading cause of prosthetic implant failure. The dense biofilm structure prevents antibiotic penetration, while the highly acidic and H2O2‐rich biofilm microenvironment (BME) dampens the immunological response of antimicrobial macrophages. Conventional treatments that fail to consistently suppress escaping planktonic bacteria from biofilm result in refractory recolonization, allowing BAIs to persist. Herein, a BME‐responsive copper‐doped polyoxometalate clusters (Cu‐POM) combination with mild photothermal therapy (PTT) and macrophage immune re‐rousing for BAI eradication at all stages is proposed. The self‐assembly of Cu‐POM in BME converts endogenous H2O2 to toxic ·OH through chemodynamic therapy (CDT) and generates a mild PTT effect to induce bacterial metabolic exuberance, resulting in loosening the membrane structure of the bacteria, enhancing copper transporter activity and increasing intracellular Cu‐POM flux. Metabolomics reveals that intracellular Cu‐POM overload restricts the TCA cycle and peroxide…

The Hoffmeister effect of inorganic salts is verified as a promising way to toughen hydrogels, however, the high concentration of inorganic salts may be accompanied by poor biocompatibility. In this work, it is found that polyelectrolytes can obviously elevate the mechanical performances of hydrogels through the Hoffmeister effect. The introduction of anionic poly(sodium acrylate) into poly(vinyl alcohol) (PVA) hydrogel induces the aggregation and crystallization of the PVA to boost the mechanical properties of the resulting double-network hydrogel: elevation of 73, 64, 28, 135, and 19 times in the tensile strength, compressive strength, Young's modulus, toughness, and fracture energy compared with poly(acrylic acid), respectively. It is noteworthy that the mechanical performances of the hydrogels can be flexibly tuned by the variation of polyelectrolyte concentration, ionization degree, relative hydrophobicity of the ionic component, and polyelectrolyte type in a wide range. This strategy is verified to work for other Hoffmeister-effect-sensitive polymers and polyelectrolytes.…

Abstract High‐valence metal species generated in peroxymonosulfate (PMS)‐based Fenton‐like processes are promising candidates for selective degradation of contaminants in water, the formation of which necessitates the cleavage of OH and OO bonds as well as efficient electron transfer. However, the high dissociation energy of OH bond makes its cleavage quite challenging, largely hampering the selective generation of reactive oxygen species. Herein, an asymmetrical configuration characterized by a single cobalt atom coordinated with boron and nitrogen (CoB 1 N 3 ) is established to offer a strong local electric field, upon which the cleavage of OH bond is thermodynamically favored via a promoted coupled electron–proton transfer process, which serves an essential step to further allow OO bond cleavage and efficient electron transfer. Accordingly, the selective formation of Co(IV)O in a single‐atom Co/PMS system enables highly efficient removal performance toward various organic pollutants. The proposed strategy also holds true in other heteroatom doping systems to configure…

Amorphous polymers with ultralong room-temperature phosphorescence (RTP) are highly promising for various applications. Particularly, polymer-based RTP materials with multiple functions such as color-tunability or stimulus-response are highly desirable for multilevel anti-counterfeiting but are rarely reported. Herein, a facile strategy is presented to achieve a series of polymer-based RTP materials with ultralong lifetime, multicolor afterglow, and reversible response to UV irradiation by simply embedding pyridine-substituted triphenylamine derivatives into the polymer matrix poly(vinyl alcohol) (PVA) and poly(methyl methacrylate) (PMMA), respectively. Notably, the pyridine group with the capabilities of promoting intersystem crossing and forming hydrogen-bonding interactions is essential for triggering ultralong RTP from the doping PVA system, among which the doping film TPA-2Py@PVA exhibits excellent RTP property with an ultralong lifetime of 798.4 ms and a high quantum yield of 15.2%. By further co-doping with the commercially available fluorescent dye, multicolor afterglow is…

Abstract The highly selective photoreduction of CO 2 into valuable small‐molecule chemical feedstocks such as CO is an effective strategy for addressing the energy crisis and environmental problems. However, it remains a challenge because the complex CO 2 photoreduction process usually generates multiple possible products and requires a subsequent separation step. In this paper, 2D monolayer and bilayer porphyrin‐based metal‐organic frameworks (MOFs) are successfully constructed by adjusting the reaction temperature and solvent polarity with 5,10,15,20‐tetrakis(4‐pyridyl)porphyrin as the light‐harvesting ligand. The bilayer MOF is a low‐dimensional MOF with a special structure in which the upper and lower layers are arranged in dislocation and are bridged by halogen ions. This bilayer MOF exhibits 100% ultra‐high selectivity for the reduction of CO 2 to CO under simulated sunlight without any cocatalyst or photosensitizer and can be recycled at least three times. The intrinsic mechanism of this photocatalytic CO 2 reduction process is explored through experimental characterization…

Abstract Covalent organic frameworks (COFs) have shown great promise for photocatalytic hydrogen evolution via water splitting. However, the four‐electron oxidation of water remains elusive toward oxygen evolution. Enabling this water oxidation pathway is critical to improve the yield and maximize atom utilization efficiency. A Z‐scheme heterojunction is proposed for overcoming fundamental issues in COF‐based photocatalytic overall water splitting (OWS), such as inefficient light absorption, charge recombination, and poor water oxidation ability. It is shown that the construction of a novel 2D/2D Z‐scheme heterojunction through in situ growth of COFs on the O‐vacancy WO 3 nanosheets (Ov‐WO 3 ) via the WOC chemical bond can remarkably promote photocatalytic OWS. Benefiting from the synergistic effect between the enhanced built‐in electric field by the interfacial WOC bond, the strong water oxidation ability of Ov‐WO 3, and the ultrathin structure of TSCOF, both separation and utilization efficiency of photogenerated electron–hole pairs can be significantly enhanced. An impressive…

Shock-induced low-frequency vibration damage is extremely harmful to bionic soft robots and machines that may incur the malfunction of fragile electronic elements. However, current skin-like self-healable ionic elastomers as the artificial sensing and protecting layer still lack the ability to dampen vibrations, due to their almost opposite design for molecular frictions to material's elasticity. Inspired by the two-phase structure of adipose tissue (the natural damping skin layer), here, a highly damping ionic elastomer with energy-dissipating nanophases embedded in an elastic matrix is introduced, which is formed by polymerization-induced dynamic phase separation of sticky fluorinated copolymers in the presence of lithium salts. Such a supramolecular design decouples the elastic and damping functions into two distinct phases, and thus reconciles a few intriguing properties including ionic conductivity, high stretchability, softness, strain-stiffening, elastic recovery, room-temperature self-healability, recyclability, and most importantly, record-high damping capacity at the human…

Covalent organic frameworks (COFs) are new organic porous materials constructed by covalent bonds, with the advantages of pre-designable topology, adjustable pore size, and abundant active sites. Many research studies have shown that COFs exhibit great potential in gas adsorption, molecular separation, catalysis, drug delivery, energy storage, etc. However, the electrons and holes of intrinsic COF are prone to compounding in transport, and the carrier lifetime is short. The donor-acceptor (D-A) type COFs, which are synthesized by introducing D and A units into the COFs backbone, combine separated electron and hole migration pathway, tunable band gap and optoelectronic properties of D-A type polymers with the unique advantages of COFs and have made great progress in related research in recent years. Here, the synthetic strategies of D-A type COFs are first outlined, including the rational design of linkages and D-A units as well as functionalization approaches. Then the applications of D-A type COFs in catalytic reactions, photothermal therapy, and electronic materials are…

Abstract Emerging sodium‐ion batteries (NIBs) and potassium‐ion batteries (KIBs) show promise in complementing lithium‐ion battery (LIB) technology and diversifying the battery market. Hard carbon is a potential anode candidate for LIBs, NIBs, and KIBs due to its high capacity, sustainability, wide availability, and stable physicochemical properties. Herein, a series of hard carbons is synthesized by hydrothermal carbonization and subsequent pyrolysis at different temperatures to finely tune their structural properties. When tested as anodes, the hard carbons exhibit differing ion‐storage trends for Li, Na, and K, with NIBs achieving the highest reversible capacity. Extensive materials and electrochemical characterizations are carried out to study the correlation of structural features with electrochemical performance and to explain the specific mechanisms of alkali‐ion storage in hard carbons. In addition, the best‐performing hard carbon is tested against a sodium cathode Na 3 V 2 (PO 4 ) 3 in a Na‐ion pouch cell, displaying a high power density of 2172 W kg −1 at an energy density…

Hydrogels have emerged as powerful building blocks to develop various soft bioelectronics because of their tissue-like mechanical properties, superior bio-compatibility, the ability to conduct both electrons and ions, and multiple stimuli-responsiveness. However, hydrogels are vulnerable to mechanical damage, which limits their usage in developing durable hydrogel-based bioelectronics. Self-healing hydrogels aim to endow bioelectronics with the property of repairing specific functions after mechanical failure, thus improving their durability, reliability, and longevity. This review discusses recent advances in self-healing hydrogels, from the self-healing mechanisms, material chemistry, and strategies for multiple properties improvement of hydrogel materials, to the design, fabrication, and applications of various hydrogel-based bioelectronics, including wearable physical and biochemical sensors, supercapacitors, flexible display devices, triboelectric nanogenerators (TENGs), implantable bioelectronics, etc. Furthermore, the persisting challenges hampering the development of…

Abstract CO 2 electroreduction is of great significance to reduce CO 2 emissions and complete the carbon cycle. However, the unavoidable carbonate formation and low CO 2 utilization efficiency in neutral or alkaline electrolytes hinder its application at commercial scale. The development of CO 2 reduction under acidic conditions provides a promising strategy, but the inhibition of the hydrogen evolution reaction is difficult. Herein, the first work to design a Ni–Cu dual atom catalyst supported on hollow nitrogen‐doped carbon is reported for pH‐universal CO 2 electroreduction to CO. The catalyst shows a high CO Faradaic efficiency of ≈99% in acidic, neutral, and alkaline electrolytes, and the partial current densities of CO reach 190 ± 11, 225 ± 10, and 489 ± 14 mA cm −2 , respectively. In particular, the CO 2 utilization efficiency under acidic conditions reaches 64.3%, which is twice as high as that of alkaline conditions. Detailed study indicates the existence of electronic interaction between Ni and Cu atoms. The Cu atoms push the Ni d‐band center further toward the Fermi level,…

Abstract The development of rechargeable zinc–air batteries is heavily dependent on bifunctional oxygen electrocatalysts to offer exceptional oxygen reduction/evolution reaction (ORR/OER) activities. However, the design of such electrocatalysts with high activity and durability is challenging. Herein, a strategy is proposed to create an electrocatalyst comprised of copper‐cobalt diatomic sites on a highly porous nitrogen‐doped carbon matrix (Cu‐Co/NC) with abundantly accessible metal sites and optimal geometric and electronic structures. Experimental findings and theoretical calculations demonstrate that the synergistic effect of Cu‐Co dual‐metal sites with metal‐N 4 coordination induce asymmetric charge distributions with moderate adsorption/desorption behavior with oxygen intermediates. This electrocatalyst exhibits extraordinary bifunctional oxygen electrocatalytic activities in alkaline media, with a half‐wave potential of 0.92 V for ORR and a low overpotential of 335 mV at 10 mA cm −2 for OER. In addition, it demonstrates exceptional ORR activity in acidic (0.85 V) and neutral…

Smart windows nowadays undertake the esteemed obligation of reducing energy consumption as well as upgrading living experience. This project aims to devise a smart window that responds to both electricity and heat, with the intention of achieving energy efficiency, privacy preservation, and enhanced decorative attributes. Through the implementation of a novel electrochromic material design, coupled with the optimization of electrochromic devices (ECDs), a high-performance ECD is obtained, demonstrating coloring/bleaching time of 0.53/0.16 s, a transmittance modulation of 78% (from 99% to 21%), and superior performance in six dimensions. Furthermore, temperature-responsive units and an ionic liquid are incorporated into the electrolyte system to create a novel thermochromic gel electrolyte with transmittance modulation from 80% to 0%, and excellent thermal insulation (6.4 °C reduction). Ultimately, an electro- and thermochromic device is developed, featuring an ultrafast color-switching speed of 0.82/0.60 s and multiple working modes. Overall, this work showcases a prospective design…

; LCO) cathode that powers them. Increasing operating voltage is exclusively effective in boosting LCO capacity and energy density but is inhibited by the innate high-voltage instability of the LCO structure that serves as the foundation and determinant of its electrochemical behavior in lithium-ion batteries. This has stimulated extensive research on LCO structural stabilization. Here, it is focused on the fundamental structural understanding of LCO cathode from long-term studies. Multi-scale structures concerning LCO bulk and surface and various structural issues along with their origins and corresponding stabilization strategies with specific mechanisms are uncovered and elucidated at length, which will certainly deepen and advance the knowledge of LCO structure and further its inherent relationship with electrochemical performance. Based on these understandings, remaining questions and opportunities for future stabilization of the LCO structure are also emphasized.

Abstract Improving the selective ammonia production capacity of electrocatalytic nitrate reduction reaction (NO 3 RR) at ambient conditions is critical to the future development and industrial application of electrosynthesis of ammonia. However, the reaction involves multi‐proton and electron transfer as well as the desorption and underutilization of intermediates, posing a challenge to the selectivity of NO 3 RR. Here the electrodeposition site of Co is modulated by depositing Bi at the bottom of the catalyst, thus obtaining the Co+Bi@Cu NW catalyst with a Bi‐Co corridor structure. In 50 m m NO 3 − , Co+Bi@Cu NW exhibits a highest Faraday efficiency of ≈100% (99.51%), an ammonia yield rate of 1858.2 µg h −1 cm −2 and high repeatability at −0.6 V versus the reversible hydrogen electrode. Moreover, the change of NO 2 − concentration on the catalyst surface observed by in situ reflection absorption imaging and the intermediates of the NO 3 RR process detected by electrochemical in situ Raman spectroscopy together verify the NO 2 − trapping effect of the Bi‐Co corridor structure. It is…

Abstract High‐temperature polymer dielectrics have broad application prospects in next‐generation microelectronics and electrical power systems. However, the capacitive energy densities of dielectric polymers at elevated temperatures are severely limited by carrier excitation and transport. Herein, a molecular engineering strategy is presented to regulate the bulk‐limited conduction in the polymer by bonding amino polyhedral oligomeric silsesquioxane (NH 2 ‐POSS) with the chain ends of polyimide (PI). Experimental studies and density functional theory (DFT) calculations demonstrate that the terminal group NH 2 ‐POSS with a wide‐bandgap of E g ≈ 6.6 eV increases the band energy levels of the PI and induces the formation of local deep traps in the hybrid films, which significantly restrains carrier transport. At 200 °C, the hybrid film exhibits concurrently an ultrahigh discharged energy density of 3.45 J cm −3 and a high gravimetric energy density of 2.74 J g −1 , with the charge‐discharge efficiency >90%, far exceeding those achieved in the dielectric polymers and nearly all other…

Single-atom catalysts (SACs) have attracted considerable attention in heterogeneous catalysis because of their well-defined active sites, maximum atomic utilization efficiency, and unique unsaturated coordinated structures. However, their effectiveness is limited to reactions requiring active sites containing multiple metal atoms. Furthermore, the loading amounts of single-atom sites must be restricted to prevent aggregation, which can adversely affect the catalytic performance despite the high activity of the individual atoms. The introduction of nanoscale metal particles (NMPs) into SACs (NMP-SACs) has proven to be an efficient approach for improving their catalytic performance. A comprehensive review is urgently needed to systematically introduce the synthesis, characterization, and application of NMP-SACs and the mechanisms behind their superior catalytic performance. This review first presents and classifies the different mechanisms through which NMPs enhance the performance of SACs. It then summarizes the currently reported synthetic strategies and state-of-the-art…

Graphene has long been recognized as a potential anode for next-generation lithium-ion batteries (LIBs). The past decade has witnessed the rapid advancement of graphene anodes, and considerable breakthroughs are achieved so far. In this review, the aim is to provide a research roadmap of graphene anodes toward practical LIBs. The Li storage mechanism of graphene is started with and then the approaches to improve its electrochemical performance are comprehensively summarized. First, morphologically engineered graphene anodes with porous, spheric, ribboned, defective and holey structures display improved capacity and rate performance owing to their highly accessible surface area, interconnected diffusion channels, and sufficient active sites. Surface-modified graphene anodes with less aggregation, fast electrons/ions transportation, and optimal solid electrolyte interphase are discussed, demonstrating the close connection between the surface structure and electrochemical activity of graphene. Second, graphene derivatives anodes prepared by heteroatom doping and covalent…

Abstract For current single‐atom catalysts (SACs), modulating the coordination environments of rare‐earth (RE) single atoms with complex electronic orbital and flexible chemical states is still limited. Herein, cerium (Ce) SAs supported on a P, S, and N co‐doped hollow carbon substrate (Ce SAs/PSNC) for the oxygen reduction reaction (ORR) are reported. The as‐prepared Ce SAs/PSNC possesses a half‐wave potential of 0.90 V, a turnover frequency value of 52.2 s−1 at 0.85 V, and excellent stability for the ORR, which exceeds the commercial Pt/C and most recent SACs. Ce SAs/PSNC‐based liquid zinc–air batteries (ZABs) exhibit a high and stable open‐circuit voltage of 1.49 V and a maximum power density of 212 mW cm−2. As the catalyst of the air cathode, it also displays remarkable performance in flexible electronic devices. Theoretical calculations reveal that the introduction of S and P sites induces significant electronic modulations to the Ce SA active sites. The P and S dopings promote the electroactivity of Ce SAs and improve the overall site‐to‐site electron transfer within the Ce…

Abstract Photocatalytic hydrogen evolution (PHE) via water splitting using semiconductor photocatalysts is an effective path to solve the current energy crisis and environmental pollution. Heterojunction photocatalysts, containing two or more semiconductors, exhibit better PHE rates than those with only one semiconductor owing to the altered band alignment at the interface and stronger driving force for charge separation. Traditional binary metal sulfide (BMS)‐based heterojunction photocatalysts, such as CdS, MoS 2 , and PbS, demonstrate excellent PHE performance. However, the recently developed multinary metal sulfide (MMS)‐based photocatalysts possess favorable chemical stability, tunable band structure, and flexible element compositions, and have considerable potential to realize higher PHE rates than those of BMSs. In this review article, the mechanism of PHE is first elucidated and then various single and heterojunction MMS‐based photocatalysts and their charge transfer behaviors and PHE performances are systematically summarized. A perspective on potential future research…

The Internet of Things (IoT) is poised to accelerate the construction of smart cities. However, it requires more than 30 billion sensors to realize the IoT vision, posing great challenges and opportunities for industries of self-powered sensors. Triboelectric nanogenerator (TENG), an emerging new technology, is capable of easily converting energy from surrounding environment into electricity, thus TENG has tremendous application potential in self-powered IoT sensors. At present, TENG encounters a bottleneck to boost output for large-scale commercial use if just by promoting triboelectric charge generation, because the output is decided by the triboelectric charge dynamic equilibrium between generation and decay. To break this bottleneck, the strategy of reducing triboelectric charge decay to enhance TENG output is focused. First, multiple mechanisms of triboelectric charge decay are summarized in detail with basic theoretical principles for future research. Furthermore, recent advances in reducing triboelectric charge decay are thoroughly reviewed and outlined in three aspects:…

Abstract Developing highly efficient multifunctional electrocatalysts is crucial for future sustainable energy pursuits, but remains a great challenge. Herein, a facile synthetic strategy is used to confine atomically thin Pd–PdO nanodomains to amorphous Ru metallene oxide (RuO 2 ). The as‐synthesized electrocatalyst (Pd 2 RuOx‐0.5 h) exhibits excellent catalytic activity toward the pH‐universal hydrogen evolution reaction (η 10 = 14 mV in 1 m KOH, η 10 = 12 mV in 0.5 m H 2 SO 4 , and η 10 = 22 mV in 1 m PBS), alkaline oxygen evolution reaction (η 10 = 225 mV), and overall water splitting ( E 10 = 1.49 V) with high mass activity and operational stability. Further reduction endows the material (Pd 2 RuOx‐2 h) with a promising alkaline oxygen reduction activity, evidenced by high halfway potential, four‐electron selectivity, and excellent poison tolerance. The enhanced catalytic activity is attributed to the rational integration of favorable nanostructures, including 1) the atomically thin nanosheet morphology, 2) the coexisting amorphous and defective crystalline phases, and 3) the…

High-entropy alloys nanoparticles (HEANPs) are receiving extensive attention due to their broad compositional tunability and unlimited potential in bioapplication. However, developing new methods to prepare ultra-small high-entropy alloy nanoparticles (US-HEANPs) faces severe challenges owing to their intrinsic thermodynamic instability. Furthermore, there are few reports on studying the effect of HEANPs in tumor therapy. Herein, the fabricated PtPdRuRhIr US-HEANPs act as bifunctional nanoplatforms for the highly efficient treatment of tumors. The US-HEANPs are engineered by the universal metal-ligand cross-linking strategy. This simple and scalable strategy is based on the aldol condensation of organometallics to form the target US-HEANPs. The synthesized US-HEANPs exhibit excellent peroxidase-like (POD-like) activity and can catalyze the endogenous hydrogen peroxide to produce highly toxic hydroxyl radicals. Furthermore, the US-HEANPs possess a high photothermal conversion effect for converting 808 nm near-infrared light into heat energy. In vivo and in vitro experiments…

Abstract Guaranteeing satisfactory catalytic behavior while ensuring high metal utilization has become the problem that needs to be addressed when designing noble‐metal‐based catalysts for electrochemical reactions. Here, well‐dispersed ruthenium (Ru) based clusters with adjacent Ru single atoms (SAs) on layered sodium cobalt oxide (Ru/NC) are demonstrated as a superb electrocatalyst for alkaline HER. The Ru/NC catalyst demonstrates an activity increase by a factor of two relative to the commercial Pt/C. Operando characterizations in conjunction with density functional theory (DFT) simulations uncover the origin of the superior activity and establish a structure–performance relationship, that is, under HER condition, the real active species are Ru SAs and metallic Ru clusters supported on the NC substrate. The excellent alkaline HER activity of the Ru/NC catalyst can be understood by a spatially decoupled water dissociation and hydrogen desorption mechanism, where the NC substrate accelerates the water dissociation rate, and the generated H intermediates would then migrate to the Ru…

Abstract Developing non‐precious catalysts with long‐term catalytic durability and structural stability under industrial conditions is the key to practical alkaline anion exchange membrane (AEM) water electrolysis. Here, an energy‐saving approach is proposed to synthesize defect‐rich iron nickel oxyhydroxide for stability and efficiency toward the oxygen evolution reaction. Benefiting from in situ cation exchange, the nanosheet‐nanoflake‐structured catalyst is homogeneously embedded in, and tightly bonded to, its substrate, making it ultrastable at high current densities. Experimental and theoretical calculation results reveal that the introduction of Ni in FeOOH reduces the activation energy barrier for the catalytic reaction and that the purposely created oxygen defects not only ensure the exposure of active sites and maximize the effective catalyst surface but also modulate the local coordination environment and chemisorption properties of both Fe and Ni sites, thus lowering the energy barrier from *O to *OOH. Consequently, the optimized d‐(Fe,Ni)OOH catalyst exhibits outstanding…

Hydrogels are widely used in tissue engineering, soft robots, wearable electronics, etc. However, it remains a great challenge to develop hydrogels possessing simultaneously high strength, large stretchability, great fracture energy, and good fatigue threshold to suit different applications. Herein, a novel solvent-exchange-assisted wet-annealing strategy is proposed to prepare high performance poly(vinyl alcohol) hydrogels by extensively tuning the macromolecular chain movement and optimizing the polymer network. The reinforcing and toughening mechanisms are found to be “macromolecule crystallization and entanglement”. These hydrogels have large tensile strengths up to 11.19 ± 0.27 MPa and extremely high fracture strains of 1879 ± 10%. In addition, the fracture energy and fatigue threshold can reach as high as 25.39 ± 6.64 kJ m−2 and ≈1233 J m−2, respectively. These superb mechanical properties compare favorably to those of other tough hydrogels, organogels, and even natural tendons and synthetic rubbers. This work provides a new and effective method to fabricate superstrong,…

Abstract Electrochemical CO 2 reduction reaction (CO 2 RR) offers a promising approach to close the anthropogenic carbon cycle and store intermittent renewable energy in fuels or chemicals. On the path to commercializing this technology, achieving the long‐term operation stability is a central requirement but still confronts challenges. This motivates to organize the present review to systematically discuss the stability issue of CO 2 RR. This review starts from the fundamental understanding on the destabilization mechanisms of CO 2 RR, with focus on the degradation of electrocatalyst and change of reaction microenvironment during continuous electrolysis. Subsequently, recent efforts on catalyst design to stabilize the active sites are summarized, where increasing atomic binding strength to resist surface reconstruction is highlighted. Next, the optimization of electrolysis system to enhance the operation stability by maintaining reaction microenvironment especially mitigating flooding and carbonate problems is demonstrated. The manipulation on operation conditions also enables to…

Immunotherapy has made remarkable strides in cancer therapy over the past decade. However, such emerging therapy still suffers from the low response rates and immune-related adverse events. Various strategies have been developed to overcome these serious challenges. Therein, sonodynamic therapy (SDT), as a non-invasive treatment, has received ever-increasing attention especially in the treatment of deep-seated tumors. Significantly, SDT can effectively induce immunogenic cell death to trigger systemic anti-tumor immune response, termed sonodynamic immunotherapy. The rapid development of nanotechnology has revolutionized SDT effects with robust immune response induction. As a result, more and more innovative nanosonosensitizers and synergistic treatment modalities are established with superior efficacy and safe profile. In this review, the recent advances in cancer sonodynamic immunotherapy are summarized with a particular emphasis on how nanotechnology can be explored to harness SDT for amplifying anti-tumor immune response. Moreover, the current challenges in this field and the…

Metamaterials are artificial materials designed to exhibit effective material parameters that go beyond those found in nature. Composed of unit cells with rich designability that are assembled into multiscale systems, they hold great promise for realizing next-generation devices with exceptional, often exotic, functionalities. However, the vast design space and intricate structure-property relationships pose significant challenges in their design. A compelling paradigm that could bring the full potential of metamaterials to fruition is emerging: data-driven design. This review provides a holistic overview of this rapidly evolving field, emphasizing the general methodology instead of specific domains and deployment contexts. Existing research is organized into data-driven modules, encompassing data acquisition, machine learning-based unit cell design, and data-driven multiscale optimization. The approaches are further categorized within each module based on shared principles, analyze and compare strengths and applicability, explore connections between different modules, and identify…

The galvanostatic lithiation/sodiation voltage profiles of hard carbon anodes are simple, with a sloping drop followed by a plateau. However, a precise understanding of the corresponding redox sites and storage mechanisms is still elusive, which hinders further development in commercial applications. Here, a comprehensive comparison of the lithium- and sodium-ion storage behaviors of hard carbon is conducted, yielding the following key findings: 1) the sloping voltage section is presented by the lithium-ion intercalation in the graphitic lattices of hard carbons, whereas it mainly arises from the chemisorption of sodium ions on their inner surfaces constituting closed pores, even if the graphitic lattices are unoccupied; 2) the redox sites for the plateau capacities are the same as those for the closed pores regardless of the alkali ions; 3) the sodiation plateau capacities are mostly determined by the volume of the available closed pore, whereas the lithiation plateau capacities are primarily affected by the intercalation propensity; and 4) the intercalation preference and the…

Microneedles provide an effective strategy for transdermal drug delivery. Many endeavors have been devoted to developing smart microneedles that can respond to and interact with pathophysiological environments. Here, novel bioinspired adaptable indwelling microneedles with therapeutic exosome encapsulation are presented for diabetic wound healing by a combined fabrication strategy of template replication and 3D transfer printing. Such microneedles are composed of mesenchymal stem cell (MSC)-exosomes-encapsulated adjustable poly(vinyl alcohol) (PVA) hydrogel needle tips and detachable 3M medical tape supporting substrate. As the mechanical strength of the PVA hydrogel is ionically responsive due to Hofmeister effects, the hardness of the resultant microneedle tips can be upregulated by sulfate ions to ensure skin penetration and be softened by nitrate ions after tip-substrate detachment to adapt to the surrounding tissue and release exosomes. Because the MSC-exosomes can effectively activate fibroblasts, vascular endothelial cells, and macrophages, the indwelling microneedles are…

Abstract Anion‐exchange‐membrane fuel cells (AEMFCs) are a cost‐effective alternative to proton‐exchange‐membrane fuel cells (PEMFCs). The development of high‐performance and durable AEMFCs requires highly conductive and robust anion‐exchange membranes (AEMs). However, AEMs generally exhibit a trade‐off between conductivity and dimensional stability. Here, a fluorination strategy to create a phase‐separated morphological structure in poly(aryl piperidinium) AEMs is reported. The highly hydrophobic perfluoroalkyl side chains augment phase separation to construct interconnected hydrophilic channels for anion transport. As a result, these fluorinated PAP (FPAP) AEMs simultaneously possess high conductivity (>150 mS cm−1 at 80 °C) and high dimensional stability (swelling ratio <20% at 80 °C), excellent mechanical properties (tensile strength >80 MPa and elongation at break >40%) and chemical stability (>2000 h in 3 m KOH at 80 °C). AEMFCs with a non‐precious Co–Mn spinel cathode using the present FPAP AEMs achieve an outstanding peak power density of 1.31 W cm−2. The AEMs remain stable…

Sodium-ion batteries (SIBs) are a viable alternative to meet the requirements of future large-scale energy storage systems due to the uniform distribution and abundant sodium resources. Among the various cathode materials for SIBs, phosphate-based polyanionic compounds exhibit excellent sodium-storage properties, such as high operation voltage, remarkable structural stability, and superior safety. However, their undesirable electronic conductivities and specific capacities limit their application in large-scale energy storage systems. Herein, the development history and recent progress of phosphate-based polyanionic cathodes are first overviewed. Subsequently, the effective modification strategies of phosphate-based polyanionic cathodes are summarized toward high-performance SIBs, including surface coating, morphological control, ion doping, and electrolyte optimization. Besides, the electrochemical performance, cost, and industrialization analysis of phosphate-based polyanionic cathodes for SIBs are discussed for accelerating commercialization development. Finally, the future…

Abstract Zn‐metal batteries (ZnBs) are safe and sustainable because of their operability in aqueous electrolytes, abundance of Zn, and recyclability. However, the thermodynamic instability of Zn metal in aqueous electrolytes is a major bottleneck for its commercialization. As such, Zn deposition (Zn2+ → Zn(s)) is continuously accompanied by the hydrogen evolution reaction (HER) (2H+ → H2) and dendritic growth that further accentuate the HER. Consequently, the local pH around the Zn electrode increases and promotes the formation of inactive and/or poorly conductive Zn passivation species (Zn + 2H2O → Zn(OH)2 + H2) on the Zn. This aggravates the consumption of Zn and electrolyte and degrades the performance of ZnB. To propel HER beyond its thermodynamic potential (0 V vs standard hydrogen electrode (SHE) at pH 0), the concept of water‐in‐salt‐electrolyte (WISE) has been employed in ZnBs. Since the publication of the first article on WISE for ZnB in 2016, this research area has progressed continuously. Here, an overview and discussion on this promising research direction for…

Abstract High‐efficiency electromagnetic (EM) functional materials are the core building block of high‐performance EM absorbers and devices, and they are indispensable in various fields ranging from industrial manufacture to daily life, or even from national defense security to space exploration. Searching for high‐efficiency EM functional materials and realizing high‐performance EM devices remain great challenges. Herein, a simple solution‐process is developed to rapidly grow gram‐scale organic–inorganic (MAPbX 3 , X = Cl, Br, I) perovskite microcrystals. They exhibit excellent EM response in multi bands covering microwaves, visible light, and X‐rays. Among them, outstanding microwave absorption performance with multiple absorption bands can be achieved, and their intrinsic EM properties can be tuned by adjusting polar group. An ultra‐wideband bandpass filter with high suppression level of −71.8 dB in the stopband in the GHz band, self‐powered photodetectors with tunable broadband or narrowband photoresponse in the visible‐light band, and a self‐powered X‐ray detector with high…

Abstract The buried interface in perovskite solar cells (PSCs) is pivotal for achieving high efficiency and stability. However, it is challenging to study and optimize the buried interface due to its non‐exposed feature. Here, a facile and effective strategy is developed to modify the SnO 2 /perovskite buried interface by passivating the buried defects in perovskite and modulating carrier dynamics via incorporating formamidine oxalate (FOA) in SnO 2 nanoparticles. Both formamidinium and oxalate ions show a longitudinal gradient distribution in the SnO 2 layer, mainly accumulating at the SnO 2 /perovskite buried interface, which enables high‐quality upper perovskite films, minimized defects, superior interface contacts, and matched energy levels between perovskite and SnO 2 . Significantly, FOA can simultaneously reduce the oxygen vacancies and tin interstitial defects on the SnO 2 surface and the FA + /Pb 2+ associated defects at the perovskite buried interface. Consequently, the FOA treatment significantly improves the efficiency of the PSCs from 22.40% to 25.05% and their storage‐…

Abstract Flexible zinc‐ion batteries (ZIBs) with high capacity and long cycle stability are essential for wearable electronic devices. Hydrogel electrolytes have been developed to provide ion‐transfer channels while maintaining the integrity of ZIBs under mechanical strain. However, hydrogel matrices are typically swollen with aqueous salt solutions to increase ionic conductivity, which can hinder intimate contact with electrodes and reduce mechanical properties. To address this, a single‐Zn‐ion‐conducting hydrogel electrolyte (SIHE) is developed by integrating polyacrylamide network and pseudo‐polyrotaxane structure. The SIHE exhibits a high Zn2+ transference number of 0.923 and a high ionic conductivity of 22.4 mS cm−1 at room temperature. Symmetric batteries with SIHE demonstrate stable Zn plating/stripping performance for over 160 h, with a homogenous and smooth Zn deposition layer. Full cells with La‐V2O5 cathodes exhibit a high capacity of 439 mA h g−1 at 0.1 A g−1 and excellent capacity retention of 90.2% after 3500 cycles at 5 A g−1. Moreover, the flexible ZIBs display…

The transfection potency of lipid nanoparticle (LNP) mRNA systems is critically dependent on the ionizable cationic lipid component. LNP mRNA systems composed of optimized ionizable lipids often display distinctive mRNA-rich "bleb" structures. Here, it is shown that such structures can also be induced for LNPs containing nominally less active ionizable lipids by formulating them in the presence of high concentrations of pH 4 buffers such as sodium citrate, leading to improved transfection potencies both in vitro and in vivo. Induction of bleb structure and improved potency is dependent on the type of pH 4 buffer employed, with LNP mRNA systems prepared using 300 mm sodium citrate buffer displaying maximum transfection. The improved transfection potencies of LNP mRNA systems displaying bleb structure can be attributed, at least in part, to enhanced integrity of the encapsulated mRNA. It is concluded that enhanced transfection can be achieved by optimizing formulation parameters to improve mRNA stability and that optimization of ionizable lipids to achieve enhanced potency may well…