The 100 most-cited articles in Angewandte Chemie International Edition, 2024

Abstract Although oxygen vacancies (Ovs) have been intensively studied in single semiconductor photocatalysts, exploration of intrinsic mechanisms and in‐depth understanding of Ovs in S‐scheme heterojunction photocatalysts are still limited. Herein, a novel S‐scheme photocatalyst made from WO 3 ‐Ov/In 2 S 3 with Ovs at the heterointerface is rationally designed. The microscopic environment and local electronic structure of the S‐scheme heterointerface are well optimized by Ovs. Femtosecond transient absorption spectroscopy (fs‐TAS) reveals that Ovs trigger additional charge movement routes and therefore increase charge separation efficiency. In addition, Ovs have a synergistic effect on the thermodynamic and kinetic parameters of S‐scheme photocatalysts. As a result, the optimal photocatalytic performance is significantly improved, surpassing that of single component WO 3 ‐Ov and In 2 S 3 (by 35.5 and 3.9 times, respectively), as well as WO 3 /In 2 S 3 heterojunction. This work provides new insight into regulating the photogenerated carrier dynamics at the heterointerface and also…

Abstract Given the merits of abundant resource, low cost and high electrochemical activity, hard carbons have been regarded as one of the most commercializable anode material for sodium‐ion batteries (SIBs). However, poor rate capability is one of the main obstacles that severely hinder its further development. In addition, the relationships between preparation method, material structure and electrochemical performance have not been clearly elaborated. Herein, a simple but effective strategy is proposed to accurately construct the multiple structural features in hard carbon via adjusting the components of precursors. Through detailed physical characterization of the hard carbons derived from different regulation steps, and further combined with in‐situ Raman and galvanostatic intermittent titration technique (GITT) analysis, the network of multiple relationships between preparation method, microstructure, sodium storage behavior and electrochemical performance have been successfully established. Simultaneously, exceptional rate capability about 108.8 mAh g −1 at 8 A g −1 have been…

Abstract Despite many additives have been reported for aqueous zinc ion batteries, steric‐hindrance effect of additives and its correlation with Zn 2+ solvation structure have been rarely reported. Herein, large‐sized sucrose biomolecule is selected as a paradigm additive, and steric‐hindrance electrolytes (STEs) are developed to investigate the steric‐hindrance effect for solvation structure regulation. Sucrose molecules do not participate in Zn 2+ solvation shell, but significantly homogenize the distribution of solvated Zn 2+ and enlarge Zn 2+ solvation shell with weakened Zn 2+ −H 2 O interaction due to the steric‐hindrance effect. More importantly, STEs afford the water‐shielding electric double layer and in situ construct the organic and inorganic hybrid solid electrolyte interface, which effectively boost Zn anode reversibility. Remarkably, Zn//NVO battery presents high capacity of 3.9 mAh ⋅ cm −2 with long cycling stability for over 650 cycles at lean electrolyte of 4.5 μL ⋅ mg −1 and low N/P ratio of 1.5, and the stable operation at wide temperature (−20 °C~+40 °C).

Abstract The solar‐driven photocatalytic production of hydrogen peroxide (H 2 O 2 ) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H 2 O 2 production is often restricted by the low photo‐generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed‐linker strategy to build a donor‐acceptor‐acceptor (D–A–A) type covalent organic framework (COF) photocatalyst, FS‐OHOMe‐COF. The FS‐OHOMe‐COF structure features extended π–π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS‐OHOMe‐COF has a low exciton binding energy, long excited‐state lifetime and high photo‐stability that leads to high performance for photocatalytic H 2 O 2 production (up to 1.0 mM h −1 ) with an H 2 O 2 output of 19 mM after 72 hours of irradiation. Furthermore, the…

Abstract The lattice oxygen mechanism (LOM) endows NiFe layered double hydroxide (NiFe‐LDH) with superior oxygen evolution reaction (OER) activity, yet the frequent evolution and sluggish regeneration of lattice oxygen intensify the dissolution of active species. Herein, we overcome this challenge by constructing the NiFe hydroxide/Ni4Mo alloy (NiFe‐LDH/Ni4Mo) heterojunction electrocatalyst, featuring the Ni4Mo alloy as the oxygen pump to provide oxygenous intermediates and electrons for NiFe‐LDH. The released lattice oxygen can be timely offset by the oxygenous species during the LOM process, balancing the regeneration of lattice oxygen and assuring the enhancement of the durability. In consequence, the durability of NiFe‐LDH is significantly enhanced after the modification of Ni4Mo with an impressive durability for over 60 h, much longer than that of NiFe‐LDH counterpart with only 10 h. In situ spectra and first‐principle simulations reveal that the adsorption of OH− is significantly strengthened owing to the introduction of Ni4Mo, ensuring the rapid regeneration of lattice…

Abstract Hydrogen peroxide (H 2 O 2 ) is a crucial chemical applied in various industry sectors. However, the current industrial anthraquinone process for H 2 O 2 synthesis is carbon‐intensive. With sunlight and renewable electricity as energy inputs, photocatalysis and electrocatalysis have great potential for green H 2 O 2 production from oxygen (O 2 ) and water (H 2 O). Herein, we review the advances in pairing two‐electron O 2 reduction and two‐electron H 2 O oxidation reactions for dual‐pathway H 2 O 2 synthesis. The basic principles, paired redox reactions, and catalytic device configurations are introduced initially. Aligning with the energy input, the latest photocatalysts, electrocatalysts, and photo‐electrocatalysts for dual‐pathway H 2 O 2 production are discussed afterward. Finally, we outlook the research opportunities in the future. This minireview aims to provide insights and guidelines for the broad community who are interested in catalyst design and innovative technology for on‐site H 2 O 2 synthesis.

Abstract The global crisis of bacterial infections is exacerbated by the escalating threat of microbial antibiotic resistance. Nanozymes promise to provide ingenious solutions. Here, we reported a homogeneous catalytic structure of Pt nanoclusters with finely tuned metal–organic framework (ZIF‐8) channel structures for the treatment of infected wounds. Catalytic site normalization showed that the active site of the Pt aggregates structure with fine‐tuned pore modifications structure had a catalytic capacity of 14.903×10 5 min −1 , which was 18.7 times higher than that of the Pt particles in monodisperse state in ZIF‐8 (0.793×10 5 min −1 ). In situ tests revealed that the change from homocleavage to heterocleavage of hydrogen peroxide at the interface of the nanozyme was one of the key reasons for the improvement of nanozyme activity. Density‐functional theory and kinetic simulations of the reaction interface jointly determine the role of the catalytic center and the substrate channel together. Metabolomics analysis showed that the developed nanozyme, working in conjunction with…

Abstract During the electrocatalytic NO 3 − reduction reaction (NO 3 − RR) under neutral condition, the activation of H 2 O to generate H* and the inhibition of inter‐H* species binding, are critically important but remain challenging for suppressing the non‐desirable hydrogen evolution reaction (HER). Here, a Mn‐doped Co(OH) 2 (named as Mn‐Co(OH) 2 ) has been synthesized by in situ reconstruction in the electrolyte, which is able to dissociate H 2 O molecules but inhibits the binding of H* species between each other owing to the increased interatomic spacing by the Mn‐doping. The Mn‐Co(OH) 2 electrocatalyst offers a faradaic efficiency (FE) of as high as 98.9±1.7% at −0.6 V vs. the reversible hydrogen electrode (RHE) and an energy efficiency (EE) of 49.90±1.03% for NH 3 production by NO 3 − RR, which are among the highest of the recently reported state‐of‐the‐art catalysts in neutral electrolyte. Moreover, negligible degradation at −200 mA cm −2 has been found for at least 500 h, which is the longest catalytic durations ever reported. This work paves a novel approach for the design…

Abstract The electrocatalytic CO 2 reduction reaction (CO 2 RR) is a sustainable route for converting CO 2 into value‐added fuels and feedstocks, advancing a carbon‐neutral economy. The electrolyte critically influences CO 2 utilization, reaction rate and product selectivity. While typically conducted in neutral/alkaline aqueous electrolytes, the CO 2 RR faces challenges due to (bi)carbonate formation and its crossover to the anolyte, reducing efficiency and stability. Acidic media offer promise by suppressing these processes, but the low Faradaic efficiency, especially for multicarbon (C 2+ ) products, and poor electrocatalyst stability persist. The effective regulation of the reaction environment at the cathode is essential to favor the CO 2 RR over the competitive hydrogen evolution reaction (HER) and improve long‐term stability. This review examines progress in the acidic CO 2 RR, focusing on reaction environment regulation strategies such as electrocatalyst design, electrode modification and electrolyte engineering to promote the CO 2 RR. Insights into the reaction mechanisms…

Abstract Zinc ion batteries (ZIBs) exhibit significant promise in the next generation of grid‐scale energy storage systems owing to their safety, relatively high volumetric energy density, and low production cost. Despite substantial advancements in ZIBs, a comprehensive evaluation of critical parameters impacting their practical energy density (Epractical) and calendar life is lacking. Hence, we suggest using formulation‐based study as a scientific tool to accurately calculate the cell‐level energy density and predict the cycling life of ZIBs. By combining all key battery parameters, such as the capacity ratio of negative to positive electrode (N/P), into one formula, we assess their impact on Epractical. When all parameters are optimized, we urge to achieve the theoretical capacity for a high Epractical. Furthermore, we propose a formulation that correlates the N/P and Coulombic efficiency of ZIBs for predicting their calendar life. Finally, we offer a comprehensive overview of current advancements in ZIBs, covering cathode and anode, along with practical evaluations. This…

Abstract The development of photocatalysts with continuous electron extraction and rapid proton transfer could kinetically accelerate the artificial photosynthesis, but remains a challenge. Herein, we report the topology‐guided synthesis of a high‐crystalline triazine covalent organic framework (COF) decorated by uniformly distributed polar oxygen functional groups (sulfonic group or carboxyl) as the strong electron/proton extractor for efficient photocatalytic H2O2 production. It was found that the polarity‐based proton transfer as well as electron enrichment in as‐obtained COFs played a crucial role in improving the H2O2 photosynthesis efficiency (i.e., with an activity order of sulfonic acid‐ (SO3H‐COF)>carboxyl‐ (COOH‐COF)>hydrogen‐ (H‐COF) functionalized COFs). The strong polar sulfonic acid group in the high‐crystalline SO3H‐COF triggered a well‐oriented built‐in electric field and more hydrophilic surface, which serves as an efficient carrier extractor enabling a continuous transportation of the photogenerated electrons and interfacial proton to the active sites (i.e., C…

Abstract Triggering the lattice oxygen oxidation mechanism is crucial for improving oxygen evolution reaction (OER) performance, because it could bypass the scaling relation limitation associated with the conventional adsorbate evolution mechanism through the direct formation of oxygen–oxygen bond. High‐valence transition metal sites are favorable for activating the lattice oxygen, but the deep oxidation of pre‐catalysts suffers from a high thermodynamic barrier. Here, taking advantage of the Jahn–Teller (J–T) distortion induced structural instability, we incorporate high‐spin Mn 3+ ( ) dopant into Co 4 N. Mn dopants enable a surface structural transformation from Co 4 N to CoOOH, and finally to CoO 2 , as observed by various in situ spectroscopic investigations. Furthermore, the reconstructed surface on Mn‐doped Co 4 N triggers the lattice oxygen activation, as evidenced experimentally by pH‐dependent OER, tetramethylammonium cation adsorption and online electrochemical mass spectrometry measurements of 18 O‐labelled catalysts. In general, this work not only offers the introducing…

Abstract The practical implementation of aqueous zinc‐iodine batteries (ZIBs) is hindered by the rampant Zn dendrites growth, parasite corrosion, and polyiodide shuttling. In this work, ionic liquid EMIM[OAc] is employed as an all‐round solution to mitigate challenges on both the Zn anode and the iodine cathode side. First, the EMIM + embedded lean‐water inner Helmholtz plane (IHP) and inert solvation sheath modulated by OAc − effectively repels H 2 O molecules away from the Zn anode surface. The preferential adsorption of EMIM + on Zn metal facilitates uniform Zn nucleation via a steric hindrance effect. Second, EMIM + can reduce the polyiodide shuttling by hindering the iodine dissolution and forming an EMIM + ‐I 3 − dominated phase. These effects holistically enhance the cycle life, which is manifested by both Zn || Zn symmetric cells and Zn‐I 2 full cells. ZIBs with EAc deliver a capacity decay rate of merely 0.01 ‰ per cycle after over 18,000 cycles at 4 A g −1 , and lower self‐discharge and better calendar life than the ZIBs without ionic liquid EAc additive.

Abstract Singlet oxygen ( 1 O 2 ) is an essential reactive species responsible for selective oxidation of organic matter, especially in Fenton‐like processes. However, due to the great limitations in synthesizing catalysts with well‐defined active sites, the controllable production and practical application of 1 O 2 remain challenging. Herein, guided by theoretical simulations, a series of boron nitride‐based single‐atom catalysts (BvBN/M, M=Co, Fe, Cu, Ni and Mn) were synthesized to regulate 1 O 2 generation by activating peroxymonosulfate (PMS). All the fabricated BvBN/M catalysts with explicit M−N 3 sites promoted the self‐decomposition of the two PMS molecules to generate 1 O 2 with high selectivity, where BvBN/Co possessed moderate adsorption energy and d ‐band center exhibited superior catalytic activity. As an outcome, the BvBN/Co‐PMS system coupled with membrane filtration technology could continuously transform aromatic alcohols to aldehydes with nearly 100 % selectivity and conversion rate under mild conditions, suggesting the potential of this novel catalytic system for…

Abstract The development of highly thermally conductive composites that combine visible light/infrared camouflage and information encryption has been endowed with great significance in facilitating the application of 5G communication technology in military fields. This work uses aramid nanofibers (ANF) as the matrix, hetero‐structured silver nanowires@boron nitride nanosheets (AgNWs@BNNS) prepared by in situ growth as fillers, which are combined to fabricate sandwich structured thermally conductive and electrically insulating (BNNS/ANF)‐(AgNWs@BNNS)‐(BNNS/ANF) (denoted as BAB) composite films by “filtration self‐assembly, air spraying, and hot‐pressing” method. When the mass ratio of AgNWs@BNNS to BNNS is 1 : 1 and the total mass fraction is 50 wt %, BAB composite film has the maximum in‐plane thermal conductivity coefficient ( λ ∥ of 10.36 W/(m ⋅ K)), excellent electrical insulation (breakdown strength and volume resistivity of 41.5 kV/mm and 1.21×10 15 Ω ⋅ cm, respectively) and mechanical properties (tensile strength of 170.9 MPa). 50 wt % BAB composite film could efficiently…

Abstract RuO2 has been considered as the most likely acidic oxygen evolution reaction (OER) catalyst to replace IrO2, but its performance, especially long‐term stability under harsh acidic conditions, is still unacceptable. Here, we propose a grain boundary (GB) engineering strategy by fabricating the ultrathin porous RuO2 nanosheet with abundant of grain boundaries (GB‐RuO2) as an efficient acid OER catalyst. The involvement of GB induces significant tensile stress and creates an unsaturated coordination environment, effectively optimizing the adsorption of intermediates and stabilizing active site structure during OER process. Notably, the GB‐RuO2 not only exhibits a low overpotential (η10=187 mV) with an ultra‐low Tafel slope (34.5 mV dec−1), but also steadily operates for over 550 h in 0.1 M HClO4. Quasi in situ/operando methods confirm that the improved stability is attributed to GB preventing Ru dissolution and greatly inhibiting the lattice oxygen oxidation mechanism (LOM). A proton exchange membrane water electrolysis (PEMWE) using the GB‐RuO2 catalyst operates a low voltage…

Abstract The synthesis of hydrogen peroxide through artificial photosynthesis is a green and promising technology with advantages in sustainability, economy and safety. However, superoxide radical (⋅O2−), an important intermediate in photocatalytic oxygen reduction to H2O2 production, has strong oxidizing properties that potentially destabilize the catalyst. Therefore, avoiding the accumulation of ⋅O2− for its rapid conversion to H2O2 is of paramount significance in improving catalyst stability and H2O2 yield. In this work, a strategy was developed to utilize protonated groups for the rapid depletion of converted ⋅O2−, thereby the efficiency of photocatalytic synthesis of H2O2 from CN was successfully enhanced by 47‐fold. The experimental findings demonstrated that polydopamine not only improved carrier separation efficiency, and more importantly, provided the adsorption reduction active site for ⋅O2− for efficient H2O2 production. This work offers a versatile approach for synthesizing efficient and stable photocatalysts.

Aqueous zinc-ion batteries (AZIBs) are considered as the promising candidates for large-scale energy storage because of their high safety, low cost and environmental benignity. The large-scale applications of AZIBs will inevitably result in a large amount of spent AZIBs, which not only induce the waste of resources, but also pose environmental risks. Therefore, sustainable AZIBs have to be considered to minimize the risk of environmental pollution and maximize the utilization of spent compounds. Herein, this minireview focuses on the sustainability of AZIBs from material design and recycling techniques. The structure and degradation mechanism of AZIBs are discussed to guide the recycling design of the materials. Subsequently, the sustainability of component materials in AZIBs is further analysed to pre-evaluate their recycling behaviors and mentor the selection of more sustainable component materials, including active materials in cathodes, Zn anodes, and aqueous electrolytes, respectively. According to the features of component materials, corresponding green and economic approaches…

Abstract Alkaline water electrolysis (AWE) plays a crucial role in the realization of a hydrogen economy. The design and development of efficient and stable bifunctional catalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are pivotal to achieving high‐efficiency AWE. Herein, WC 1‐x /Mo 2 C nanoparticle‐embedded carbon nanofiber (WC 1‐x /Mo 2 C@CNF) with abundant interfaces is successfully designed and synthesized. Benefiting from the electron transfer behavior from Mo 2 C to WC 1‐x , the electrocatalysts of WC 1‐x /Mo 2 C@CNF exhibit superior HER and OER performance. Furthermore, when employed as anode and cathode in membrane electrode assembly devices, the WC 1‐x /Mo 2 C@CNF catalyst exhibits enhanced catalytic activity and remarkable stability for 100 hours at a high current density of 200 mA cm −2 towards overall water splitting. The experimental characterizations and theoretical simulation reveal that modulation of the d‐band center for WC 1‐x /Mo 2 C@CNF, achieved through the asymmetric charge distribution resulting from the built‐in…

The closed pores play a critical role in improving the sodium storage capacity of hard carbon (HC) anode, however, their formation mechanism as well as the efficient modulation strategy at molecular level in the polymer-derived HCs is still lacking. In this work, the steric hindrance effect has been proposed to create closed pores in the polymer-derived HCs for the first time through grafting the aromatic rings within and between the main chains in the precursor. The experimental data and theoretical calculation demonstrate that steric-hindrance effect from the aromatic ring side group can increase backbone rigidity and the internal free volumes in the polymer precursor, which can prevent the over graphitization and facilitate the formation of closed pores during the carbonization process. As a result, the as-prepared HC anode exhibits a remarkably enhanced discharge capacity of 340.3 mAh/g at 0.1 C, improved rate performance (210.7 mAh/g at 5 C) as well as boosted cycling stability (86.4 % over 1000 cycles at 2 C). This work provides a new insight into the formation mechanisms of…

Abstract Electrocatalytic urea synthesis under ambient conditions offers a promising alternative strategy to the traditional energy‐intensive urea industry protocol. Limited by the electrostatic interaction, the reduction reaction of anions at the cathode in the electrocatalytic system is not easily achievable. Here, we propose a novel strategy to overcome electrostatic interaction via pulsed electroreduction. We found that the reconstruction‐resistant CuSiO x nanotube, with abundant atomic Cu−O−Si interfacial sites, exhibits ultrastability in the electrosynthesis of urea from nitrate and CO 2 . Under a pulsed potential approach with optimal operating conditions, the Cu−O−Si interfaces achieve a superior urea production rate (1606.1 μg h −1 mg cat. −1 ) with high selectivity (79.01 %) and stability (the Faradaic efficiency is retained at 80 % even after 80 h of testing), outperforming most reported electrocatalytic synthesis urea catalysts. We believe our strategy will incite further investigation into pulsed electroreduction increasing substrate transport, which may guide the…

Abstract Efficient dual‐single‐atom catalysts are crucial for enhancing atomic efficiency and promoting the commercialization of fuel cells, but addressing the sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline media and the facile dual‐single‐atom site generation remains formidable challenges. Here, we break the local symmetry of ultra‐small ruthenium (Ru) nanoparticles by embedding cobalt (Co) single atoms, which results in the release of Ru single atoms from Ru nanoparticles on reduced graphene oxide (Co 1 Ru 1,n /rGO). In situ operando spectroscopy and theoretical calculations reveal that the oxygen‐affine Co atom disrupts the symmetry of ultra‐small Ru nanoparticles, resulting in parasitic Ru and Co dual‐single‐atom within Ru nanoparticles. The interaction between Ru single atoms and nanoparticles forms effective active centers. The parasitism of Co atoms modulates the adsorption of OH intermediates on Ru active sites, accelerating HOR kinetics through faster formation of *H 2 O. As anticipated, Co 1 Ru 1,n /rGO exhibits ultrahigh mass activity (7.68 A mg Ru −1…

Abstract The concept of molecular design, integrating diagnostic and therapeutic functions, aligns with the general trend of modern medical advancement. Herein, we rationally designed the smart molecule ER‐ZS for endoplasmic reticulum (ER)‐targeted diagnosis and treatment in cell and animal models by combining hemicyanine dyes with ER‐targeted functional groups (p‐toluenesulfonamide). Owing to its ability to target the ER with a highly specific response to viscosity, ER‐ZS demonstrated substantial fluorescence turn‐on only after binding to the ER, independent of other physiological environments. In addition, ER‐ZS, being a small molecule, allows for the diagnosis of nonalcoholic fatty liver disease (NAFLD) via liver imaging based on high ER stress. Importantly, ER‐ZS is a type I photosensitizer, producing O2⋅− and ⋅OH under light irradiation. Thus, after irradiating for a certain period, the photodynamic therapy inflicted severe oxidative damage to the ER of tumor cells in hypoxic (2 % O2) conditions and activated the unique pyroptosis pathway, demonstrating excellent antitumor…

Abstract Covalent organic frameworks (COFs) are promising photocatalysts for H 2 O 2 production from water via oxygen reduction reaction (ORR). The design of COFs for efficient H 2 O 2 production indubitably hinges on an in‐depth understanding of their ORR mechanisms. In this work, taking an imine‐linked COF as an example, we demonstrate that protonation of the functional units such as imine, amine, and triazine, is a highly efficient strategy to upgrade the activity levels for H 2 O 2 synthesis. The protonation not only extends the light absorption of the COF but also provides proton sources that directly participate in H 2 O 2 generation. Notably, the protonation simplifies the reaction pathways of ORR to H 2 O 2 , i.e. from an indirect superoxide radical ( ) mediated route to a direct one‐step two‐electron route. Theoretical calculations confirm that the protonation favors H 2 O 2 synthesis due to easy access of protons near the reaction sites that removes the energy barrier for generating *OOH intermediate. These findings not only extend the mechanistic insight into H 2 O 2…

Abstract A high‐efficiency PtZnCd nanozyme was screened with density functional theory (DFT) and unique d‐orbital coupling features for sensitive enrichment and real‐time analysis of CO‐releasing molecule‐3 (CORM‐3). Multicatalytic sites in the nanozyme showed a high reactivity of up to 72.89 min −1 for peroxidase (POD)‐like reaction, which was 2.2, 4.07, and 14.67 times higher than that of PtZn (32.67 min −1 ), PtCd (17.89 min −1 ), and Pt (4.97 min −1 ), respectively. Normalization of the catalytic sites showed that the catalytic capacity of the active site in PtZnCd was 2.962 U μmol −1 , which was four times higher than that of a pure Pt site (0.733 U μmol −1 ). DFT calculations showed that improved d‐orbital coupling between different metals reduces the position of the center of the shifted whole d‐band relative to the Fermi energy level, thereby increasing the contribution of the sites to the electron transfer from the active center, accompanied by enhanced substrate adsorption and intermediate conversion in the catalytic process. The potential adsorption principle and color…

The development of high-efficiency organic solar cells (OSCs) processed from non-halogenated solvents is crucially important for their scale-up industry production. However, owing to the difficulty of regulating molecular aggregation, there is a huge efficiency gap between non-halogenated and halogenated solvent processed OSCs. Herein, we fabricate o-xylene processed OSCs with approaching 20 % efficiency by incorporating a trimeric guest acceptor named Tri-V into the PM6:L8-BO-X host blend. The incorporation of Tri-V effectively restricts the excessive aggregation of L8-BO-X, regulates the molecular packing and optimizes the phase-separation morphology, which leads to mitigated trap density states, reduced energy loss and suppressed charge recombination. Consequently, the PM6:L8-BO-X:Tri-V-based device achieves an efficiency of 19.82 %, representing the highest efficiency for non-halogenated solvent-processed OSCs reported to date. Noticeably, with the addition of Tri-V, the ternary device shows an improved photostability than binary PM6:L8-BO-X-based device, and maintains 80 % of…

Abstract The artificial photosynthesis of H 2 O 2 from water and oxygen using semiconductor photocatalysts is attracting increasing levels of attention owing to its green, environmentally friendly, and energy‐saving characteristics. Although covalent organic frameworks (COFs) are promising materials for promoting photocatalytic H 2 O 2 production owing to their structural and functional diversity, they typically suffer from low charge‐generation and ‐transfer efficiencies as well as rapid charge recombination, which restricts their use as catalysts for photocatalytic H 2 O 2 production. Herein, we report a strategy for anchoring vinyl moieties to a COF skeleton to facilitate charge separation and migration, thereby promoting photocatalytic H 2 O 2 generation. This vinyl‐group‐bearing COF photocatalyst exhibits a H 2 O 2 ‐production rate of 84.5 μmol h −1 (per 10 mg), which is ten‐times higher than that of the analog devoid of vinyl functionality and superior to most reported COF photocatalysts. Both experimental and theoretical studies provide deep insight into the origin of the…

Systematic evolution of ligands by exponential enrichment (SELEX) has been used to discover thousands of aptamers since its development in 1990. Aptamers are short single-stranded oligonucleotides capable of binding to targets with high specificity and selectivity through structural recognition. While aptamers offer advantages over other molecular recognition elements such as their ease of production, smaller size, extended shelf-life, and lower immunogenicity, they have yet to show significant success in real-world applications. By analyzing the importance of structured library designs, reviewing different SELEX methodologies, and the effects of chemical modifications, we provide a comprehensive overview on the production of aptamers for applications in drug delivery systems, therapeutics, diagnostics, and molecular imaging.

Abstract Poly(vinylidene fluoride) (PVDF)‐based polymer electro‐lytes are attracting increasing attention for high‐voltage solid‐state lithium metal batteries because of their high room temperature ionic conductivity, adequate mechanical strength and good thermal stability. However, the presence of highly reactive residual solvents, such as N, N‐dimethylformamide (DMF), severely jeopardizes the long‐term cycling stability. Herein, we propose a solvation‐tailoring strategy to confine residual solvent molecules by introducing low‐cost 3 Å zeolite molecular sieves as fillers. The strong interaction between DMF and the molecular sieve weakens the ability of DMF to participate in the solvation of Li + , leading to more anions being involved in solvation. Benefiting from the tailored anion‐rich coordination environment, the interfacial side reactions with the lithium anode and high‐voltage NCM811 cathode are effectively suppressed. As a result, the solid‐state Li||Li symmetrical cells demonstrates ultra‐stable cycling over 5100 h at 0.1 mA cm −2 , and the Li||NCM811 full cells achieve…

In recent years, self-assembled monolayers (SAMs) anchored on metal oxides (MO) have greatly boosted the performance of inverted (p-i-n) perovskite solar cells (PVSCs) by serving as hole-selective contacts due to their distinct advantages in transparency, hole-selectivity, passivation, cost-effectiveness, and processing efficiency. While the intrinsic monolayer nature of SAMs provides unique advantages, it also makes them highly sensitive to external pressure, posing a significant challenge for long-term device stability. At present, the stability issue of SAM-based PVSCs is gradually attracting attention. In this minireview, we discuss the fundamental stability issues arising from the structural characteristics, operating mechanisms, and roles of SAMs, and highlight representative works on improving their stability. We identify the buried interface stability concerns in three key aspects: 1) SAM/MO interface, 2) SAM inner layer, and 3) SAM/perovskite interface, corresponding to the anchoring group, linker group, and terminal group in the SAMs, respectively. Finally, we have…

Abstract Bipyridine‐based covalent organic frameworks (COFs) have emerged as promising contenders for the photocatalytic generation of hydrogen peroxide (H 2 O 2 ). However, the presence of imine nitrogen alters the mode of H 2 O 2 generation from an efficient one‐step two‐electron (2e − ) route to a two‐step 2e − oxygen reduction pathway. In this work, we introduce 3,3′‐bipyridine units into imine‐based COF skeletons, creating a pyridyl‐imine structure with two adjacent nitrogen atoms between the pyridine ring and imine linkage. This unique bipyridine‐like architecture can effectively suppress the two‐step 2e − ORR process at the single imine‐nitrogen site, facilitating a more efficient one‐step 2e − pathway. Consequently, the optimized pyridyl‐imine COF (PyIm‐COF) exhibits a remarkable H 2 O 2 production rate of up to 5850 μmol h −1 g −1 , nearly double that of pristine bipyridine COFs. This work provides valuable insight into the rational design of functionalized COFs for enhanced H 2 O 2 production in photocatalysis.

Abstract Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C−C coupling to unravel their structure‐performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu−Cu dual sites with different site distance coordinated by halogen at the first‐shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long‐range Cu−Cu (Cu−I−Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1 %, and excellent stability. In addition, the linear relationships that the long‐range Cu−Cu dual sites are accelerated to C2H4 generation and short‐range Cu−Cu (Cu−Cl−Cu) dual sites are beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long‐range Cu−Cu…

Abstract Designing and synthesizing narrow band gap acceptors that exhibit high photoluminescence quantum yield (PLQY) and strong crystallinity is a highly effective, yet challenging, approach to reducing non‐radiative energy losses (▵ E nr ) and boosting the performance of organic solar cells (OSCs). We have successfully designed and synthesized an A–D–A type fused‐ring electron acceptor, named DM‐F, which features a planar molecular backbone adorned with bulky three‐dimensional camphane side groups at its central core. These bulky substituents effectively hinder the formation of H‐aggregates of the acceptors, promoting the formation of more J‐aggregates and notably elevating the PLQY of the acceptor in the film. As anticipated, DM‐F showcases pronounced near‐infrared absorption coupled with impressive crystallinity. Organic solar cells (OSCs) leveraging DM‐F exhibit a high EQE EL value and remarkably low ▵ E nr of 0.14 eV‐currently the most minimal reported value for OSCs. Moreover, the power conversion efficiency (PCE) of binary and ternary OSCs utilizing DM‐F has reached 16.16 %…

Abstract The development of novel metal–organic frameworks (MOFs) as efficient photocatalysts for hydrogen peroxide production from water and oxygen is particularly interesting, yet remains a challenge. Herein, we have prepared four cyclic trinuclear units (CTUs) based MOFs, exhibiting good light absorption ability and suitable band gaps for photosynthesis of H2O2. However, Cu‐CTU‐based MOFs are not able to photocatalyzed the formation of H2O2, while the alteration of metal nodes from Cu‐CTU to Ag‐CTU dramatically enhances the photocatalytic performance for H2O2 production and the production rates can reach as high as 17476 μmol g−1 h−1 with an apparent quantum yield of 4.72 %, at 420 nm, which is much higher than most reported MOFs. The photocatalytic mechanism is comprehensively studied by combining the isotope labeling experiments and DFT calculation. This study provides new insights into the preparation of MOF photocatalysts with high activity for H2O2 production through molecular engineering.

Abstract The solid‐state electrolyte interface (SEI) between the solid‐state polymer electrolyte and the lithium metal anode dramatically affects the overall battery performance. Increasing the content of lithium fluoride (LiF) in SEI can help the uniform deposition of lithium and inhibit the growth of lithium dendrites, thus improving the cycle stability performance of lithium batteries. Currently, most methods of constructing LiF SEI involve decomposing the lithium salt by the polar groups of the filler. However, there is a lack of research reports on how to affect the SEI layer of Li‐ion batteries by increasing the charge transfer number. In this study, a porous organic polymer with “charge storage” properties was prepared and doped into a polymer composite solid electrolyte to study the effect of sufficient charge transfer on the decomposition of lithium salts. The results show in contrast to porphyrins, the unique structure of POF allows for charge transfer between each individual porphyrin. Therefore, during TFSI− decomposition to the formation of LiF, TFSI− can obtain…

Abstract Achieving the complete mineralization of persistent pollutants in wastewater is still a big challenge. Here, we propose an efficient photo‐self‐Fenton reaction for the degradation of different pollutants using the high‐density (Ag: 22 wt %) of atomically dispersed AgCo dual sites embedded in graphic carbon nitride (AgCo−CN). Comprehensive experimental measurements and density functional theory (DFT) calculations demonstrate that the Ag and Co dual sites in AgCo−CN play a critical role in accelerating the photoinduced charge separation and forming the self‐Fenton redox centers, respectively. The bimetallic AgCo−CN exhibited excellent photocatalytic performance toward the phenol even under extreme conditions due to an efficient degradation pathway and in situ generation of the hydrogen peroxide producing the main active oxygen species (⋅OH and 1 O 2 ) and showed long‐term activity in a self‐design photo‐Filter reactor for the purification of the phenol. Our discoveries pave the way for the design of efficient single‐atoms photocatalysts‐based photo‐self‐Fenton reaction for…

Abstract Constructing artificial solid electrolyte interface on the Zn anode surface is recognized as an appealing method to inhibit zinc dendrites and side reactions, whereas the current techniques are complex and time‐consuming. Here, a robust and zincophilic zinc tungstate (ZnWO 4 ) layer has been in situ constructed on the Zn anode surface (denoted as ZWO@Zn) by an ultrafast chemical solution reaction. Comprehensive characterizations and theoretical calculations demonstrate that the ZWO layer can effectively modulate the interfacial electric field distribution and promote the Zn 2+ uniform diffusion, thus facilitating the uniform Zn 2+ nucleation and suppressing zinc dendrites. Besides, ZWO layer can prevent direct contact between the Zn/water and increase the hydrogen evolution reaction overpotential to eliminate side reactions. Consequently, the in situ constructed ZWO layer facilitates remarkable reversibility in the ZWO@Zn||Ti battery, achieving an impressive Coulombic efficiency of 99.36 % under 1.0 mA cm −2 , unprecedented cycling lifespan exceeding 1800 h under 1.0 mA cm…

Abstract Understanding the structure and dynamic process of interfacial water molecules at the catalyst‐electrolyte interface on acidic oxygen evolution reaction (OER) kinetics is highly desirable for the development of proton exchange membrane water electrolyzers. Herein, we construct a series of p ‐block metal elements (Ga, In, Sn) doped RuO 2 catalysts with manipulated electronic structure and Ru−O covalency to investigate the effect of electrochemical interfacial engineering on the improvement of acidic OER activity. Associated with operando attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements and theoretical analysis, we uncover the free‐H 2 O enriched local environment and dynamic evolution from 4‐coordinated hydrogen‐bonded water and 2‐coordinated hydrogen‐bonded water to free‐H 2 O on the surface of Ga−RuO 2 , are responsible for the optimized connectivity of hydrogen bonding network in the electrical double layer by promoting solvent reorganization. In addition, the structurally ordered interfacial water molecules facilitate…

Abstract Hydrogen represents a clean and sustainable energy source with wide applications in fuel cells and hydrogen energy storage systems. Photocatalytic strategies emerge as a green and promising solution for hydrogen production, which still reveals several critical challenges in enhancing the efficiency and stability and improving the whole value. This review systematically elaborates on various coupling approaches for photocatalytic hydrogen production, aiming to improve both efficiency and value through different oxidation half‐reactions. Firstly, the fundamental mechanism is discussed for photocatalytic hydrogen production. Then, the advances, challenges, and opportunities are expanded for the coupling of photocatalytic hydrogen production, which focuses on the integration of value‐added reactions including O 2 production, H 2 O 2 production, biomass conversion, alcohol oxidation, and pollutants treatment. Finally, the challenges and outlook of photocatalytic H 2 production technology are analyzed from the aspects of coupling hydrogen production value, photocatalyst design…

Abstract Photocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H 2 O 2 production. Nonetheless, constructing effective photocatalysts for H 2 O 2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H 2 O 2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sites of the monomers, we synthesized a pair of novel COFs with similar chemical components on the backbones but distinct topologies. Without sacrificial agents, TBD‐COF with cpt topology exhibited superior H 2 O 2 photoproduction performance (6085 and 5448 μmol g −1 h −1 in O 2 and air) than TBC‐COF with hcb topology through the O 2 ‐O 2 ⋅ − ‐H 2 O 2 , O 2 ‐O 2 ⋅ − ‐O 2 1 ‐H 2 O 2 , and H 2 O‐H 2 O 2 three paths. Further experimental and theoretical investigations confirmed that during the H 2 O 2 photosynthetic process, the charge carrier separation…

Abstract Efficient water dissociation to atomic hydrogen (H*) with restrained recombination of H* is crucial for improving the H* utilization for electrochemical dechlorination, but is currently limited by the lack of feasible electrodes. Herein, we developed a monolithic single‐atom electrode with Co single atoms anchored on the inherent oxide layer of titanium foam (Co1−TiOx/Ti), which can efficiently dissociate water into H* and simultaneously inhibit the recombination of H*, by taking advantage of the single‐atom reverse hydrogen spillover effect. Experimental and theoretical calculations demonstrated that H* could be rapidly generated on the oxide layer of titanium foam, and then overflowed to the adjacent Co single atom for the reductive dechlorination. Using chloramphenicol as a proof‐of‐concept verification, the resulting Co1−TiOx/Ti monolithic electrode exhibited an unprecedented performance with almost 100 % dechlorination at −1.0 V, far superior to that of traditional indirect reduction‐driven commercial Pd/C (52 %) and direct reduction‐driven Co1−N−C (44 %). Moreover,…

Abstract Spinel oxides have emerged as highly active catalysts for the oxygen evolution reaction (OER). Owing to covalency competition, the OER process on spinel oxides often follows an arduous adsorbate evolution mechanism (AEM) pathway. Herein, we propose a novel rare‐earth sites substitution strategy to tune the lattice oxygen redox of spinel oxides and bypass the AEM scaling relationship limitation. Taking NiCo 2 O 4 as a model, the incorporation of Ce into the octahedral site induces the formation of Ce−O−M (M=Ni, Co) bridge, which triggers charge redistribution within NiCo 2 O 4 . The developed Ce−NiCo 2 O 4 exhibits remarkable OER activity with a low overpotential, satisfactory electrochemical stability, and good practicability in anion‐exchange membrane water electrolyzer. Theoretical analyses reveal that OER on Ce−NiCo 2 O 4 surface follows a more favorable lattice oxygen mechanism (LOM) pathway and non‐concerted proton‐electron transfers compared to pure NiCo 2 O 4 , as also verified by pH‐dependent behavior and in situ Raman analysis. The 18 O‐labeled electrochemical mass…

Abstract The single‐atom Fe−N−C catalyst has shown great promise for the oxygen reduction reaction (ORR), yet the intrinsic activity is not satisfactory. There is a pressing need to gain a deeper understanding of the charge configuration of the Fe−N−C catalyst and to develop rational modulation strategies. Herein, we have prepared a single‐atom Fe catalyst with the co‐coordination of N and O (denoted as Fe−N/O−C) and adjacent defect, proposing a strategy to optimize the d‐orbital spin‐electron filling of Fe sites by fine‐tuning the first coordination shell. The Fe−N/O−C exhibits significantly better ORR activity compared to its Fe−N−C counterpart and commercial Pt/C, with a much more positive half‐wave potential (0.927 V) and higher kinetic current density. Moreover, using the Fe−N/O−C catalyst, the Zn‐air battery and proton exchange membrane fuel cell achieve peak power densities of up to 490 and 1179 mW cm −2 , respectively. Theoretical studies and in situ electrochemical Raman spectroscopy reveal that Fe−N/O−C undergoes charge redistribution and negative shifting of the d‐band…

Abstract Directly electrochemical conversion of nitrate (NO 3 − ) is an efficient and environmentally friendly technology for ammonia (NH 3 ) production but is challenged by highly selective electrocatalysts. High‐entropy alloys (HEAs) with unique properties are attractive materials in catalysis, particularly for multi‐step reactions. Herein, we first reported the application of HEA (FeCoNiAlTi) for electrocatalytic NO 3 − reduction to NH 3 (NRA). The bulk HEA is active for NRA but limited by the unsatisfied NH 3 yield of 0.36 mg h −1 cm −2 and Faradaic efficiency (FE) of 82.66 %. Through an effective phase engineering strategy, uniform intermetallic nanoparticles are introduced on the bulk HEA to increase electrochemical active surface area and charge transfer efficiency. The resulting nanostructured HEA (n‐HEA) delivers enhanced electrochemical NRA performance in terms of NH 3 yield (0.52 mg h −1 cm −2 ) and FE (95.23 %). Further experimental and theoretical investigations reveal that the multi‐active sites (Fe, Co, and Ni) dominated electrocatalysis for NRA over the n‐HEA.…

Abstract The direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch–Meiser process in industry. The simultaneous activation of carbon dioxide and nitrate, however, as well as efficient C−N coupling on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based on synthesizing an Ag−CuNi(OH) 2 composite to cascade carbon dioxide and nitrate reduction reactions for urea electrosynthesis. The strongly coupled metal/hydroxide heterostructure interface integrates two distinct sites for carbon dioxide and nitrate activation, and facilitates the coupling of *CO (on silver, where * denotes an active site) and *NH 2 (on hydroxide) for urea formation. Moreover, the strongly coupled interface optimizes the water splitting process and facilitates the supply of active hydrogen atoms, thereby expediting the deoxyreduction processes essential for urea formation. Consequently, our Ag−CuNi(OH) 2 composite delivers a high urea yield rate of 25.6 mmol g cat. −1 h −1 and high urea…

Abstract High‐rate and stable Zn‐ion batteries working at low temperatures are highly desirable for practical applications, but are challenged by sluggish kinetics and severe corrosion. Herein, inspired by frost‐resistant plants, we report trace hydroxyl‐rich electrolyte additives that implement a dual remodeling effect for high‐performance low‐temperature Zn‐ion batteries. The additive with high Zn absorbability not only remodels Zn 2+ primary solvent shell by alternating H 2 O molecules, but also forms a shielding layer thus remodeling the Zn surface, which effectively enhances fast Zn 2+ de‐solvation reaction kinetics and prohibits Zn anode corrosion. Taking trace α‐D‐glucose (αDG) as a demonstration, the electrolyte obtains a low freezing point of −55.3 °C, and the Zn//Zn cell can stably cycle for 2000 h at 5 mA cm −2 under −25 °C, with a high cumulative capacity of 5000 mAh cm −2 . A full battery that stably operates for 10000 cycles at −50 °C is also demonstrated.

Abstract Membranes are important in the pharmaceutical industry for the separation of antibiotics and salts. However, its widespread adoption has been hindered by limited control of the membrane microstructure (pore architecture and free‐volume elements), separation threshold, scalability, and operational stability. In this study, 4,4′,4′′,4′′′‐methanetetrayltetrakis(benzene‐1,2‐diamine) (MTLB) as prepared as a molecular building block for fabricating thin‐film composite membranes (TFCMs) via interfacial polymerization. The relatively large molecular size and rigid molecular structure of MTLB, along with its non‐coplanar and distorted conformation, produced thin and defect‐free selective layers (~27 nm) with ideal microporosities for antibiotic desalination. These structural advantages yielded an unprecedented high performance with a water permeance of 45.2 L m −2 h −1 bar −1 and efficient antibiotic desalination (NaCl/adriamycin selectivity of 422). We demonstrated the feasibility of the industrial scaling of the membrane into a spiral‐wound module (with an effective area of 2.0 m…

Abstract The sodium extraction/insertion in layered transition‐metal oxide (TMO) cathode materials are typically accompanied by slab sliding and lattice changes, leading to microstructure destruction and capacity decay. Herein, negative lattice expansion is observed in an O3 type Ni‐based layered cathode of Na 0.9 Ni 0.32 Zn 0.08 Fe 0.1 Mn 0.3 Ti 0.2 O 2 upon Na + extraction. It is attributed to the weak Zn 2+ −O 2− orbital hybridization and increased electron density of the surrounding oxygen for reinforced interlayer O−O repulsive force. This enables gliding of TMO slabs for the intergrowth phase transition of P3→OP2 to alleviate lattice strain with moderate lattice shrinkage, which exhibits general interslab spacings and volume changes as low as 2.4 % and 1.9 %, respectively. The strong Ti−O bonds accommodate the internal distortion of TMO 6 octahedra due to the flexibility of TiO 6 octahedra during cycling. These endow a high specific capacity of 144.9 mAh g −1 and excellent cycling performance of pouch‐type sodium‐ion batteries with 93 % capacity retention after 3600 cycles.

Abstract Photocatalytic oxygen reduction to produce hydrogen peroxide (H 2 O 2 ) is a promising route to providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts for efficient overall H 2 O 2 production in pure water has impeded ongoing research and practical thrusts. Here we present a cyanide‐based covalent organic framework (TBTN‐COFs) combining 2,4,6‐trimethylbenzene‐1,3,5‐tricarbonitrile (TBTN) and benzotrithiophene‐2,5,8‐tricarbaldehyde (BTT) building blocks with water‐affinity and charge‐separation. The ultrafast intramolecular electron transfer (<500 fs) and prolonged excited state lifetime (748 ps) can be realized by TBTN‐COF, resulting in a hole accumulated BTT and electron‐rich TBTN building block. Under one sun, the 11013 μmol h −1 g −1 yield rate of H 2 O 2 can be achieved without any sacrificial agent, outperforming most previous reports. Furthermore, the DFT calculation and in situ DRIFTS spectrums suggesting a Yeager‐type absorption of *O 2 ⋅ − intermediate in the cyanide active site, which prohibits the formation of…

Abstract The carbonate electrolyte chemistry is a primary determinant for the development of high‐voltage lithium metal batteries (LMBs). Unfortunately, their implementation is greatly plagued by sluggish electrode interfacial dynamics and insufficient electrolyte thermodynamic stability. Herein, lithium trifluoroacetate‐lithium nitrate (LiTFA−LiNO 3 ) dual‐salt additive‐reinforced carbonate electrolyte (LTFAN) is proposed for stabilizing high‐voltage LMBs. We reveal that 1) the in situ generated inorganic‐rich electrode‐electrolyte interphase (EEI) enables rapid interfacial dynamics, 2) TFA − preferentially interacts with moisture over PF 6 − to strengthen the moisture tolerance of designed electrolyte, and 3) NO 3 − is found to be noticeably enriched at the cathode interface on charging, thus constructing Li + ‐enriched, solvent‐coordinated, thermodynamically favorable electric double layer (EDL). The superior moisture tolerance of LTFAN and the thermodynamically stable EDL constructed at cathode interface play a decisive role in upgrading the compatibility of carbonate…

Abstract Carbon‐based single‐atom catalysts (SACs) have attracted tremendous interest in heterogeneous catalysis. However, the common electric heating techniques to produce carbon‐based SACs usually suffer from prolonged heating time and tedious operations. Herein, a general and facile microwave‐assisted rapid pyrolysis method is developed to afford carbon‐based SACs within 3 min without inert gas protection. The obtained carbon‐based SACs present high porosity and comparable carbonization degree to those obtained by electric heating techniques. Specifically, the single‐atom Ni implanted N‐doped carbon (Ni 1 −N−C) derived from a Ni‐doped metal–organic framework (Ni‐ZIF‐8) exhibits remarkable CO Faradaic efficiency (96 %) with a substantial CO partial current density (j CO ) up to 1.06 A/cm 2 in CO 2 electroreduction, far superior to the counterpart obtained by traditional pyrolysis with electric heating. Mechanism investigations reveal that the resulting Ni 1 −N−C presents abundant defective sites and mesoporous structure, greatly facilitating CO 2 adsorption and mass transfer. This…

Abstract Electrocatalytic reduction of nitrate (NO 3 RR) to synthesize ammonia (NH 3 ) provides a competitive manner for carbon neutrality and decentralized NH 3 synthesis. Atomically precise nanoclusters, as an advantageous platform for investigating the NO 3 RR mechanisms and actual active sites, remain largely underexplored due to the poor stability. Herein, we report a (NH 4 ) 9 [Ag 9 (mba) 9 ] nanoclusters (Ag 9 NCs) loaded on Ti 3 C 2 MXene (Ag 9 /MXene) for highly efficient NO 3 RR performance towards ambient NH 3 synthesis with improved stability in neutral medium. The composite structure of MXene and Ag 9 NCs enables a tandem catalysis process for nitrate reduction, significantly increasing the selectivity and FE of NH 3 . Besides, compared with individual Ag 9 NCs, Ag 9 /MXene has better stability with the current density performed no decay after 108 hours of reaction. This work provides a strategy for improving the catalytic activity and stability of atomically precise metal NCs, expanding the mechanism research and application of metal NCs.

Abstract Anion exchange membranes (AEMs) are core components in anion exchange membrane water electrolyzers (AEM‐WEs). However, the stability of functional quaternary ammonium cations, especially under high temperatures and harsh alkaline conditions, seriously affects their performance and durability. Herein, we synthesized a 1‐methyl‐3,3‐diphenylquinuclidinium molecular building unit. Density functional theory (DFT) calculations and accelerated aging analysis indicated that the quinine ring structure was exceedingly stable, and the S N 2 degradation mechanism dominated. Through acid‐catalyzed Friedel–Crafts polymerization, a series of branched poly(aryl‐quinuclidinium) (PAQ‐x) AEMs with controllable molecular weight and adjustable ion exchange capacity (IEC) were prepared. The stable quinine structure in PAQ‐x was verified and retained in the ex situ alkaline stability. Furthermore, the branched polymer structure reduces the swelling rate and water uptake to achieve a tradeoff between dimensional stability and ionic conductivity, significantly improving the membrane's overall…

Abstract Covalent organic frameworks (COFs) are promising photocatalysts for hydrogen peroxide (H 2 O 2 ) synthesis. However, the nature of organic polymers makes the balance between high activity and stability challenging. We demonstrate that the linkage position matters in the design of robust COF photocatalysts with durable high activity without sacrificial reagents. COFs with ortho‐ and para‐linkages ( o ‐COFs and p ‐COFs) were constructed by 1,3,5‐triformylphloroglucinol with benzene‐, pyridine‐, pyrazine‐orthodiamines and paradiamines. The pyrzaine‐containing o ‐COFs with two pyridinic nitrogen atoms exhibited a H 2 O 2 production rate of 4396 μmol g −1 h −1 together with long‐time continuous H 2 O 2 photosynthesis performance in pure water (48 h), superior to the corresponding p ‐COFs. A four‐step reaction mechanism is proposed by density function calculations. Moreover, the active sites and origin of stability enhancement for o ‐COFs are clarified. This work provides a simple and effective molecular design strategy in the design of robust COF photocatalysts for artificial H…

Abstract The intrinsic helical π‐conjugated skeleton makes helicenes highly promising for circularly polarized electroluminescence (CPEL). Generally, carbon helicenes undergo low external quantum efficiency (EQE), while the incorporation of a multi‐resonance thermally activated delayed fluorescence (MR‐TADF) BN structure has led to an improvement. However, the reported B,N‐embedded helicenes all show low electroluminescence dissymmetry factors ( g EL ), typically around 1×10 −3 . Therefore, the development of B,N‐embedded helicenes with both a high EQE and g EL value is crucial for achieving highly efficient CPEL. Herein, a facile approach to synthesize B,N‐embedded hetero[9]helicenes, BN[9]H , is presented. BN[9]H shows a bright photoluminescence with a maximum at 578 nm with a high luminescence dissymmetry factor (| g lum |) up to 5.8×10 −3 , attributed to its inherited MR‐TADF property and intrinsic helical skeleton. Furthermore, circularly polarized OLED devices incorporating BN[9]H as an emitter show a maximum EQE of 35.5 %, a small full width at half‐maximum of 48 nm, and,…

Abstract For heterojunction system, the lack of stable interfacial driving force and definite charge transfer channel makes the charge separation and transfer efficiency unsatisfactory. The photoreaction mechanism occurring at the interface also receives less attention. Herein, a 2D/2D Z‐scheme junction BiOBr@NiFe‐LDH with large‐area contact featured by short interface hydrogen bonds and strong interfacial electric field (IEF) is synthesized, and in situ photoinduced metallic species assisting charge transfer mechanism is demonstrated. The hydrogen bonds between O atoms from BiOBr and H atoms from NiFe‐LDH induce a significant interfacial charge redistribution, establishing a robust IEF. Notably, during photocatalytic reaction, Bi 0 and Ni 0 are in situ performed in heterojunction, which separately act as electron transport mediator and electron trap to further accelerate charge transfer efficiency up to 71.2 %. Theoretical calculations further demonstrate that the existence of Bi 0 strengthens the IEF. Therefore, high‐speed spatial charge separation is realized in Bi 0 /BiOBr@Ni 0…

Abstract Urea electrosynthesis from carbon dioxide (CO 2 ) and nitrate (NO 3 − ) is an alternative approach to traditional energy‐intensive urea synthesis technology. Herein, we report a CuAu single‐atom alloy (SAA) with electronic metal support interaction (EMSI), achieving a high urea yield rate of 813.6 μg h −1 mg cat −1 at −0.94 V versus reversible hydrogen electrode (vs. RHE) and a Faradaic efficiency (FE) of 45.2 % at −0.74 V vs. RHE. In situ experiments and theoretical calculations demonstrated that single‐atom Cu sites modulate the adsorption behavior of intermediate species. Bimetallic sites synergistically accelerate C−N bond formation through spontaneous coupling of *CO and *NO to form *ONCO as key intermediates. More importantly, electronic metal support interaction between CuAu SAA and CeO 2 carrier further modulates electron structure and interfacial microenvironment, endowing electrocatalysts with superior activity and durability. This work constructs SAA electrocatalysts with EMSI effect to tailor C−N coupling at the atomic level, which can provide guidance for the…

Abstract Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light‐induced instability and the difficulty of utilizing the photogenerated carriers for photocatalysis pose significant challenges. Here, MAg 24 (M=Ag, Pd, Pt, and Au) NCs doped with diverse single heteroatoms have been encapsulated in a metal–organic framework (MOF), UiO‐66‐NH 2 , affording MAg 24 @UiO‐66‐NH 2 . Strikingly, compared with Ag 25 @UiO‐66‐NH 2 , the MAg 24 @UiO‐66‐NH 2 doped with heteroatom exhibits much enhanced activity in photocatalytic hydrogen production, among which AuAg 24 @UiO‐66‐NH 2 presents the best activity up to 3.6 mmol g −1 h −1 , far superior to all other counterparts. Moreover, they display excellent photocatalytic recyclability and stability. X‐ray photoelectron spectroscopy and ultrafast transient absorption spectroscopy demonstrate that MAg 24 NCs encapsulated into the MOF create a favorable charge transfer pathway, similar to a Z‐scheme heterojunction, when exposed to visible light. This…

Abstract Energy storage in supercapacitors and hybrid zinc ion capacitors (ZIC) using porous carbon materials offers a promising alternative method for clean energy solutions. The unique combination of hierarchical porous structure and nitrogen doping in these materials has demonstrated significant capacity for energy storage. Nevertheless, the full potential of these materials, particularly the relationship between pore structure configuration and performance, remains underexplored. Herein, a confined pyrolysis strategy based on the polymerization characteristics of polydopamine (PDA) was developed to construction of hollow carbon spheres with microporous/mesoporous dual shell structure. The depth of micropores and cavity can be controlled by adjusting the duration of heat treatment and hydrothermal treatment, in accordance with the decomposition and polymerization characteristics of PDA. Due to the elasticity of this structure, the relationship between the micro/mesoporous depth of the prepared carbon spheres and the energy storage performance in supercapacitors and ZIC is…

Abstract Electrocatalytic reduction of nitrate to ammonia provides a green alternate to the Haber–Bosch method, yet it suffers from sluggish kinetics and a low yield rate. The nitrate reduction follows a tandem reaction of nitrate reduction to nitrite and subsequent nitrite hydrogenation to generate ammonia, and the ammonia Faraday efficiency (FE) is limited by the competitive hydrogen evolution reaction. Herein, we design a heterostructure catalyst to remedy the above issues, which consists of Ni nanosphere core and Ni(OH)2 nanosheet shell (Ni/Ni(OH)2). In situ Raman spectroscopy reveals Ni and Ni(OH)2 are interconvertible according to the applied potential, facilitating the cascade nitrate reduction synergistically. Consequently, it attains superior electrocatalytic nitrate reduction performance with an ammonia FE of 98.50 % and a current density of 0.934 A cm−2 at −0.476 V versus reversible hydrogen electrode, and exhibits an average ammonia yield rate of 84.74 mg h−1 cm−2 during the 102‐hour stability test, which is highly superior to the reported catalysts tested under similar…

Abstract Electrochemical C−N coupling reaction based on carbon dioxide and nitrate have been emerged as a new “green synthetic strategy” for the synthesis of urea, but the catalytic efficiency is seriously restricted by the inherent scaling relations of adsorption energies of the active sites, the improvement of catalytic activity is frequently accompanied by the decrease in selectivity. Herein, a doping engineering strategy was proposed to break the scaling relationship of intermediate binding and minimize the kinetic barrier of C−N coupling. A thus designed SrCo 0.39 Ru 0.61 O 3−δ catalyst achieves a urea yield rate of 1522 μg h −1 mg cat. −1 and faradic efficiency of 34.1 % at −0.7 V versus reversible hydrogen electrode. A series of characterizations revealed that Co doping not only induces lattice distortion but also creates rich oxygen vacancies (O V ) in the SrRuO 3 . The oxygen vacancies weaken the adsorption of *CO and *NH 2 intermediates on the Co and Ru sites respectively, and the strain effects over the Co−Ru dual sites promoting the occurrence of C−N coupling of the two…

Abstract Constructing stable and efficient photocatalysts for H 2 O 2 production is of great importance and is challenging. In this study, the synthesis of three photoactive cyclooctatetrathiophene (COTh)‐based porous aromatic frameworks (COTh‐PAFs) in an alternating donor‐acceptor (D−A) fashion is presented. In combination with a triazine‐derived electron acceptor, PAF‐363 exhibits high efficiency for the photosynthesis of H 2 O 2 with production rates of 11733 μmol g −1 h −1 (with sacrificial agent) and 3930 μmol g −1 h −1 (without sacrificial agent) from water and oxygen under visible light irradiation. Experimental results and theoretical calculations reveal that the charge transfer positions and the O 2 adsorption sites in PAF‐363 are both concentrated on COTh fragments, which facilitate the H 2 O 2 production through the oxygen reduction reaction (ORR) pathway. This work highlights that the rational design of COTh‐PAFs with consideration of D−A direction, charge transfer positions, and O 2 adsorption sites provides a feasible access to efficient H 2 O 2 production…

Abstract Direct electrochemical seawater splitting is a renewable, scalable, and potentially economic approach for green hydrogen production in environments where ultra‐pure water is not readily available. However, issues related to low durability caused by complex ions in seawater pose great challenges for its industrialization. In this review, a mechanistic analysis of durability issues of electrolytic seawater splitting is discussed. We critically analyze the development of seawater electrolysis and identify the durability challenges at both the anode and cathode. Particular emphasis is given to elucidating rational strategies for designing electrocatalysts/electrodes/interfaces with long lifetimes in realistic seawater including inducing passivating anion layers, preferential OH − adsorption, employing anti‐corrosion materials, fabricating protective layers, immobilizing Cl − on the surface of electrocatalysts, tailoring Cl − adsorption sites, inhibition of OH − binding to Mg 2+ and Ca 2+ , inhibition of Mg and Ca hydroxide precipitation adherence, and co‐electrosynthesis of…

Abstract RuO 2 is one of the benchmark electrocatalysts used as the anode material in proton exchange membrane water electrolyser. However, its long‐term stability is compromised due to the participation of lattice oxygen and metal dissolution during oxygen evolution reaction (OER). In this work, weakened covalency of Ru−O bond was tailored by introducing tensile strain to RuO 6 octahedrons in a binary Ru−Sn oxide matrix, prohibiting the participation of lattice oxygen and the dissolution of Ru, thereby significantly improving the long‐term stability. Moreover, the tensile strain also optimized the adsorption energy of intermediates and boosted the OER activity. Remarkably, the RuSnO x electrocatalyst exhibited excellent OER activity in 0.1 M HClO 4 and required merely 184 mV overpotential at a current density of 10 mA cm −2 . Moreover, it delivered a current density of 10 mA cm −2 for at least 150 h with negligible potential increase. This work exemplifies an effective strategy for engineering Ru‐based catalysts with extraordinary performance toward water splitting.

Abstract Singlet oxygen ( 1 O 2 ) is an exceptional reactive oxygen species in advanced oxidation processes for environmental remediation. Despite single‐atom catalysts (SACs) representing the promising candidate for the selective generation of 1 O 2 from peroxymonosulfate (PMS), the necessity to meticulously regulate the coordination environment of metal centers poses a significant challenge in the precisely‐controlled synthetic method. Another dilemma to SACs is their high surface free energy, which results in an inherent tendency for the surface migration and aggregation of metal atoms. We here for the first time reported that Ru nanoparticles (NPs) synthesized by the facile pyrolysis method behave as robust Fenton‐like catalysts, outperforming Ru SACs, towards efficient activation of PMS to produce 1 O 2 with nearly 100 % selectivity, remarkably improving the degradation efficiency for target pollutants. Density functional theory calculations have unveiled that the boosted PMS activation can be attributed to two aspects: (i) enhanced adsorption of PMS molecules onto Ru NPs, and…

Abstract The high entropy alloy (HEA) possesses distinctive thermal stability and electronic characteristics, which exhibits substantial potential for diverse applications in electrocatalytic reactions. The nanosize of HEA also has a significant impact on its catalytic performance. However, accurately controlling nanosize and synthesizing small HEA nanomaterials remains a challenge, especially for the ultrasmall HEA nanoparticles. Herein, we firstly calculate and illustrate the impact of size on the electronic structure of HEA as well as the adsorption energies of crucial intermediates involved in typical electrocatalytic processes, such as the hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), CO 2 electroreduction (CO 2 RR) and NO 3 − electroreduction (NO 3 RR). Under the guidance of theoretical calculations, we synthesize a range of ultrasmall PtRuPdCoNi HEA nanoparticles with adjustable sizes (1.7, 2.3, 3.0, and 3.9 nm) using a one‐step spatially confined approach, without any further treatment. Experimentally, the smaller size of HEAs is more favorable for the…

Abstract Photo‐driven cross‐coupling of o ‐arylenediamines and alcohols has emerged as an alternative for the synthesis of bio‐active benzimidazoles. However, tackling the key problem related to efficient adsorption and activation of both coupling partners over photocatalysts towards activity enhancement remains a challenge. Here, we demonstrate an efficient interface synergy strategy by coupling exposed oxygen vacancies (V O ) and Pd Lewis acid sites for benzimidazole and hydrogen (H 2 ) coproduction over Pd‐loaded TiO 2 nanospheres with the highest photoredox activity compared to previous works so far. The results show that the introduction of V O optimizes the energy band structure and supplies coordinatively unsaturated sites for adsorbing and activating ethanol molecules, affording acetaldehyde active intermediates. Pd acts as a Lewis acid site, enhancing the adsorption of alkaline amine molecules via Lewis acid‐base pair interactions and driving the condensation process. Furthermore, V O and Pd synergistically promote interfacial charge transfer and separation. This work…

Abstract Zn deposition with a surface‐preferred (002) crystal plane has attracted extensive attention due to its inhibited dendrite growth and side reactions. However, the nucleation and growth of the Zn(002) crystal plane are closely related to the interfacial properties. Herein, oriented growth of Zn(002) crystal plane is realized on Ag‐modified surface that is directly visualized by in situ atomic force microscopy. A solid solution HCP‐Zn (~1.10 at. % solubility of Ag, 30 °C) is formed on the Ag coated Zn foil (Zn@Ag) and possesses the same crystal structure as Zn to reduce its nucleation barrier caused by their lattice mismatch. It merits oriented Zn deposition and corrosion‐resistant surface, and presents long cycling stability in symmetric cells and full cells coupled with V 2 O 5 cathode. This work provides insights into interfacial regulation of Zn anodes for high‐performance aqueous zinc metal batteries.

Abstract Traditional H 2 O 2 cleavage mediated by macroscopic electron transfer (MET) not only has low utilization of H 2 O 2 , but also sacrifices the stability of catalysts. We present a non‐redox hydroxyl‐enriched spinel (CuFe 2 O 4 ) catalyst with dual Lewis acid sites to realize the homolytic cleavage of H 2 O 2 . The results of systematic experiments, in situ characterizations, and theoretical calculations confirm that tetrahedral Cu sites with optimal Lewis acidity and strong electron delocalization can synergistically elongate the O−O bonds (1.47 Å → 1.87 Å) in collaboration with adjacent bridging hydroxyl (another Lewis acid site). As a result, the free energy of H 2 O 2 homolytic cleavage is decreased (1.28 eV → 0.98 eV). H 2 O 2 can be efficiently split into ⋅OH induced by hydroxyl‐enriched CuFe 2 O 4 without MET, which greatly improves the catalyst stability and the H 2 O 2 utilization (65.2 %, nearly 2 times than traditional catalysts). The system assembled with hydroxyl‐enriched CuFe 2 O 4 and H 2 O 2 affords exceptional performance for organic pollutant elimination.…

Abstract Electrooxidation of biomass‐derived glycerol which is regarded as a main byproduct of industrial biodiesel production, is an innovative strategy to produce value‐added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high‐efficiency electrooxidation of glycerol into formate via a Cu doped NiCo alloy catalyst supported on nickel foam (Cu−NiCo/NF) in a coupled system paired with nitrate reduction. The designed Cu−NiCo/NF delivers only 1.23 V vs . RHE at 10 mA cm −2 , and a record Faraday efficiency of formate of 93.8 %. The superior performance is ascribed to the rapid generation of Ni III −OOH and Co III −OOH species and favorable coupling of surface *O with reactive intermediates. Using Cu−NiCo/NF as a bifunctional catalyst, the coupled system synchronously produces NH 3 and formate, showing 290 mV lower than the coupling of hydrogen evolution reaction, together with excellent long‐term stability for up to 144 h. This work lays out new guidelines and reliable strategies from catalyst design to…

Electrochemiluminescence (ECL) is rapidly evolving from an analytical method into an optical microscopy. The orthogonality of the electrochemical trigger and the optical readout distinguishes it from classic microscopy and electrochemical techniques, owing to its near-zero background, remarkable sensitivity, and absence of photobleaching and phototoxicity. In this minireview, we summarize the recent advances in ECL imaging technology, emphasizing original configurations which enable the imaging of biological entities and the improvement of the analytical properties by increasing the complexity and multiplexing of bioassays. Additionally, mapping the (electro)chemical reactivity in space provides valuable information on nanomaterials and facilitates deciphering ECL mechanisms for improving their performances in diagnostics and (electro)catalysis. Finally, we highlight the recent achievements in imaging at the ultimate limits of single molecules, single photons or single chemical reactions, and the current challenges to translate the ECL imaging advances to other fields such as…

Abstract Aqueous zinc‐metal batteries (AZMBs) usually suffered from poor reversibility and limited lifespan because of serious water induced side‐reactions, hydrogen evolution reactions (HER) and rampant zinc (Zn) dendrite growth. Reducing the content of water molecules within Zn‐ion solvation sheaths can effectively suppress those inherent defects of AZMBs. In this work, we originally discovered that the two carbonyl groups of N‐Acetyl‐ϵ‐caprolactam (N‐ac) chelating ligand can serve as dual solvation sites to coordinate with Zn 2+ , thereby minimizing water molecules within Zn‐ion solvation sheaths, and greatly inhibit water‐induced side‐reactions and HER. Moreover, the N‐ac chelating additive can form a unique physical barrier interface on Zn surface, preventing the harmful contacting with water. In addition, the preferential adsorption of N‐ac on Zn (002) facets can promote highly reversible and dendrite‐free Zn 2+ deposition. As a result, Zn//Cu half‐cell within N‐ac added electrolyte delivered ultra‐high 99.89 % Coulombic efficiency during 8000 cycles. Zn//Zn symmetric cells…

Abstract Although great efforts on the delicate construction of a built‐in electric field (BIEF) to modify the electronic properties of active sites have been conducted, the substantial impact of BIEF coupled with electrode potential on the electrochemical reactions has not been clearly investigated. Herein, we designed an alkaline hydrogen evolution reaction (HER) catalyst composed of heterogeneous Ru−CoP urchin arrays on carbon cloth (Ru−CoP/CC) with a strong BIEF with the guidance of density functional theory (DFT) calculations. Impressively, despite its unsatisfactory activity at 10 mA cm −2 (overpotential of 44 mV), Ru−CoP/CC exhibited better activity (357 mV) than the benchmark Pt/C catalyst (505 mV) at 1 A cm −2 . Experimental and theoretical studies revealed that strong hydrogen adsorption on the interfacial Ru atoms created a high energy barrier for hydrogen desorption and spillover, resulting in unsatisfactory activity at low current densities. However, as the electrode potential became more negative (i.e., the current density increased), the barrier for hydrogen spillover…

(0.76 Å), it was generally believed that the Sb anode would experience even worse capacity degradation in SIBs due to more substantial volumetric variations during cycling when compared to LIBs. However, the Sb anode in SIBs unexpectedly exhibited both better electrochemical and structural stability than in LIBs, and the mechanistic reasons that underlie this performance discrepancy remain undiscovered. Here, using substantial in situ transmission electron microscopy, X-ray diffraction, and Raman techniques complemented by theoretical simulations, we explicitly reveal that compared to the lithiation/delithiation process, sodiation/desodiation process of Sb anode displays a previously unexplored two-stage alloying/dealloying mechanism with polycrystalline and amorphous phases as the intermediates featuring improved resilience to mechanical damage, contributing to superior cycling stability in SIBs. Additionally, the better mechanical properties and weaker atomic interaction of Na-Sb alloys than Li-Sb alloys favor enabling mitigated mechanical stress, accounting for enhanced…

Abstract Electrocatalytic nitrate (NO 3 − ) reduction to ammonia (NRA) offers a promising pathway for ammonia synthesis. The interfacial electronic interactions (IEIs) can regulate the physicochemical capabilities of catalysts in electrochemical applications, while the impact of IEIs on electrocatalytic NRA remains largely unexplored in current literature. In this study, the high‐efficiency electrode Ag‐modified Co 3 O 4 (Ag 1.5 Co/CC) is prepared for NRA in neutral media, exhibiting an impressive nitrate conversion rate of 96.86 %, ammonia Faradaic efficiency of 96.11 %, and ammonia selectivity of ~100 %. Notably, the intrinsic activity of Ag 1.5 Co/CC is ~81 times that of Ag nanoparticles (Ag/CC). Multiple characterizations and theoretical computations confirm the presence of IEIs between Ag and Co 3 O 4 , which stabilize the CoO 6 octahedrons within Co 3 O 4 and significantly promote the adsorption of reactants (NO 3 − ) as well as intermediates (NO 2 − and NO), while suppressing the Heyrovsky step, thereby improving nitrate electroreduction efficiency. Furthermore, our findings…

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to achieve remediation of nitrate‐polluted wastewater and sustainable production of ammonia. However, it is still restricted by the low activity, selectivity and Faraday efficiency for ammonia synthesis. Herein, we propose an effective strategy to modulate the electrolyte microenvironment in electrical double layer (EDL) by mediating alkali metal cations in the electrolyte to enhance the NO 3 RR performance. Taking bulk Cu as a model catalyst, the experimental study reveals that the NO 3 − ‐to‐NH 3 performance in different electrolytes follows the trend Li + + + + . Theoretical studies illustrate that the proton transport rate in NO 3 RR and the activity of the rate‐determining step (NO 3 − to NO 2 − ) increase in the order Li + + + + . The cation effects are also general for two typical nanostructured catalysts including copper/cuprous oxide and nickel phosphides, achieving near‐100 % Faradaic efficiency and over 99 % conversion of NO 3 − to NH 3 . Furthermore, we demonstrate that NO 3 − can be…

Abstract The electrochemical nitrate reduction reaction (NO3RR) is able to convert nitrate (NO3−) into reusable ammonia (NH3), offering a green treatment and resource utilization strategy of nitrate wastewater and ammonia synthesis. The conversion of NO3− to NH3 undergoes water dissociation to generate active hydrogen atoms and nitrogen‐containing intermediates hydrogenation tandemly. The two relay processes compete for the same active sites, especially under pH‐neutral condition, resulting in the suboptimal efficiency and selectivity in the electrosynthesis of NH3 from NO3−. Herein, we constructed a Cu1‐Fe dual‐site catalyst by anchoring Cu single atoms on amorphous iron oxide shell of nanoscale zero‐valent iron (nZVI) for the electrochemical NO3RR, achieving an impressive NO3− removal efficiency of 94.8 % and NH3 selectivity of 99.2 % under neutral pH and nitrate concentration of 50 mg L−1 NO3−−N conditions, greatly surpassing the performance of nZVI counterpart. This superior performance can be attributed to the synergistic effect of enhanced NO3− adsorption on Fe sites and…

Abstract Prussian blue analogues (PBAs) have been widely studied in aqueous zinc‐ion batteries (AZIBs) due to the characteristics of large specific surface area, open aperture, and straightforward synthesis. In this work, vanadium‐based PBA nanocubes were firstly prepared using a mild in situ conversion strategy at room temperature without the protection of noble gas. Benefiting from the multiple‐redox active sites of V 3+ /V 4+ , V 4+ /V 5+ , and Fe 2+ /Fe 3+ , the cathode exhibited an excellent discharge specific capacity of 200 mAh g −1 in AZIBs, which is much higher than those of other metal‐based PBAs nanocubes. To further improve the long‐term cycling stability of the V‐PBA cathode, a high concentration water‐in‐salt electrolyte (4.5 M ZnSO 4 +3 M Zn(OTf) 2 ), and a water‐based eutectic electrolyte (5.55 M glucose+3 M Zn(OTf) 2 ) were designed to successfully inhibit the dissolution of vanadium and improve the deposition of Zn 2+ onto the zinc anode. More importantly, the assembled AZIBs maintained 55 % of their highest discharge specific capacity even after 10000 cycles at 10…

Abstract Sodium‐ion batteries (SIBs) are recognized as promising energy storage devices. However, they suffer from rapid capacity decay at ultra‐low temperatures due to high Na + desolvation energy barrier and unstable solid electrolyte interphase (SEI). Herein, a weakly solvating electrolyte (WSE) with decreased ion‐dipole interactions is designed for stable sodium storage in hard carbon (HC) anode at ultra‐low temperatures. 2‐methyltetrahydrofuran with low solvating power is incorporated into tetrahydrofuran to regulate the interactions between Na + and solvents. The reduced Na + ‐dipole interactions facilitate more anionic coordination in the first solvation sheath, which consistently maintains anion‐enhanced solvation structures from room to low temperatures to promote inorganic‐rich SEI formation. These enable WSE with a low freezing point of −83.3 °C and faster Na + desolvation kinetics. The HC anode thus affords reversible capacities of 243.2 and 205.4 mAh g −1 at 50 mA g −1 at −40 and −60 °C, respectively, and the full cell of HC||Na 3 V 2 (PO 4 ) 3 yields an extended…

The ion extraction and electro/photo catalysis are promising methods to address environmental and energy issues. Covalent organic frameworks (COFs) are a class of promising template to construct absorbents and catalysts because of their stable frameworks, high surface areas, controllable pore environments, and well-defined catalytic sites. Among them, ionic COFs as unique class of crystalline porous materials, with charges in the frameworks or along the pore walls, have shown different properties and resulting performance in these applications with those from charge-neutral COFs. In this review, current research progress based on the ionic COFs for ion extraction and energy conversion, including cationic/anionic materials and electro/photo catalysis is reviewed in terms of the synthesis strategy, modification methods, mechanisms of adsorption and catalysis, as well as applications. Finally, we demonstrated the current challenges and future development of ionic COFs in design strategies and applications.

Abstract Endowing perovskite quantum dots (PQDs) with circularly polarized luminescence (CPL) offers great promise for innovative chiroptical applications, but the existing strategies are inefficient in acquiring stimuli‐responsive flexible chiral perovskite films with large, tunable dissymmetry factor ( g lum ) and long‐term stability. Here, we report a strategy for the design and synthesis of luminescent cholesteric liquid crystal elastomer (Lumin‐CLCE) films with mechanically tunable CPL, which is enabled by liquid crystal‐templated chiral self‐assembly and in situ covalent cross‐linking of judiciously designed photopolymerizable CsPbX 3 (X=Cl, Br, I) PQD nanomonomers into the elastic polymer networks. The resulting Lumin‐CLCE films showcase circularly polarized structural color in natural light and noticeable CPL with a maximum g lum value of up to 1.5 under UV light. The manipulation of CPL intensity and rotation direction is achieved by controlling the self‐assembled helicoidal nanostructure and the handedness of soft helices. A significant breakthrough lies in the achievement…

Abstract Ammonia borane (AB) with 19.6 wt % H 2 content is widely considered a safe and efficient medium for H 2 storage and release. Co‐based nanocatalysts present strong contenders for replacing precious metal‐based catalysts in AB hydrolysis due to their high activity and cost‐effectiveness. However, precisely adjusting the active centers and surface properties of Co‐based nanomaterials to enhance their activity, as well as suppressing the migration and loss of metal atoms to improve their stability, presents many challenges. In this study, mesoporous‐silica‐confined bimetallic Co−Cu nanoparticles embedded in nitrogen‐doped carbon (Co x Cu 1−x @NC@mSiO 2 ) were synthesized using a facile mSiO 2 ‐confined thermal pyrolysis strategy. The obtained product, an optimized Co 0.8 Cu 0.2 @NC@mSiO 2 catalyst, exhibits enhanced performance with a turnover frequency of 240.9 mol H2 ⋅ mol metal ⋅ min −1 for AB hydrolysis at 298 K, surpassing most noble‐metal‐free catalysts. Moreover, Co 0.8 Cu 0.2 @NC@mSiO 2 demonstrates magnetic recyclability and extraordinary stability, with a negligible…

Abstract As an alternative to hydrogen peroxide (H 2 O 2 ) production by complex anthraquinone oxidation process, photosynthesis of H 2 O 2 from water and oxygen without sacrificial agents is highly demanded. Herein, a covalently connected molecular heterostructure is synthesized via sequential C−H arylation and Knoevenagel polymerization reactions for visible‐light and sacrificial‐agent‐free H 2 O 2 synthesis. The subsequent copolymerization of the electron‐deficient benzodithiophene‐4,8‐dione (BTD) and the electron‐rich biphenyl (B) and p ‐phenylenediacetonitrile (CN) not only expands the π‐conjugated domain but also increases the molecular dipole moment, which largely promotes the separation and transfer of the photoinduced charge carriers. The optimal heterostructured BTDB‐CN 0.2 manifested an impressive photocatalytic H 2 O 2 production rate of 1920 μmol g −1 h −1 , which is 2.2 and 11.6 times that of BTDB and BTDCN. As revealed by the femtosecond transient absorption (fs‐TA) and theoretical calculations, the linkage serves as a channel for the rapid transfer of photogenerated…

Abstract Herein, we propose an oxygen‐containing species coordination strategy to boost CO 2 electroreduction in the presence of O 2 . A two‐dimensional (2D) conjugated metal‐covalent organic framework (MCOF), denoted as NiPc‐Salen(Co) 2 ‐COF that is composed of the Ni‐phthalocyanine (NiPc) unit with well‐defined Ni−N 4 −O sites and the salen(Co) 2 moiety with binuclear Co−N 2 O 2 sites, is developed and synthesized for enhancing the CO 2 RR under aerobic condition. In the presence of O 2 , one of the Co sites in the NiPc‐Salen(Co) 2 ‐COF that coordinated with the intermediate of *OOH from ORR could decrease the energy barrier of the activation of CO 2 molecules and stabilize the key intermediate *COOH of the CO 2 RR over the adjacent Co center. Besides, the oxygen species axially coordinated Ni−N 4 −O sites can favor in reducing the energy barrier of the intermediate *COOH formation for the CO 2 RR. Thus, NiPc‐Salen(Co) 2 ‐COF exhibits high oxygen‐tolerant CO 2 RR performance and achieves outstanding CO Faradaic efficiency (FE CO ) of 97.2 % at −1.0 V vs. the reversible hydrogen…

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview on the most important developments in the last years with a clear focus on experimental studies and on catalysts which act via such non-transient interactions.

Abstract Polyethylene oxide (PEO)‐based solid‐state batteries hold great promise as the next‐generation batteries with high energy density and high safety. However, PEO‐based electrolytes encounter certain limitations, including inferior ionic conductivity, low Li + transference number, and poor mechanical strength. Herein, we aim to simultaneously address these issues by utilizing one‐dimensional zwitterionic cellulose nanofiber (ZCNF) as fillers for PEO‐based electrolytes using a simple aqueous solution casting method. Multiple characterizations and theoretical calculations demonstrate that the unique zwitterionic structure imparts ZCNF with various functions, such as disrupting PEO crystallization, dissociating lithium salts, anchoring anions through cationic groups, accelerating Li + migration by anionic groups, as well as its inherent reinforcement effect. As a result, the prepared PL‐ZCNF electrolyte exhibits remarkable ionic conductivity (5.37×10 −4 S cm −1 ) and Li + transference number (0.62) at 60 °C without sacrificing mechanical strength (9.2 MPa), together with high…

Abstract The electrochemical reduction of CO 2 to high‐value carbon‐based chemicals provides a sustainable approach to achieving an artificial carbon cycle. In the decade, metal–organic frameworks (MOFs), a kind of porous crystalline porous materials featuring well‐defined structures, large surface area, high porosity, diverse components, easy tailorability, and controllable morphology, have attracted considerable research attention, serving as electrocatalysts to drive CO 2 reduction. In this review, the reaction mechanisms of electrochemical CO 2 reduction and the structure/component advantages of MOFs meeting the requirements of electrocatalysts for CO 2 reduction are analyzed. After that, the representative progress for the precise fabrication of MOF‐based electrocatalysts for CO 2 reduction, focusing on catalytic site design and microenvironment modulation, are systemically summarized. Furthermore, the emerging applications and promising research for more practical scenarios related to electrochemical CO 2 conversion are specifically proposed. Finally, the remaining challenges…

Abstract Regulating the electric double layer (EDL) structure of the zinc metal anode by using electrolyte additives is an efficient way to suppress interface side reactions and facilitate uniform zinc deposition. Nevertheless, there are no reports investigating the proactive design of EDL‐regulating additives before the start of experiments. Herein, a functional group assembly strategy is proposed to design electrolyte additives for modulating the EDL, thereby realizing a long‐lasting zinc metal anode. Specifically, by screening ten common functional groups, N, N‐dimethyl‐1H‐imidazole‐1‐sulfonamide (IS) is designed by assembling an imidazole group, characterized by its high adsorption capability on the zinc anode, and a sulfone group, which exhibits strong binding with Zn 2+ ions. Benefiting from the adsorption functionalization of the imidazole group, the IS molecules occupy the position of H 2 O in the inner Helmholtz layer of the EDL, forming a molecular protective layer to inhibit H 2 O‐induced side reactions. Meanwhile, the sulfone group in IS, acting as a binding site to Zn…

Abstract Electrocatalytic nitrate reduction to ammonia is a promising approach in term of pollutant appreciation. Cu‐based catalysts performs a leading‐edge advantage for nitrate reduction due to its favorable adsorption with *NO 3 . However, the formation of active hydrogen (*H) on Cu surface is difficult and insufficient, leading to the significant generation of by‐product NO 2 − . Herein, sulphur doped Cu (Cu−S) is prepared via an electrochemical conversion strategy and used for nitrate electroreduction. The high Faradaic efficiency (FE) of ammonia (~98.3 %) and an extremely low FE of nitrite (~1.4 %) are achieved on Cu−S, obviously superior to its counterpart of Cu (FE NH3 : 70.4 %, FE NO2 − : 18.8 %). Electrochemical in situ characterizations and theoretical calculations indicate that a small amount of S doping on Cu surface can promote the kinetics of H 2 O dissociation to active hydrogen. The optimized hydrogen affinity validly decreases the hydrogenation kinetic energy barrier of *NO 2 , leading to an enhanced NH 3 selectivity.

Abstract Although Ru‐based materials are among the outstanding catalysts for the oxygen evolution reaction (OER), the instability issue still haunts them and impedes the widespread application. The instability of Ru‐based OER catalysts is generally ascribed to the formation of soluble species through the over‐oxidation of Ru and structural decomposition caused by involvement of lattice oxygen. Herein, an effective strategy of selectively activating the lattice oxygen around Ru site is proposed to improve the OER activity and stability. Our synthesized spinel‐type electrocatalyst of Ru and Zn co‐doped Co3O4 showed an ultralow overpotential of 172 mV at 10 mA cm−2 and a long‐term stability reaching to 100 hours at 10 mA cm−2 for alkaline OER. The experimental results and theoretical simulations demonstrated that the lattice oxygen site jointly connected with the octahedral Ru and tetrahedral Zn atoms became more active than other oxygen sites near Ru atom, which further lowered the reaction energy barriers and avoided generating excessive oxygen vacancies to enhance the structural…

Abstract The in‐depth understanding of the composition‐property‐performance relationship of solid electrolyte interphase (SEI) is the basis of developing a reliable SEI to stablize the Zn anode‐electrolyte interface, but it remains unclear in rechargeable aqueous zinc ion batteries. Herein, a well‐designed electrolyte based on 2 M Zn(CF3SO3)2‐0.2 M acrylamide‐0.2 M ZnSO4 is proposed. A robust polymer (polyacrylamide)‐inorganic (Zn4SO4(OH)6.xH2O) hybrid SEI is in situ constructed on Zn anodes through controllable polymerization of acrylamide and coprecipitation of SO42− with Zn2+ and OH−. For the first time, the underlying SEI composition‐property‐performance relationship is systematically investigated and correlated. The results showed that the polymer‐inorganic hybrid SEI, which integrates the high modulus of the inorganic component with the high toughness of the polymer ingredient, can realize high reversibility and long‐term interfacial stability, even under ultrahigh areal current density and capacity (30 mA cm−2~30 mAh cm−2). The resultant Zn||NH4V4O10 cell also exhibits…

Tunable-lifetime room-temperature phosphorescence (RTP) materials have been widely studied due to their broad applications. However, only few reports have achieved wide-range lifetime modulation. In this work, ultra-wide range tunable-lifetime efficient dark blue RTP materials were realized by doping methyl benzoate derivatives into polyvinyl alcohol (PVA) matrix. The phosphorescence lifetimes of the doped films can be increased from 32.8 ms to 1925.8 ms. Such wide range of phosphorescence lifetime modulation is extremely rare in current reports. Moreover, the phosphorescence emission of the methyl 4-hydroxybenzoate-doped film is located in the dark blue region and the phosphorescence quantum yield reaches as high as 15.4 %, which broadens their applications in organic optoelectronic information. Further studies demonstrated that the reason for the tunable lifetime was that the magnitude of the electron-donating ability of the substituent group modulates the HOMO-LUMO and singlet-triplet energy gap of methyl benzoate derivatives, as well as the ability to non-covalent interactions…

Abstract Covalent organic frameworks (COFs) have been demonstrated as promising photocatalysts for hydrogen peroxide (H 2 O 2 ) production. However, the construction of COFs with new active sites, high photoactivity, and wide‐range light absorption for efficient H 2 O 2 production remains challenging. Herein, we present the synthesis of a novel azobenzene‐bridged 2D COF (COF‐TPT‐Azo) with excellent performance on photocatalytic H 2 O 2 production under alkaline conditions. Notably, although COF‐TPT‐Azo differs by only one atom (−N=N− vs. −C=N−) from its corresponding imine‐linked counterpart (COF‐TPT‐TPA), COF‐TPT‐Azo exhibits a significantly narrower band gap, enhanced charge transport, and prompted photoactivity. Remarkably, when employed as a metal‐free photocatalyst, COF‐TPT‐Azo achieves a high photocatalytic H 2 O 2 production rate up to 1498 μmol g −1 h −1 at pH = 11, which is 7.9 times higher than that of COF‐TPT‐TPA. Further density functional theory (DFT) calculations reveal that the −N=N− linkages are the active sites for photocatalysis. This work provides new prospects…

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have recently emerged as fascinating scaffolds for solar‐to‐chemical energy conversion because of their customizable structures and functionalities. Herein, two tris(triazolo)triazine‐based COF materials (namely COF‐JLU51 and COF‐JLU52) featuring large surface area, high crystallinity, excellent stability and photoelectric properties were designed and constructed for the first time. Remarkably, COF‐JLU51 gave an outstanding H 2 O 2 production rate of over 4200 μmol g −1 h −1 with excellent reusability in pure water and O 2 under one standard sun light, that higher than its isomorphic COF‐JLU52 and most of the reported metal‐free materials, owing to its superior generation, separation and transport of photogenerated carriers. Experimental and theoretical researches prove that the photocatalytic process undergoes a combination of indirect 2e − O 2 reduction reaction (ORR) and 4e − H 2 O oxidation reaction (WOR). Specifically, an ultrahigh yield of 7624.7 μmol g −1 h −1 with apparent quantum yield of 18.2 % for COF‐JLU52…

Abstract Developing highly active oxygen evolution reaction (OER) catalysts in acidic conditions is a pressing demand for proton‐exchange membrane water electrolysis. Manipulating proton character at the electrified interface, as the crux of all proton‐coupled electrochemical reactions, is highly desirable but elusive. Herein we present a promising protocol, which reconstructs a connected hydrogen‐bond network between the catalyst‐electrolyte interface by coupling hydrophilic units to boost acidic OER activity. Modelling on N‐doped‐carbon‐layer clothed Mn‐doped‐Co3O4 (Mn−Co3O4@CN), we unravel that the hydrogen‐bond interaction between CN units and H2O molecule not only drags the free water to enrich the surface of Mn−Co3O4 but also serves as a channel to promote the dehydrogenation process. Meanwhile, the modulated local charge of the Co sites from CN units/Mn dopant lowers the OER barrier. Therefore, Mn−Co3O4@CN surpasses RuO2 at high current density (100 mA cm−2 @ ~538 mV).

Abstract CsPbI 3 perovskite receives tremendous attention for photovoltaic applications due to its ideal band gap and good thermal stability. However, CsPbI 3 perovskite solar cells (PSCs) significantly suffer from photovoltage deficits because of serious interfacial energy losses within the PSCs, which to a large extent affects the photovoltaic performance of PSCs. Herein, a dipolar chemical bridge (DCB) is constructed between the perovskite and TiO 2 layers to lower interfacial energy losses and thus improve the charge extraction of PSCs. The results reveal that the DCB could form a beneficial interfacial dipole between the perovskite and TiO 2 layers, which could optimize the interfacial energetics of perovskite/TiO 2 layers and thus improve the energy level alignment within the PSCs. Meanwhile, the constructed DCB could also simultaneously passivate the surface defects of perovskite and TiO 2 layers, greatly lowering interfacial recombination. Consequently, the photovoltage deficit of CsPbI 3 PSCs is largely reduced, leading to a record efficiency of 21.86 % being realized.…

Abstract Photocatalytic synthesis of H 2 O 2 is an advantageous and ecologically sustainable alternative to the conventional anthraquinone process. However, achieving high conversion efficiency without sacrificial agents remains a challenge. In this study, two covalent organic frameworks (COF−O and COF−C) were prepared with identical skeletal structures but with their pore walls anchored to different alkyl chains. They were used to investigate the effect of the chemical microenvironment of pores on photocatalytic H 2 O 2 production. Experimental results reveal a change of hydrophilicity in COF−O, leading to suppressed charge recombination, diminished charge transfer resistance, and accelerated interfacial electron transfer. An apparent quantum yield as high as 10.3 % (λ=420 nm) can be achieved with H 2 O and O 2 through oxygen reduction reaction. This is among the highest ever reported for polymer photocatalysts. This study may provide a novel avenue for optimizing photocatalytic activity and selectivity in H 2 O 2 generation.

Abstract Herein, we have synthesized multifunctionalized 2‐oxa‐3‐azabicyclo[3.1.1]heptanes, which are considered potential bioisosteres for meta‐substituted arenes, through Eu(OTf)3‐catalyzed formal dipolar [4π+2σ] cycloaddition of bicyclo[1.1.0]butanes with nitrones. This methodology represents the initial instance of fabricating bicyclo[3.1.1]heptanes adorned with multiple heteroatoms. The protocol exhibits both mild reaction conditions and a good tolerance for various functional groups. Computational density functional theory calculations support that the reaction mechanism likely involves a nucleophilic addition of nitrones to bicyclo[1.1.0]butanes, succeeded by an intramolecular cyclization. The synthetic utility of this novel protocol has been demonstrated in the concise synthesis of the analogue of Rupatadine.

Abstract The aqueous zinc‐iodine battery is a promising energy storage device, but the conventional two‐electron reaction potential and energy density of the iodine cathode are far from meeting practical application requirements. Given that iodine is rich in redox reactions, activating the high‐valence iodine cathode reaction has become a promising research direction for developing high‐voltage zinc‐iodine batteries. In this work, by designing a multifunctional electrolyte additive trimethylamine hydrochloride (TAH), a stable high‐valence iodine cathode in four‐electron‐transfer I − /I 2 /I + reactions with a high theoretical specific capacity is achieved through a unique amine group, Cl bidentate coordination structure of (TA)ICl. Characterization techniques such as synchrotron radiation, in situ Raman spectra, and DFT calculations are used to verify the mechanism of the stable bidentate structure. This electrolyte additive stabilizes the zinc anode by promoting the desolvation process and shielding mechanism, enabling the zinc anode to cycle steadily at a maximum areal capacity of…

Abstract Covalent organic frameworks (COFs) have garnered attention for their potential in photocatalytic hydrogen peroxide (H 2 O 2 ) production. However, their photocatalytic efficiency is impeded by insufficient exciton dissociation and charge carrier transport. Constructing COFs with superior planarity is an effective way to enhance the π‐conjugation degree and facilitate electron‐hole separation. Nonetheless, the conventional linear linkers of COFs inevitably introduce torsional strain that disrupts coplanarity. Herein, we address this issue by introducing inherently coplanar triazine rings as linkers and fused building blocks as monomers to create covalent triazine frameworks (CTFs) with superior coplanarity. Both experimental and theoretical calculations confirm that CTFs constructed from fused building blocks significantly enhance the electron‐hole separation efficiency and improve the photocatalytic performance, compared to the CTFs constructed with non‐fused building blocks. The frontier molecular orbitals and electrostatic potentials (ESP) revealed that the oxygen…