The 50 most-cited articles in Advanced Materials, 2020

Optimizing the molecular structures of organic photovoltaic (OPV) materials is one of the most effective methods to boost power conversion efficiencies (PCEs). For an excellent molecular system with a certain conjugated skeleton, fine tuning the alky chains is of considerable significance to fully explore its photovoltaic potential. In this work, the optimization of alkyl chains is performed on a chlorinated nonfullerene acceptor (NFA) named BTP-4Cl-BO (a Y6 derivative) and very impressive photovoltaic parameters in OPV cells are obtained. To get more ordered intermolecular packing, the n-undecyl is shortened at the edge of BTP-eC11 to n-nonyl and n-heptyl. As a result, the NFAs of BTP-eC9 and BTP-eC7 are synthesized. The BTP-eC7 shows relatively poor solubility and thus limits its application in device fabrication. Fortunately, the BTP-eC9 possesses good solubility and, at the same time, enhanced electron transport property than BTP-eC11. Significantly, due to the simultaneously enhanced short-circuit current density and fill factor, the BTP-eC9-based single-junction OPV cells…

Over the past decades, interest in shape memory polymers (SMPs) has persisted, and immense efforts have been dedicated to developing SMPs and their multifunctional composites. As a class of stimuli-responsive polymers, SMPs can return to their initial shape from a programmed temporary shape under external stimuli, such as light, heat, magnetism, and electricity. The introduction of functional materials and nanostructures results in shape memory polymer composites (SMPCs) with large recoverable deformation, enhanced mechanical properties, and controllable remote actuation. Because of these unique features, SMPCs have a broad application prospect in many fields covering aerospace engineering, biomedical devices, flexible electronics, soft robotics, shape memory arrays, and 4D printing. Herein, a comprehensive analysis of the shape recovery mechanisms, multifunctionality, applications, and recent advances in SMPs and SMPCs is presented. Specifically, the combination of functional, reversible, multiple, and controllable shape recovery processes is discussed. Further, established…

Aqueous Zn batteries that provide a synergistic integration of absolute safety and high energy density have been considered as highly promising energy-storage systems for powering electronics. Despite the rapid progress made in developing high-performance cathodes and electrolytes, the underestimated but non-negligible dendrites of Zn anode have been observed to shorten battery lifespan. Herein, this dendrite issue in Zn anodes, with regard to fundamentals, protection strategies, characterization techniques, and theoretical simulations, is systematically discussed. An overall comparison between the Zn dendrite and its Li and Al counterparts, to highlight their differences in both origin and topology, is given. Subsequently, in-depth clarifications of the specific influence factors of Zn dendrites, including the accumulation effect and the cathode loading mass (a distinct factor for laboratory studies and practical applications) are presented. Recent advances in Zn dendrite protection are then comprehensively summarized and categorized to generate an overview of respective…

Abstract Although Zn metal has been regarded as the most promising anode for aqueous batteries, it persistently suffers from serious side reactions and dendrite growth in mild electrolyte. Spontaneous Zn corrosion and hydrogen evolution damage the shelf life and calendar life of Zn‐based batteries, severely affecting their industrial applications. Herein, a robust and homogeneous ZnS interphase is built in situ on the Zn surface by a vapor–solid strategy to enhance Zn reversibility. The thickness of the ZnS film is controlled via the treatment temperature, and the performance of the protected Zn electrode is optimized. The dense ZnS artificial layer obtained at 350 °C not only suppresses Zn corrosion by forming a physical barrier on the Zn surface, but also inhibits dendrite growth via guiding the Zn plating/stripping underneath the artificial layer. Accordingly, a side reaction‐free and dendrite‐free Zn electrode is developed, the effectiveness of which is also convincing in a MnO 2 /ZnS@Zn full‐cell with 87.6% capacity retention after 2500 cycles.

The reasonable design of electrode materials for rechargeable batteries plays an important role in promoting the development of renewable energy technology. With the in-depth understanding of the mechanisms underlying electrode reactions and the rapid development of advanced technology, the performance of batteries has significantly been optimized through the introduction of defect engineering on electrode materials. A large number of coordination unsaturated sites can be exposed by defect construction in electrode materials, which play a crucial role in electrochemical reactions. Herein, recent advances regarding defect engineering in electrode materials for rechargeable batteries are systematically summarized, with a special focus on the application of metal-ion batteries, lithium-sulfur batteries, and metal-air batteries. The defects can not only effectively promote ion diffusion and charge transfer but also provide more storage/adsorption/active sites for guest ions and intermediate species, thus improving the performance of batteries. Moreover, the existing challenges and…

Abstract Engineering semiconductor devices requires an understanding of charge carrier mobility. Typically, mobilities are estimated using Hall effect and electrical resistivity meausrements, which are are routinely performed at room temperature and below, in materials with mobilities greater than 1 cm 2 V ‐1 s ‐1 . With the availability of combined Seebeck coefficient and electrical resistivity measurement systems, it is now easy to measure the weighted mobility (electron mobility weighted by the density of electronic states). A simple method to calculate the weighted mobility from Seebeck coefficient and electrical resistivity measurements is introduced, which gives good results at room temperature and above, and for mobilities as low as 10 −3 cm 2 V ‐1 s ‐1 , Here, μ w is the weighted mobility, ρ is the electrical resistivity measured in mΩ cm, T is the absolute temperature in K, S is the Seebeck coefficient, and k B /e = 86.3 µV K –1 . Weighted mobility analysis can elucidate the electronic structure and scattering mechanisms in materials and is particularly helpful in…

Abstract Free‐standing films that display high strength and high electrical conductivity are critical for flexible electronics, such as electromagnetic interference (EMI) shielding coatings and current collectors for batteries and supercapacitors. 2D Ti 3 C 2 T x flakes are ideal candidates for making conductive films due to their high strength and metallic conductivity. It is, however, challenging to transfer those outstanding properties of single MXene flakes to macroscale films as a result of the small flake size and relatively poor flake alignment that occurs during solution‐based processing. Here, a scalable method is shown for the fabrication of strong and highly conducting pure MXene films containing highly aligned large MXene flakes. These films demonstrate record tensile strength up to ≈570 MPa for a 940 nm thick film and electrical conductivity of ≈15 100 S cm −1 for a 214 nm thick film, which are both the highest values compared to previously reported pure Ti 3 C 2 T x films. These films also exhibit outstanding EMI shielding performance (≈50 dB for a 940 nm thick film)…

Macrophages play an important role in cancer development and metastasis. Proinflammatory M1 macrophages can phagocytose tumor cells, while anti-inflammatory M2 macrophages such as tumor-associated macrophages (TAMs) promote tumor growth and invasion. Modulating the tumor immune microenvironment through engineering macrophages is efficacious in tumor therapy. M1 macrophages target cancerous cells and, therefore, can be used as drug carriers for tumor therapy. Herein, the strategies to engineer macrophages for cancer immunotherapy, such as inhibition of macrophage recruitment, depletion of TAMs, reprograming of TAMs, and blocking of the CD47-SIRPα pathway, are discussed. Further, the recent advances in drug delivery using M1 macrophages, macrophage-derived exosomes, and macrophage-membrane-coated nanoparticles are elaborated. Overall, there is still significant room for development in macrophage-mediated immune modulation and macrophage-mediated drug delivery, which will further enhance current tumor therapies against various malignant solid tumors, including drug-resistant tumors and…

Freeze casting, also known as ice templating, is a particularly versatile technique that has been applied extensively for the fabrication of well-controlled biomimetic porous materials based on ceramics, metals, polymers, biomacromolecules, and carbon nanomaterials, endowing them with novel properties and broadening their applicability. The principles of different directional freeze-casting processes are described and the relationships between processing and structure are examined. Recent progress in freeze-casting assisted assembly of low dimensional building blocks, including graphene and carbon nanotubes, into tailored micro- and macrostructures is then summarized. Emerging trends relating to novel materials as building blocks and novel freeze-cast geometries-beads, fibers, films, complex macrostructures, and nacre-mimetic composites-are presented. Thereafter, the means by which aligned porous structures and nacre mimetic materials obtainable through recently developed freeze-casting techniques and low-dimensional building blocks can facilitate material functionality across…

There is currently enormous and growing demand for flexible electronics for personalized mobile equipment, human-machine interface units, wearable medical-healthcare systems, and bionic intelligent robots. Cellulose is a well-known natural biopolymer that has multiple advantages including low cost, renewability, easy processability, and biodegradability, as well as appealing mechanical performance, dielectricity, piezoelectricity, and convertibility. Because of its multiple merits, cellulose is frequently used as a substrate, binder, dielectric layer, gel electrolyte, and derived carbon material for flexible electronic devices. Leveraging the advantages of cellulose to design advanced functional materials will have a significant impact on portable intelligent electronics. Herein, the unique molecular structure and nanostructures (nanocrystals, nanofibers, nanosheets, etc.) of cellulose are briefly introduced, the structure-property-application relationships of cellulosic materials summarized, and the processing technologies for fabricating cellulose-based flexible electronics…

Abstract Miniaturization of electronics demands electromagnetic interference (EMI) shielding of nanoscale dimension. The authors report a systematic exploration of EMI shielding behavior of 2D Ti3C2Tx MXene assembled films over a broad range of film thicknesses, monolayer by monolayer. Theoretical models are used to explain the shielding mechanism below skin depth, where multiple reflection becomes significant, along with the surface reflection and bulk absorption of electromagnetic radiation. While a monolayer assembled film offers ≈20% shielding of electromagnetic waves, a 24‐layer film of ≈55 nm thickness demonstrates 99% shielding (20 dB), revealing an extraordinarily large absolute shielding effectiveness (3.89 × 106 dB cm2 g−1). This remarkable performance of nanometer‐thin solution processable MXene proposes a paradigm shift in shielding of lightweight, portable, and compact next‐generation electronic devices.

The electronic metal-support interaction (EMSI), which acts as a bridge between theoretical electronic study and the design of heterogenous catalysts, has attracted much attention. Utilizing the interaction between the metal and the support is one of the most essential strategies to enhance electrocatalytic efficiency due to structural and synergetic promotion. To date, as the ideal model for realizing EMSI, many types of single-atom catalysts (SACs) have been developed. The understanding of the electronic interaction on SACs has also been pushed to a higher level. However, systematic theories and operando experiments are seldom reported, and will be necessary to put forward and be carried out, respectively. Herein, the types, characterization, mechanism, and electrocatalytic applications of EMSI are comprehensively summarized and discussed. In addition to the basic information above, the challenges, opportunities, and future development of the EMSI on SACs are also proposed to present an overall view and reference to the later research.

All-solid-state lithium batteries (ASSLBs) are considered as the next generation electrochemical energy storage devices because of their high safety and energy density, simple packaging, and wide operable temperature range. The critical component in ASSLBs is the solid-state electrolyte. Among all solid-state electrolytes, the sulfide electrolytes have the highest ionic conductivity and favorable interface compatibility with sulfur-based cathodes. The ionic conductivity of sulfide electrolytes is comparable with or even higher than that of the commercial organic liquid electrolytes. However, several critical challenges for sulfide electrolytes still remain to be solved, including their narrow electrochemical stability window, the unstable interface between the electrolyte and the electrodes, as well as lithium dendrite formation in the electrolytes. Herein, the emerging sulfide electrolytes and preparation methods are reviewed. In particular, the required properties of the sulfide electrolytes, such as the electrochemical stabilities of the electrolytes and the compatible…

Abstract Solar vapor generation has presented great potential for wastewater treatment and seawater desalination with high energy conversion and utilization efficiency. However, technology gaps still exist for achieving a fast evaporation rate and high quality of water combined with low‐cost deployment to provide a sustainable solar‐driven water purification system. In this study, a naturally abundant biomass, konjac glucomannan, together with simple‐to‐fabricate iron‐based metal‐organic framework‐derived photothermal nanoparticles is introduced into the polyvinyl alcohol networks, building hybrid hydrogel evaporators in a cost‐effective fashion ($14.9 m−2 of total materials cost). With advantageous features of adequate water transport, effective water activation, and anti‐salt‐fouling function, the hybrid hydrogel evaporators achieve a high evaporation rate under one sun (1 kW m−2) at 3.2 kg m−2 h−1 out of wastewater with wide degrees of acidity and alkalinity (pH 2–14) and high‐salinity seawater (up to 330 g kg−1). More notably, heavy metal ions are removed effectively by forming…

Hydrogen has been deemed as an ideal substitute fuel to fossil energy because of its renewability and the highest energy density among all chemical fuels. One of the most economical, ecofriendly, and high-performance ways of hydrogen production is electrochemical water splitting. Recently, 2D transition metal dichalcogenides (also known as 2D TMDs) showed their utilization potentiality as cost-effective hydrogen evolution reaction (HER) catalysts in water electrolysis. Herein, recent representative research efforts and systematic progress made in 2D TMDs are reviewed, and future opportunities and challenges are discussed. Furthermore, general methods of synthesizing 2D TMDs materials are introduced in detail and the advantages and disadvantages for some specific methods are provided. This explanation includes several important regulation strategies of creating more active sites, heteroatoms doping, phase engineering, construction of heterostructures, and synergistic modulation which are capable of optimizing the electrical conductivity, exposure to the catalytic active sites, and…

Abstract The electrochemical CO2 reduction reaction (CO2RR) is of great importance to tackle the rising CO2 concentration in the atmosphere. The CO2RR can be driven by renewable energy sources, producing precious chemicals and fuels, with the implementation of this process largely relying on the development of low‐cost and efficient electrocatalysts. Recently, a range of heterogeneous and potentially low‐cost single‐atom catalysts (SACs) containing non‐precious metals coordinated to earth‐abundant elements have emerged as promising candidates for the CO2RR. Unfortunately, the real catalytically active centers and the key factors that govern the catalytic performance of these SACs remain ambiguous. Here, this ambiguity is addressed by developing a fundamental understanding of the CO2RR‐to‐CO process on SACs, as CO accounts for the major product from CO2RR on SACs. The reaction mechanism, the rate‐determining steps, and the key factors that control the activity and selectivity are analyzed from both experimental and theoretical studies. Then, the synthesis, characterization, and the…

Stretchable electronics, which can retain their functions under stretching, have attracted great interest in recent decades. Elastic substrates, which bear the applied strain and regulate the strain distribution in circuits, are indispensable components in stretchable electronics. Moreover, the self-healing property of the substrate is a premise to endow stretchable electronics with the same characteristics, so the device may recover from failure resulting from large and frequent deformations. Therefore, the properties of the elastic substrate are crucial to the overall performance of stretchable devices. Poly(dimethylsiloxane) (PDMS) is widely used as the substrate material for stretchable electronics, not only because of its advantages, which include stable chemical properties, good thermal stability, transparency, and biological compatibility, but also because of its capability of attaining designer functionalities via surface modification and bulk property tailoring. Herein, the strategies for fabricating stretchable electronics on PDMS substrates are summarized, and the…

Abstract Traditional photothermal therapy requires high‐intensity laser excitation for cancer treatments due to the low photothermal conversion efficiency (PCE) of photothermal agents (PTAs). PTAs with ultra‐high PCEs can decrease the required excited light intensity, which allows safe and efficient therapy in deep tissues. In this work, a PTA is synthesized with high PCE of 88.3% based on a BODIPY scaffold, by introducing a CF 3 “barrier‐free” rotor on the meso ‐position (tfm‐BDP). In both the ground and excited state, the CF 3 moiety in tfm‐BDP has no energy barrier to rotation, allowing it to efficiently dissipate absorbed (NIR) photons as heat. Importantly, the barrier‐free rotation of CF 3 can be maintained after encapsulating tfm‐BDP into polymeric nanoparticles (NPs). Thus, laser irradiation with safe intensity (0.3 W cm −2 , 808 nm) can lead to complete tumor ablation in tumor‐bearing mice after intravenous injection of tfm‐BDP NPs. This strategy of “barrier‐free rotation” provides a new platform for future design of PTT agents for clinical cancer treatment.

Abstract Ultrasound theranostics features non‐invasiveness, minor energy attenuation, and high tissue‐penetrating capability, and is playing ever‐important roles in the diagnosis and therapy of diseases in clinics. Herein, ultrasound is employed as a microscopic pressure resource to generate reactive oxygen species (ROS) for piezocatalytic tumor therapy under catalytic mediation by piezoelectric tetragonal BaTiO 3 (T‐BTO). Under the ultrasonic vibration, the electrons and holes are unpaired and they are separated by the piezoelectricity, resulting in the establishment of a strong built‐in electric field, which subsequently catalyzes the generation of ROS such as toxic hydroxyl ( • OH) and superoxide radicals ( • O 2 − ) in situ for tumor eradication. This modality shows intriguing advantages over typical sonoluminescence‐activated sonodynamic therapy, such as more stable sensitizers and dynamical control of redox reaction outcomes. Furthermore, according to the finite element modeling simulation, the built‐in electric field is capable of modulating the band alignment to make the…

Abstract Nitrogen‐coordinated metal single atoms in carbon have aroused extensive interest recently and have been growing as an active research frontier in a wide range of key renewable energy reactions and devices. Herein, a step‐by‐step self‐assembly strategy is developed to allocate nickel (Ni) and iron (Fe) single atoms respectively on the inner and outer walls of graphene hollow nanospheres (GHSs), realizing separate‐sided different single‐atom functionalization of hollow graphene. The Ni or Fe single atom is demonstrated to be coordinated with four N atoms via the formation of a Ni‐N 4 or Fe‐N 4 planar configuration. The developed Ni‐N 4 /GHSs/Fe‐N 4 Janus material exhibits excellent bifunctional electrocatalytic performance, in which the outer Fe‐N 4 clusters dominantly contribute to high activity toward the oxygen reduction reaction (ORR), while the inner Ni‐N 4 clusters are responsible for excellent activity toward the oxygen evolution reaction (OER). Density functional theory calculations demonstrate the structures and reactivities of Fe‐N 4 and Ni‐N 4 for the ORR and OER.…

Mesoporous silica nanoparticles (MSNs), one of the important porous materials, have garnered interest owing to their highly attractive physicochemical features and advantageous morphological attributes. They are of particular importance for use in diverse fields including, but not limited to, adsorption, catalysis, and medicine. Despite their intrinsic stable siliceous frameworks, excellent mechanical strength, and optimal morphological attributes, pristine MSNs suffer from poor drug loading efficiency, as well as compatibility and degradability issues for therapeutic, diagnostic, and tissue engineering purposes. Collectively, the desirable and beneficial properties of MSNs have been harnessed by modifying the surface of the siliceous frameworks through incorporating supramolecular assemblies and various metal species, and through incorporating supramolecular assemblies and various metal species and their conjugates. Substantial advancements of these innovative colloidal inorganic nanocontainers drive researchers in promoting them toward innovative applications like stimuli…

Abstract Simultaneous highly efficient production of hydrogen and conversion of biomass into value‐added products is meaningful but challenging. Herein, a porous nanospindle composed of carbon‐encapsulated MoO 2 ‐FeP heterojunction (MoO 2 ‐FeP@C) is proposed as a robust bifunctional electrocatalyst for hydrogen evolution reaction (HER) and biomass electrooxidation reaction (BEOR). X‐ray photoelectron spectroscopy analysis and theoretical calculations confirm the electron transfer from MoO 2 to FeP at the interfaces, where electron accumulation on FeP favors the optimization of H 2 O and H* absorption energies for HER, whereas hole accumulation on MoO 2 is responsible for improving the BEOR activity. Thanks to its interfacial electronic structure, MoO 2 ‐FeP@C exhibits excellent HER activity with an overpotential of 103 mV at 10 mA cm −2 and a Tafel slope of 48 mV dec −1 . Meanwhile, when 5‐hydroxymethylfurfural is chosen as the biomass for BEOR, the conversion is almost 100%, and 2,5‐furandicarboxylic acid (FDCA) is obtained with the selectivity of 98.6%. The electrolyzer employing…

Soft robotics inspired by the movement of living organisms, with excellent adaptability and accuracy for accomplishing tasks, are highly desirable for efficient operations and safe interactions with human. With the emerging wearable electronics, higher tactility and skin affinity are pursued for safe and user-friendly human-robot interactions. Fabrics interlocked by fibers perform traditional static functions such as warming, protection, and fashion. Recently, dynamic fibers and fabrics are favorable to deliver active stimulus responses such as sensing and actuating abilities for soft-robots and wearables. First, the responsive mechanisms of fiber/fabric actuators and their performances under various external stimuli are reviewed. Fiber/yarn-based artificial muscles for soft-robots manipulation and assistance in human motion are discussed, as well as smart clothes for improving human perception. Second, the geometric designs, fabrications, mechanisms, and functions of fibers/fabrics for sensing and energy harvesting from the human body and environments are summarized. Effective…

Abstract The development of oxygen reduction reaction (ORR) electrocatalysts based on earth‐abundant nonprecious materials is critically important for sustainable large‐scale applications of fuel cells and metal–air batteries. Herein, a hetero‐single‐atom (h‐SA) ORR electrocatalyst is presented, which has atomically dispersed Fe and Ni coanchored to a microsized nitrogen‐doped graphitic carbon support with unique trimodal‐porous structure configured by highly ordered macropores interconnected through mesopores. Extended X‐ray absorption fine structure spectra confirm that Fe‐ and Ni‐SAs are affixed to the carbon support via FeN 4 and NiN 4 coordination bonds. The resultant Fe/Ni h‐SA electrocatalyst exhibits an outstanding ORR activity, outperforming SA electrocatalysts with only Fe‐ or Ni‐SAs, and the benchmark Pt/C. The obtained experimental results indicate that the achieved outstanding ORR performance results from the synergetic enhancement induced by the coexisting FeN 4 and NiN 4 sites, and the superior mass‐transfer capability promoted by the trimodal‐porous‐structured…

), in which the hydrogen serves as the energy carrier. That calls for a comprehensive understanding of oxygen electrocatalysis for efficient catalyst design. Current opinions on oxygen electrocatalysis have been focused on the thermodynamics of the reactant/intermediate adsorption on the catalysts. Because the oxygen molecule is paramagnetic, its production from or its reduction to diamagnetic hydroxide/water involves spin-related electron transfer. Both electron transfer and orbital interactions between the catalyst and the reactant/intermediate show spin-dependent character, making the reaction kinetics and thermodynamics sensitive to the spin configurations. Herein, a brief introduction on the spintronic explanation of the catalytic phenomena on oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is given. The local spin configurations and orbital interactions in the benchmark transition-metal-based catalysts for OER and ORR are analyzed as examples. To further understand the spintronic oxygen electrocatalysis and to develop more efficient spintronic catalysts,…

Abstract Lead‐free double perovskites have great potential as stable and nontoxic optoelectronic materials. Recently, Cs2AgBiBr6 has emerged as a promising material, with suboptimal photon‐to‐charge carrier conversion efficiency, yet well suited for high‐energy photon‐detection applications. Here, the optoelectronic and structural properties of pure Cs2AgBiBr6 and alkali‐metal‐substituted (Cs1−xYx)2AgBiBr6 (Y: Rb+, K+, Na+; x = 0.02) single crystals are investigated. Strikingly, alkali‐substitution entails a tunability to the material system in its response to X‐rays and structural properties that is most strongly revealed in Rb‐substituted compounds whose X‐ray sensitivity outperforms other double‐perovskite‐based devices reported. While the fundamental nature and magnitude of the bandgap remains unchanged, the alkali‐substituted materials exhibit a threefold boost in their fundamental carrier recombination lifetime at room temperature. Moreover, an enhanced electron–acoustic phonon scattering is found compared to Cs2AgBiBr6. The study thus paves the way for employing cation…

Ultrasound (US)-triggered sonodynamic therapy (SDT), as a promising noninvasive therapeutic modality, has received ever-increasing attention in recent years. Its specialized chemical agents, named sonosensitizers, are activated by low-intensity US to produce lethal reactive oxygen species (ROS) for oncotherapy. Compared with phototherapeutic strategies, SDT provides many noteworthy opportunities and benefits, such as deeper penetration depth, absence of phototoxicity, and fewer side effects. Nevertheless, previous studies have also demonstrated its intrinsic limitations. Thanks to the facile engineering nature of nanotechnology, numerous novel nanoplatforms are being applied in this emerging field to tackle these intrinsic barriers and achieve continuous innovations. In particular, the combination of SDT with other treatment strategies has demonstrated a superior efficacy in improving anticancer activity relative to that of monotherapies alone. Therefore, it is necessary to summarize the nanomaterial-assisted combinational sonodynamic cancer therapy applications. Herein, the design…

Abstract Electrocatalysis is at the center of many sustainable energy conversion technologies that are being developed to reduce the dependence on fossil fuels. The past decade has witnessed significant progresses in the exploitation of advanced electrocatalysts for diverse electrochemical reactions involved in electrolyzers and fuel cells, such as the hydrogen evolution reaction (HER), the oxygen reduction reaction (ORR), the CO 2 reduction reaction (CO 2 RR), the nitrogen reduction reaction (NRR), and the oxygen evolution reaction (OER). Herein, the recent research advances made in porous electrocatalysts for these five important reactions are reviewed. In the discussions, an attempt is made to highlight the advantages of porous electrocatalysts in multiobjective optimization of surface active sites including not only their density and accessibility but also their intrinsic activity. First, the current knowledge about electrocatalytic active sites is briefly summarized. Then, the electrocatalytic mechanisms of the five above‐mentioned reactions (HER, ORR, CO 2 RR, NRR, and OER),…

Abstract Prompt recombination of photogenerated electrons and holes in bulk and on the surface of photocatalysts harshly impedes the photocatalytic efficiency. However, the simultaneous manipulation of photocharges in the two locations is challenging. Herein, the synchronous promotion of bulk and surface separation of photoinduced charges for prominent CO 2 photoreduction by coupling macroscopic spontaneous polarization and surface oxygen vacancies (OVs) of BiOIO 3 single crystals is reported. The oriented growth of BiOIO 3 single‐crystal nanostrips along the [001] direction, ensuing substantial well‐aligned IO 3 polar units, renders a large enhancement for the macroscopic polarization electric field, which is capable of driving the rapid separation and migration of charges from bulk to surface. Meanwhile the introduction of surface OVs establishes a local electric field for charge migration to catalytic sites on the surface of BiOIO 3 nanostrips. Highly polarized BiOIO 3 nanostrips with ample OVs demonstrate outstanding CO 2 reduction activity for CO production with a rate of 17.33…

Abstract Nanocatalytic therapy, using artificial nanoscale enzyme mimics (nanozymes), is an emerging technology for therapeutic treatment of various malignant tumors. However, the relatively deficient catalytic activity of nanozymes in the tumor microenvironment (TME) restrains their biomedical applications. Here, a versatile and bacteria‐like PEG/Ce‐Bi@DMSN nanozyme is developed by coating uniform Bi 2 S 3 nanorods (NRs) with dendritic mesoporous silica (Bi 2 S 3 @DMSN) and then decorating ultrasmall ceria nanozymes into the large mesopores of Bi 2 S 3 @DMSN. The nanozymes exhibit dual enzyme‐mimic catalytic activities (peroxidase‐mimic and catalase‐mimic) under acidic conditions that can regulate the TME, that is, simultaneously elevate oxidative stress and relieve hypoxia. In addition, the nanozymes can effectively consume the overexpressed glutathione (GSH) through redox reaction. Photothermal therapy (PTT) is introduced to synergistically improve the dual enzyme‐mimicking catalytic activities and depletion of the overexpressed GSH in the tumors by photonic hyperthermia. This is…

The memristor, a composite word of memory and resistor, has become one of the most important electronic components for brain-inspired neuromorphic computing in recent years. This device has the ability to control resistance with multiple states by memorizing the history of previous electrical inputs, enabling it to mimic a biological synapse in the neural network of the human brain. Among many candidates for memristive materials, including metal oxides, organic materials, and low-dimensional nanomaterials, 2D layered materials have been widely investigated owing to their outstanding physical properties and electrical tunability, low-power-switching capability, and hetero-integration compatibility. Hence, a large number of experimental demonstrations on 2D material-based memristors have been reported showing their unique memristive characteristics and novel synaptic functionalities, distinct from traditional bulk-material-based systems. Herein, an overview of the latest advances in the structures, mechanisms, and memristive characteristics of 2D material-based memristors is…

Abstract An ionic‐liquid‐based Zn salt electrolyte is demonstrated to be an effective route to solve both the side‐reaction of the hydrogen evolution reaction (HER) and Zn‐dendrite growth in Zn‐ion batteries. The developed electrolyte enables hydrogen‐free, dendrite‐free Zn plating/stripping over 1500 h cycle (3000 cycles) at 2 mA cm –2 with nearly 100% coulombic efficiency. Meanwhile, the oxygen‐induced corrosion and passivation are also effectively suppressed. These features bring Zn‐ion batteries an unprecedented long lifespan over 40 000 cycles at 4 A g –1 and high voltage of 2.05 V with a cobalt hexacyanoferrate cathode. Furthermore, a 28.6 µm thick solid polymer electrolyte of a poly(vinylidene fluoride‐hexafluoropropylene) film filled with poly(ethylene oxide)/ionic‐liquid‐based Zn salt is constructed to build an all‐solid‐state Zn‐ion battery. The all‐solid‐state Zn‐ion batteries show excellent cycling performance of 30 000 cycles at 2 A g –1 at room temperature and withstand high temperature up to 70 °C, low temperature to –20 °C, as well as abuse test of bending…

Incorporating molecular photoswitches into various materials provides unique opportunities for controlling their properties and functions with high spatiotemporal resolution using remote optical stimuli. The great and largely still untapped potential of these photoresponsive systems has not yet been fully exploited due to the fundamental challenges in harnessing geometrical and electronic changes on the molecular level to modulate macroscopic and bulk material properties. Herein, progress made during the past decade in the field of photoswitchable materials is highlighted. After pointing to some general design principles, materials with an increasing order of the integrated photoswitchable units are discussed, spanning the range from amorphous settings over surfaces/interfaces and supramolecular ensembles, to liquid crystalline and crystalline phases. Finally, some potential future directions are pointed out in the conclusion. In view of the exciting recent achievements in the field, the future emergence and further development of light-driven and optically programmable…

Metal halide perovskites (MHPs) have been a hot research topic due to their facile synthesis, excellent optical and optoelectronic properties, and record-breaking efficiency of corresponding optoelectronic devices. Nowadays, the development of miniaturized high-performance photodetectors (PDs) has been fueling the demand for novel photoactive materials, among which low-dimensional MHPs have attracted burgeoning research interest. In this report, the synthesis, properties, photodetection performance, and stability of low-dimensional MHPs, including 0D, 1D, 2D layered and nonlayered nanostructures, as well as their heterostructures are reviewed. Recent advances in the synthesis approaches of low-dimensional MHPs are summarized and the key concepts for understanding the optical and optoelectronic properties related to the PD applications of low-dimensional MHPs are introduced. More importantly, recent progress in novel PDs based on low-dimensional MHPs is presented, and strategies for improving the performance and stability of perovskite PDs are highlighted. By discussing recent…

Abstract There is a huge requirement of elastomers for use in tires, seals, and shock absorbers every year worldwide. In view of a sustainable society, the next generation of elastomers is expected to combine outstanding healing, recycling, and damage‐tolerant capacities with high strength, elasticity, and toughness. However, it remains challenging to fabricate such elastomers because the mechanisms for the properties mentioned above are mutually exclusive. Herein, the fabrication of healable, recyclable, and mechanically tough polyurethane (PU) elastomers with outstanding damage tolerance by coordination of multiblock polymers of poly(dimethylsiloxane) (PDMS)/polycaprolactone (PCL) containing hydrogen and coordination bonding motifs with Zn 2+ ions is reported. The organization of bipyridine groups coordinated with Zn 2+ ions, carbamate groups cross‐linked with hydrogen bonds, and crystallized PCL segments generates phase‐separated dynamic hierarchical domains. Serving as rigid nanofillers capable of deformation and disintegration under an external force, the dynamic hierarchical…

The commercialization of fuel cells, such as proton exchange membrane fuel cells and direct methanol/formic acid fuel cells, is hampered by their poor stability, high cost, fuel crossover, and the sluggish kinetics of platinum (Pt) and Pt-based electrocatalysts for both the cathodic oxygen reduction reaction (ORR) and the anodic hydrogen oxidation reaction (HOR) or small molecule oxidation reaction (SMOR). Thus far, the exploitation of active and stable electrocatalysts has been the most promising strategy to improve the performance of fuel cells. Accordingly, increasing attention is being devoted to modulating the surface/interface electronic structure of electrocatalysts and optimizing the adsorption energy of intermediate species by defect engineering to enhance their catalytic performance. Defect engineering is introduced in terms of defect definition, classification, characterization, construction, and understanding. Subsequently, the latest advances in defective electrocatalysts for ORR and HOR/SMOR in fuel cells are scientifically and systematically summarized. Furthermore,…

Abstract Y3Al5O12:Ce3+ (YAG:Ce3+) transparent ceramic phosphors (TCPs) are regarded as the most promising luminescent converter for laser‐driven (LD) lighting. High‐quality YAG:Ce3+ TCPs are still urgent for high efficiency LD lighting devices. YAG:Ce3+ TCPs in a vacuum ambience by using nano‐sized raw materials are prepared. Controlling defects by adding nano‐sized MgO and SiO2 simultaneously enables a high transmittance nearly 80%. After annealing in air furthermore, the luminous efficiency is enhanced greatly from 106 to 223 lm W−1, which is the best result reported now for LD lighting. These results demonstrate that the optimizing YAG:Ce3+ TCPs in a fitting strategy will brighten once again in the next‐generation LD lighting. Based on scanning electron microscopy (SEM) coupled with a cathodoluminescence system, defects and Ce3+ distributions in grains are identified directly for the first time.

High-strength petroleum-based materials like plastics have been widely used in various fields, but their nonbiodegradability has caused serious pollution problems. Cellulose, as the most abundant sustainable polymer, has a great chance to act as the ideal substitute for plastics due to its low cost, wide availability, biodegradability, etc. Herein, the recent achievements for developing cellulose "green" solvents and regenerated cellulose materials with high strength via the "bottom-up" route are presented. Cellulose can be regenerated to produce films/membranes, hydrogels/aerogels, filaments/fibers, microspheres/beads, bioplastics, etc., which show potential applications in textiles, biomedicine, energy storage, packaging, etc. Importantly, these cellulose-based materials can be biodegraded in soil and oceans, reducing environmental pollution. The cellulose solvents, dissolving mechanism, and strategies for constructing the regenerated cellulose functional materials with high strength and performances, together with the current achievements and urgent challenges are summarized, and…

Abstract Rechargeable zinc‐ion batteries (ZIBs) are emerging as a promising alternative for Li‐ion batteries. However, the developed cathodes suffer from sluggish Zn 2+ diffusion kinetics, leading to poor rate capability and inadequate cycle life. Herein, an in situ polyaniline (PANI) intercalation strategy is developed to facilitate the Zn 2+ (de)intercalation kinetics in V 2 O 5 . In this way, a remarkably enlarged interlayer distance (13.90 Å) can be constructed alternatively between the VO layers, offering expediting channels for facile Zn 2+ diffusion. Importantly, the electrostatic interactions between the Zn 2+ and the host O 2− , which is another key factor in hindering the Zn 2+ diffusion kinetics, can be effectively blocked by the unique π‐conjugated structure of PANI. As a result, the PANI‐intercalated V 2 O 5 exhibits a stable and highly reversible electrochemical reaction during repetitive Zn 2+ insertion and extraction, as demonstrated by in situ synchrotron X‐ray diffraction and Raman studies. Further first‐principles calculations clearly reveal a remarkably lowered…

Owing to the promise of high safety and energy density, all-solid-state batteries are attracting incremental interest as one of the most promising next-generation energy storage systems. However, their widespread applications are inhibited by many technical challenges, including low-conductivity electrolytes, dendrite growth, and poor cycle/rate properties. Particularly, the interfacial dynamics between the solid electrolyte and the electrode is considered as a crucial factor in determining solid-state battery performance. In recent years, intensive research efforts have been devoted to understanding the interfacial behavior and strategies to overcome these challenges for all-solid-state batteries. Here, the interfacial principle and engineering in a variety of solid-state batteries, including solid-state lithium/sodium batteries and emerging batteries (lithium-sulfur, lithium-air, etc.), are discussed. Specific attention is paid to interface physics (contact and wettability) and interface chemistry (passivation layer, ionic transport, dendrite growth), as well as the strategies to…

MXenes are emerging rapidly as a new family of multifunctional nanomaterials with prospective applications rivaling that of graphenes. Herein, a timely account of the design and performance evaluation of MXene-based membranes is provided. First, the preparation and physicochemical characteristics of MXenes are outlined, with a focus on exfoliation, dispersion stability, and processability, which are crucial factors for membrane fabrication. Then, different formats of MXene-based membranes in the literature are introduced, comprising pristine or intercalated nanolaminates and polymer-based nanocomposites. Next, the major membrane processes so far pursued by MXenes are evaluated, covering gas separation, wastewater treatment, desalination, and organic solvent purification. The potential utility of MXenes in phase inversion and interfacial polymerization, as well as layer-by-layer assembly for the preparation of nanocomposite membranes, is also critically discussed. Looking forward, exploiting the high electrical conductivity and catalytic activity of certain MXenes is put into…

Abstract The introduction of the redox couple of triiodide/iodide (I 3 − /I − ) into aqueous rechargeable zinc batteries is a promising energy‐storage resource owing to its safety and cost‐effectiveness. Nevertheless, the limited lifespan of zinc–iodine (Zn–I 2 ) batteries is currently far from satisfactory owing to the uncontrolled shuttling of triiodide and unfavorable side‐reactions on the Zn anode. Herein, space‐resolution Raman and micro‐IR spectroscopies reveal that the Zn anode suffers from corrosion induced by both water and iodine species. Then, a metal–organic framework (MOF) is exploited as an ionic sieve membrane to simultaneously resolve these problems for Zn–I 2 batteries. The multifunctional MOF membrane, first, suppresses the shuttling of I 3 − and restrains related parasitic side‐reaction on the Zn anode. Furthermore, by regulating the electrolyte solvation structure, the MOF channels construct a unique electrolyte structure (more aggregative ion associations than in saturated electrolyte). With the concurrent improvement on both the iodine cathode and the Zn anode,…

Abstract Zinc metal anode has garnered a great deal of scientific and technological interest. Nevertheless, major bottlenecks restricting its large‐scale utilization lie in the poor electrochemical stability and unsatisfactory cycling life. Herein, a Janus separator is developed via directly growing vertical graphene (VG) carpet on one side of commercial glass fiber separator throughout chemical vapor deposition. A simple air plasma treatment further renders the successful incorporation of oxygen and nitrogen heteroatoms on bare graphene. Thus‐derived 3D VG scaffold affording large surface area and porous structure can be viewed as a continuation of planar zinc anode. In turn, the Janus separator harvests homogenous electric field distribution and lowered local current density at the interface of the anode/electrolyte, as well as harnesses favorable zincophilic feature for building‐up uniform Zn ionic flux. Such a separator engineering enables an impressive rate and cycle performance (93% over 5000 cycles at 5 A g −1 ) for Zn‐ion hybrid capacitors and outstanding energy density (182…

Ionic liquids (ILs) are widely studied as a safer alternative electrolyte for lithium-ion batteries. The properties of IL electrolytes compared to conventional electrolytes make them more thermally stable, but they also have poor wetting with commercial separators. In a lithium-ion battery, the electrolyte should completely wet out the separator and electrodes to reduce the cell internal resistance. Investigations of cell materials with IL electrolytes have shown that the wetting issues in IL-electrolyte cells are most likely due to poor separator compatibility, not electrode compatibility. A compatible separator must be developed before IL electrolytes can be used in commercial lithium-ion batteries. Herein, separators for IL electrolytes, including commercial and novel separators, are reviewed. Separators with different processing methods, polymers, additives, and different IL electrolytes are considered. Collated, the separator studies show a strong correlation between ionic conductivity and membrane porosity, even more than the electrolyte type. The challenge of a suitable…

Development of high-performance carbon dots (CDs) with emission wavelength longer than 660 nm (deep red emission) is critical in deep-tissue bioimaging, yet it is still a major challenge to obtain CDs with both narrow full width at half maximum (FWHM) and high deep red/near-infrared emission yield. Here, deep red emissive carbonized polymer dots (CPDs) with unprecedented FWHM of 20 nm are synthesized. The purified CPDs in dimethyl sulfoxide (DMSO) solution possess quantum yield (QY) as high as 59% under 413 nm excitation, as well as recorded QY of 31% under 660 nm excitation in the deep red fluorescent window. Detailed characterizations identify that CPDs have unique polymer characteristics, consisting of carbon cores and the shells of polymer chains, and π conjugated system formed with N heterocycles and aromatic rings governs the single photoluminescence (PL) center, which is responsible for high QY in deep red emissive CPDs with narrow FWHM. The CPDs exhibit strong absorption and emission in the deep red light region, low toxicity, and good biocompatibility, making them an…

Abstract Establishing highly effective charge transfer channels in carbon nitride (C 3 N 4 ) for enhancing its photocatalytic activity is still a challenging issue. Herein, for the first time, the engineering of C 3 N 4 layers with single‐atom Cu bonded with compositional N (CuN x ) is demonstrated to address this challenge. The CuN x is formed by intercalation of chlorophyll sodium copper salt into a melamine‐based supramolecular precursor followed by controlled pyrolysis. Two groups of CuN x are identified: in one group each of Cu atoms is bonded with three in‐plane N atoms, while in the other group each of Cu atoms is bonded with four N atoms of two neighboring C 3 N 4 layers, thus forming both in‐plane and interlayer charge transfer channels. Importantly, ultrafast spectroscopy has further proved that CuN x can greatly improve in‐plane and interlayer separation/transfer of charge carriers and in turn boost the photocatalytic efficiency. Consequently, the catalyst exhibits a superior visible‐light photocatalytic hydrogen production rate (≈212 µmol h −1 /0.02 g catalyst), 30…

Abstract Carbon‐based materials have been considered as the most promising anode materials for both sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs), owing to their good chemical stability, high electrical conductivity, and environmental benignity. However, due to the large sizes of sodium and potassium ions, it is a great challenge to realize a carbon anode with high reversible capacity, long cycle life, and high rate capability. Herein, by rational design, N‐doped 3D mesoporous carbon nanosheets (N‐CNS) are successfully synthesized, which can realize unprecedented electrochemical performance for both SIBs and PIBs. The N‐CNS possess an ultrathin nanosheet structure with hierarchical pores, ultrahigh level of pyridinic N/pyrrolic N, and an expanded interlayer distance. The beneficial features that can enhance the Na‐/K‐ion intercalation/deintercalation kinetic process, shorten the diffusion length for both ions and electrons, and accommodate the volume change are demonstrated. Hence, the N‐CNS‐based electrode delivers a high capacity of 239 mAh g −1 at 5 A g −1 after…

Covalent adaptable networks (CANs), unlike typical thermosets or other covalently crosslinked networks, possess a unique, often dormant ability to activate one or more forms of stimuli-responsive, dynamic covalent chemistries as a means to transition their behavior from that of a viscoelastic solid to a material with fluid-like plastic flow. Upon application of a stimulus, such as light or other irradiation, temperature, or even a distinct chemical signal, the CAN responds by transforming to a state of temporal plasticity through activation of either reversible addition or reversible bond exchange, either of which allows the material to essentially re-equilibrate to an altered set of conditions that are distinct from those in which the original covalently crosslinked network is formed, often simultaneously enabling a new and distinct shape, function, and characteristics. As such, CANs span the divide between thermosets and thermoplastics, thus offering unprecedented possibilities for innovation in polymer and materials science. Without attempting to comprehensively review the…

Molecular science entails the study of structures and properties of materials at the level of single molecules or small interacting complexes of molecules. Moving beyond single molecules and well-defined complexes, aggregates (i.e., irregular clusters of many molecules) serve as a particularly useful form of materials that often display modified or wholly new properties compared to their molecular components. Some unique structures and phenomena such as polymorphic aggregates, aggregation-induced symmetry breaking, and cluster excitons are only identified in aggregates, as a few examples of their exotic features. Here, by virtue of the flourishing research on aggregation-induced emission, the concept of "aggregate science" is put forward to fill the gaps between molecules and aggregates. Structures and properties on the aggregate scale are also systematically summarized. The structure-property relationships established for aggregates are expected to contribute to new materials and technological development. Ultimately, aggregate science may become an interdisciplinary research field…

) and their derivatives, a review article focusing on MON-based nanoplatforms has not been reported yet. Herein, the representative progresses of MONs on synthesis, heterogene, properties, surface modification, toxicity, imaging, biodetection, and therapy are mainly introduced. First, five kinds of primary synthetic methods of MONs are presented, including thermal decomposition method, exfoliation strategy, permanganates reduction method, adsorption-oxidation method, and hydro/solvothermal. Second, the preparations of hollow MONs and MON-based composite materials are summarized specially. Then, the chemical properties, surface modification, and toxicity of MONs are discussed. Next, the diagnostic applications including imaging and sensing are outlined. Finally, some representative rational designs of MONs in photodynamic therapy, photothermal therapy, chemodynamic therapy, sonodynamic therapy, radiotherapy, magnetic hyperthermia, chemotherapy, gene therapy, starvation therapy, ferroptosis, immunotherapy, and various combination therapy are highlighted.