The 100 most-cited articles in Angewandte Chemie, 2024

Abstract 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…

Abstract MnO 2 is commonly used as the cathode material for aqueous zinc‐ion batteries (AZIBs). The strong Coulombic interaction between Zn ions and the MnO 2 lattice causes significant lattice distortion and, combined with the Jahn–Teller effect, results in Mn 2+ dissolution and structural collapse. While proton intercalation can reduce lattice distortion, it changes the electrolyte pH, producing chemically inert byproducts. These issues greatly affect the reversibility of Zn 2+ intercalation/extraction, leading to significant capacity degradation of MnO 2 . Herein, we propose a novel method to enhance the cycling stability of δ‐MnO 2 through selenium doping (Se−MnO 2 ). Our work indicates that varying the selenium doping content can regulate the intercalation ratio of H + in MnO 2 , thereby suppressing the formation of ZnMn 2 O 4 by‐products. Se doping mitigates the lattice strain of MnO 2 during Zn 2+ intercalation/deintercalation by reducing Mn−O octahedral distortion, modifying Mn−O bond length upon Zn 2+ insertion, and alleviating Mn dissolution caused by the Jahn–Teller…

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 Nanoconfined polymer molecules exhibit profound transformations in their properties and behaviors. Here, we present the synthesis of a polymer‐in‐MOF single ion conducting solid polymer electrolyte, where polymer segments are partially confined within nanopores ZIF‐8 particles through Lewis acid‐base interactions for solid‐state sodium‐metal batteries (SSMBs). The unique nanoconfinement effectively weakens Na ion coordination with the anions, facilitating the Na ion dissociation from salt. Simultaneously, the well‐defined nanopores within ZIF‐8 particles provide oriented and ordered migration channels for Na migration. As a result, this pioneering design allows the solid polymer electrolyte to achieve a Na ion transference number of 0.87, Na ion conductivity of 4.01×10 −4 S cm −1 , and an extended electrochemical voltage window up to 4.89 V vs. Na/Na + . The assembled SSMBs (with Na 3 V 2 (PO 4 ) 3 as the cathode) exhibit dendrite‐free Na‐metal deposition, promising rate capability, and stable cycling performance with 96 % capacity retention over 300 cycles. This innovative…

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 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…

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 Mg2+ and Ca2+, inhibition of Mg and Ca hydroxide precipitation adherence, and co‐electrosynthesis of nano‐sized…

Abstract Variable stiffness materials have shown considerable application in soft robotics. However, previously reported materials often struggle to reconcile high stiffness, stretchability, toughness, and self‐healing ability, because of the inherently conflicting requisite of these properties in molecular design. Herein, we propose a novel strategy that involves incorporating acid‐base ionic pairs capable of from strong crosslinking sites into a dense and robust hydrogen‐bonding network to construct rigid self‐healing polymers with tunable stiffness and excellent toughness. To demonstrate these distinct features, the polymer was employed to serve as the strain‐regulation layers within a fiber‐reinforced pneumatic actuator (FPA). The exceptional synergy between the configuration versatility of FPA and the dynamic molecular behavior of the supramolecular polymers equips the actuator with simultaneous improvement in motion dexterity, multimodality, loading capacity, robustness, and durability. Additionally, the concept of integrating high dexterity at both macro‐ and micro‐scale is…

Abstract Developing ethanol oxidation electrocatalysts with high catalytic activity, durability, and resistance to CO poisoning remains a major challenge. In recent years, high‐entropy alloys (HEAs) with unique physical and chemical properties have garnered substantial attention. Herein, a class of HEA nanodendrites are designed by a simple wet‐chemical method. The mass activity and specific activity of the septenary PtIrRhCoFeNiCu high‐entropy alloy catalyst are 2.13 A mg Pt −1 /1.05 A mg Pt+Ir+Rh −1 and 2.95 mA cm −2 , which reach 5.76‐/2.84‐fold and 5.57‐fold improvements relative to commercial Pt/C (0.37 A mg Pt −1 and 0.53 mA cm −2 ), respectively. Remarkably, after the i‐t test of up to 100,000 s and the accelerated durability test of 1500 cycles, 81.22 % and 68.54 % of the initial mass activity are well retained, respectively. The lattice distortion‐associated local tensile strain as demonstrated by increased Pt−Pt bond length enhances ethanol adsorption and reduces reaction barriers. Moreover, hysteresis diffusion effect induced by lattice distortion in the HEA nanodendrites…

Abstract Lithium iron phosphate (LFP)/graphite batteries have long dominated the energy storage battery market and are anticipated to become the dominant technology in the global power battery market. However, the poor fast‐charging capability and low‐temperature performance of LFP/graphite batteries seriously hinder their further spread. These limitations are strongly associated with the interfacial lithium (Li)‐ion transport. Here we report a wide‐temperature‐range ester‐based electrolyte that exhibits high ionic conductivity, fast interfacial kinetics and excellent film‐forming ability by regulating the anion chemistry of Li salt. The interfacial barrier of the battery is quantitatively unraveled by employing three‐electrode system and distribution of relaxation time technique. The superior role of the proposed electrolyte in preventing Li 0 plating and sustaining homogeneous and stable interphases are also systematically investigated. The LFP/graphite cells exhibit rechargeability in an ultrawide temperature range of −80 °C to 80 °C and outstanding fast‐charging capability…

Abstract During the electrocatalytic NO3− reduction reaction (NO3−RR) under neutral condition, the activation of H2O 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 H2O 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 NH3 production by NO3−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 and synthesis of…

Abstract Surface chemistry of MXenes is of great interest as the terminations can define the intrinsic properties of this family of materials. The diverse and tunable terminations also distinguish MXenes from many other 2D materials. Conventional fluoride‐containing reagents etching approaches resulted in MXenes with mixed fluoro‐, oxo‐, and hydroxyl surface groups. The relatively strong chemical bonding of MXenes’ surface metal atoms with oxygen and fluorine makes post‐synthetic covalent surface modifications of such MXenes unfavorable. In this minireview, we focus on the recent advances in MXenes with uniform surface terminations. Unconventional methods, including Lewis acidic molten salt etching (LAMS) and bottom‐up direct synthesis, have been proven successful in producing halide‐terminated MXenes. These synthetic strategies have opened new possibilities for MXenes because weaker surface chemical bonds in halide‐terminated MXenes facilitate post‐synthetic covalent surface modifications. Both computational and experimental results on surface termination‐dependent properties are…

Abstract 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 Rechargeable aqueous zinc batteries are promising but hindered by unfavorable dendrite growth and side reactions on zinc anodes. In this study, we demonstrate a fast melting‐solidification approach for effectively converting commercial Zn foils into single (002)‐textured Zn featuring millimeter‐sized grains. The melting process eliminates initial texture, residual stress, and grain size variations in diverse commercial Zn foils, guaranteeing the uniformity of commercial Zn foils into single (002)‐textured Zn. The single (002)‐texture ensures large‐scale epitaxial and dense Zn deposition, while the reduction in grain boundaries significantly minimizes intergranular reactions. These features enable large grain single (002)‐textured Zn shows planar and dense Zn deposition under harsh conditions (100 mA cm−2, 100 mAh cm−2), impressive reversibility in Zn||Zn symmetric cell (3280 h under 1 mA cm−2, 830 h under 10 mAh cm−2), and long cycling stability over 180 h with a high depth of discharge value of 75 %. This study successfully addresses the issue of uncontrollable texture…

Abstract Gel polymer electrolytes (GPEs) hold great promise for the practical application of lithium metal batteries. However, conventional GPEs hardly resists lithium dendrites growth and maintains long‐term cycling stability of the battery due to its poor mechanical performance. Inspired by the slide‐ring structure of polyrotaxanes (PRs), herein we developed a dynamic slide‐crosslinked gel polymer electrolyte (SCGPE) with extraordinary stretchability of 970.93 % and mechanical strength of 1.15 MPa, which is helpful to buffer the volume change of electrodes and maintain mechanical integrity of the battery structure during cycling. Notably, the PRs structures can provide fast ion transport channels to obtain high ionic conductivity of 1.73×10 −3 S cm −1 at 30 °C. Additionally, the strong polar groups in SCGPE restrict the free movement of anions to achieve high lithium‐ion transference number of 0.71, which is favorable to enhance Li + transport dynamics and induce uniform Li + deposition. Benefiting from these features, the constructed Li|SCGPE‐3|LFP cells exhibit ultra‐long and…

Abstract Hydrogen‐bonded organic frameworks (HOFs) demonstrate significant potential for application in photocatalysis. However, the low efficiency of electron‐hole separation and limited stability inhibit their practical utilization in photocatalytic hydrogen evolution from water splitting. Herein, the novel dual‐pyrene‐base supramolecular HOF/COF 2D/2D S‐scheme heterojunction between HOF‐H 4 TBAPy (Py‐HOF, H 4 TBAPy represents the 1,3,6,8‐tetrakis (p‐benzoic acid) pyrene) and Py‐COF was successfully established using a rapid self‐assembly solution dispersion method. Experimental and theoretical investigations confirm that the size‐matching of two crystalline porous materials enables the integrated heterostructure material with abundant surface reaction sites, strong interaction, and an enhanced S‐scheme built‐in electric field, thus significantly improving the efficiency of photogenerated charge carrier separation and stability. Notably, the optimal HOF/COF heterojunction achieves a photocatalytic hydrogen evolution rate of 390.68 mmol g −1 h −1 , which is 2.28 times higher than…

Abstract Formamidinium lead iodide (FAPbI 3 ) represents an optimal absorber material in perovskite solar cells (PSCs), while the application of FAPbI 3 in inverted‐structured PSCs has yet to be successful, mainly owing to its inferior film‐forming on hydrophobic or defective hole‐transporting substrates. Herein, we report a substantial improvement of FAPbI 3 ‐based inverted PSCs, which is realized by a multifunctional amphiphilic molecular hole‐transporter, (2‐(4‐(10 H ‐phenothiazin‐10‐yl)phenyl)‐1‐cyanovinyl)phosphonic acid (PTZ−CPA). The phenothiazine (PTZ) based PTZ−CPA, carrying a cyanovinyl phosphonic acid (CPA) group, forms a superwetting hole‐selective underlayer that enables facile deposition of high‐quality FAPbI 3 thin films. Compared to a previously established carbazole‐based hole‐selective material (2‐(3,6‐dimethoxy‐9 H ‐carbazol‐9‐yl)ethyl)phosphonic acid (MeO−2PACz), the crystallinity of FAPbI 3 is enhanced and the electronic defects are passivated by the PTZ−CPA more effectively, resulting in remarkable increases in photoluminescence quantum yield (four‐fold) and…

Abstract Light‐driven photoredox catalysis presents a promising approach for the activation and conversion of methane (CH 4 ) into high value‐added chemicals under ambient conditions. However, the high C−H bond dissociation energy of CH 4 and the absence of well‐defined C−H activation sites on catalysts significantly limit the highly efficient conversion of CH 4 toward multicarbon (C 2+ ) hydrocarbons, particularly ethylene (C 2 H 4 ). Herein, we demonstrate a bimetallic design of Ag nanoparticles (NPs) and Pd single atoms (SAs) on ZnO for the cascade conversion of CH 4 into C 2 H 4 with the highest production rate compared with previous works. Mechanistic studies reveal that the synergistic effect of Ag NPs and Pd SAs, upon effecting key bond‐breaking and ‐forming events, lowers the overall energy barrier of the activation process of both CH 4 and the resulting C 2 H 6 , constituting a truly synergistic catalytic system to facilitate the C 2 H 4 generation. This work offers a novel perspective on the advancement of photocatalytic directional CH 4 conversion toward high value‐added…

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 Electrochemical reduction of nitrate to ammonia (NO3RR) is a promising and eco‐friendly strategy for ammonia production. However, the sluggish kinetics of the eight‐electron transfer process and poor mechanistic understanding strongly impedes its application. To unveil the internal laws, herein, a library of Pd‐based bimetallene with various transition metal dopants (PdM (M=Fe, Co, Ni, Cu)) are screened to learn their structure–activity relationship towards NO3RR. The ultra‐thin structure of metallene greatly facilitates the exposure of active sites, and the transition metals dopants break the electronic balance and upshift its d‐band center, thus optimizing intermediates adsorption. The anisotropic electronic characteristics of these transition metals make the NO3RR activity in the order of PdCu>PdCo≈PdFe>PdNi>Pd, and a record‐high NH3 yield rate of 295 mg h−1 mgcat−1 along with Faradaic efficiency of 90.9 % is achieved in neutral electrolyte on PdCu bimetallene. Detailed studies further reveal that the moderate N‐species (*NO3 and *NO2) adsorption ability, enhanced *NO…

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 Electrochemical nitrate reduction method (NitRR) is a low‐carbon, environmentally friendly, and efficient method for synthesizing ammonia, which has received widespread attention in recent years. Copper‐based catalysts have a leading edge in nitrate reduction due to their good adsorption of *NO 3 . However, the formation of active hydrogen (*H) on Cu surfaces is difficult and insufficient, resulting in a large amount of the by‐product NO 2 − . In this work, Pd single atoms suspended on the interlayer unsaturated bonds of CuO atoms formed due to dislocations (Pd−CuO) were prepared by low temperature treatment, and the Pd single atoms located on the dislocations were subjected to shear stress and the dynamic effect of support formation to promote the conversion of nitrate into ammonia. The catalysis had an ammonia yield of 4.2 mol. g cat −1 . h −1 , and a Faraday efficiency of 90 % for ammonia production at −0.5 V vs. RHE. Electrochemical in situ characterization and theoretical calculations indicate that the dynamic effects of Pd single atoms and carriers under shear stress…

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 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 Zn2+ ions. Benefiting from the adsorption functionalization of the imidazole group, the IS molecules occupy the position of H2O in the inner Helmholtz layer of the EDL, forming a molecular protective layer to inhibit H2O‐induced side reactions. Meanwhile, the sulfone group in IS, acting as a binding site to Zn2+,…

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 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 Prussian blue analogues (PBAs) have been widely applied in many fields, especially as cathode materials of sodium‐ion batteries on account of their low cost and open framework for fast ions transport. However, the capacity of reported PBAs has a great distance from its theoretical value. Herein, we proposed that [Fe(CN)6] vacancies are crucial point for the high specific capacity for the first time. The [Fe(CN)6] vacancies may create net electrons and reduce obstacles to ionic transport, which is conducive to rate performance of PBAs by increasing electronic and ionic conductivity to some extent. As a proof of concept, a series of PBAs have been prepared by co‐precipitation method. And then, a novel precipitation conversion method has been designed, by which unique PBAs with a specific quantity of [Fe(CN)6] vacancies was successfully synthesized. Remarkably, the as‐prepared PBAs possessing hierarchical hollow morphology have reached a unprecedent level of high capacity (168 mAh g−1 at 25 mA g−1, close to PBAs’ theoretical capacity 170 mAh g−1), high rate performance (90 mAh…

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 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 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…

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 The design of aqueous zinc (Zn) chemistry energy storage with high rate‐capability and long serving life is a great challenge due to its inhospitable coordination environment and dismal interfacial chemistry. To bridge this big gap, herein, we build a highly reversible aqueous Zn battery by taking advantages of the biomass‐derived cellulose nanocrystals (CNCs) electrolyte additive with unique physical and chemical characteristics simultaneously. The CNCs additive not only serves as fast ion carriers for enhancing Zn2+ transport kinetics but regulates the coordination environment and interface chemistry to form dynamic and self‐repairing protective interphase, resulting in building ultra‐stable Zn anodes under extreme conditions. As a result, the engineered electrolyte system achieves a superior average coulombic efficiency of 97.27 % under 140 mA cm−2, and steady charge–discharge for 982 h under 50 mA cm−2, 50 mAh cm−2, which proposes a universal pathway to challenge aqueous Zn chemistry in green, sustainable, and large‐scale applications.

Abstract Hydrogen spillover in metal‐supported catalysts can largely enhance electrocatalytic hydrogenation performance and reduce energy consumption. However, its fundamental mechanism, especially at the metal–metal interface, remains further explored, impeding relevant catalyst design. Here, we theoretically profile that a large free energy difference in hydrogen adsorption on two different metals (|ΔG H‐metal(i) −ΔG H‐metal(ii) |) induces a high kinetic barrier to hydrogen spillover between the metals. Minimizing the difference in their d‐band centers (Δϵ d ) should reduce |ΔG H‐metal(i) −ΔG H‐metal(ii) |, lowering the kinetic barrier to hydrogen spillover for improved electrocatalytic hydrogenation. We demonstrated this concept using copper‐supported ruthenium–platinum alloys with the smallest Δϵ d , which delivered record high electrocatalytic nitrate hydrogenation performance, with ammonia production rate of 3.45±0.12 mmol h −1 cm −2 and Faraday efficiency of 99.8±0.2 %, at low energy consumption of 21.4 kWh kg amm −1 . Using these catalysts, we further achieve continuous…

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 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 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 Dual‐atom catalysts (DACs) are promising for applications in electrochemical CO2 reduction due to the enhanced flexibility of the catalytic sites and the synergistic effect between dual atoms. However, precisely controlling the atomic distance and identifying the dual‐atom configuration of DACs to optimize the catalytic performance remains a challenge. Here, the Ni and Fe atomic pairs were constructed on nitrogen‐doped carbon support in three different configurations: NiFe‐isolate, NiFe‐N bridge, and NiFe‐bonding. It was found that the NiFe‐N bridge catalyst with NiN4 and FeN4 sharing two N atoms exhibited superior CO2 reduction activity and promising stability when compared to the NiFe‐isolate and NiFe‐bonding catalysts. A series of characterizations and density functional theory calculations suggested that the N‐bridged NiFe sites with an appropriate distance between Ni and Fe atoms can exert a more pronounced synergy. It not only regulated the suitable adsorption strength for the *COOH intermediate but also promoted the desorption of *CO, thus accelerating the CO2…

Abstract Electrochemical impedance spectroscopy (EIS), characterized by its non‐destructive and in situ nature, plays a crucial role in comprehending the thermodynamic and kinetic processes occurring within Li‐ion batteries. However, there is a lack of consistent and coherent physical interpretations for the EIS of porous electrodes. Therefore, it is imperative to conduct thorough investigations into the underlying physical mechanisms of EIS. Herein, by employing reference electrode in batteries, we revisit the associated physical interpretation of EIS at different frequencies. Combining different battery configurations, temperature‐dependent experiments, and elaborated distribution of relaxation time analysis, we find that the ion transport in porous electrode channels and pseudo‐capacitance behavior dominate the high‐frequency and mid‐frequency impedance arcs, respectively. This work offers a perspective for the physical interpretation of EIS and also sheds light on the understanding of EIS characteristics in other advanced energy storage systems.

Abstract Unstable Zn interface with serious detrimental parasitic side‐reactions and uncontrollable Zn dendrites severely plagues the practical application of aqueous zinc‐ion batteries. The interface stability was closely related to the electrolyte configuration and Zn 2+ depositional behavior. In this work, a unique Zn‐ion anchoring strategy is originally proposed to manipulate the coordination structure of solvated Zn‐ions and guide the Zn‐ion depositional behavior. Specifically, the amphoteric charged ion additives (denoted as DM), which act as zinc‐ion anchors, can tightly absorb on the Zn surface to guide the uniform zinc‐ion distribution by using its positively charged −NR 4 + groups. While the negatively charged −SO 3 − groups of DM on the other hand, reduces the active water molecules within solvation sheaths of Zn‐ions. Benefiting from the special synergistic effect, Zn metal exhibits highly ordered and compact (002) Zn deposition and negligible side‐reactions. As a result, the advanced Zn||Zn symmetric cell delivers extraordinarily 7000 hours long lifespan (0.25 mA cm −2…

Abstract Singlet oxygen (1O2) 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 1O2 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 1O2 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 (ii)…

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 ( E practical ) 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 E practical . When all parameters are optimized, we urge to achieve the theoretical capacity for a high E practical . 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 For piezoelectric catalysis, the catalytic mechanism is a topic of great controversy, with debates centered around whether it belongs to the energy band theory or the screening charge effect which are similar to mechanisms of photocatalysis and electrochemical catalysis, respectively. Due to the formation of different intermediate active‐species during two‐electron oxygen reduction reaction (ORR) via electro‐ and photo‐catalysis, the key to solving this problem is precisely monitoring the active species involved in ORR during electro‐, photo‐, and piezo‐catalysis under identical condition. Here, a semiconductor material, BiOBr with abundant oxygen vacancies (BOB‐OV) was found remarkable catalytic activity in H 2 O 2 production by all three catalytic methods. By employing in situ electron paramagnetic resonance (EPR) spectroscopy, the H 2 O 2 evolution pathway through piezo‐catalysis over BOB‐OV was monitored, which showed a similar reaction pathway to that observed in photo‐catalytic process. This finding represents solid evidence supporting the notion that piezo‐catalytic…

Abstract Lattice mismatch significantly influences microscopic transport in semiconducting devices, affecting interfacial charge behavior and device efficacy. This atomic‐level disordering, often overlooked in previous research, is crucial for device efficiency and lifetime. Recent studies have highlighted emerging challenges related to lattice mismatch in perovskite solar cells, especially at heterojunctions, revealing issues like severe tensile stress, increased ion migration, and reduced carrier mobility. This review systematically discusses the effects of lattice mismatch on strain, material stability, and carrier dynamics. It also includes detailed characterizations of these phenomena and summarizes current strategies including epitaxial growth and buffer layer, as well as explores future solutions to mitigate mismatch‐induced issues. We also provide the challenges and prospects for lattice mismatch, aiming to enhance the efficiency and stability of perovskite solar cells, and contribute to renewable energy technology advancements.

Abstract The artificial photosynthesis of H2O2 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 H2O2 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 H2O2 production. Herein, we report a strategy for anchoring vinyl moieties to a COF skeleton to facilitate charge separation and migration, thereby promoting photocatalytic H2O2 generation. This vinyl‐group‐bearing COF photocatalyst exhibits a H2O2‐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 improved…

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 Single atom catalysts with defined local structures and favorable surface microenvironments are significant for overcoming slow kinetics and accelerating O2 electroreduction. Here, enriched tip‐like FeN4 sites (T−Fe SAC) on spherical carbon surfaces were developed to investigate the change in surface microenvironments and catalysis behavior. Finite element method (FEM) simulations, together with experiments, indicate the strong local electric field of the tip‐like FeN4 and the more denser interfacial water layer, thereby enhancing the kinetics of the proton‐coupled electron transfer process. In situ spectroelectrochemical studies and the density functional theory (DFT) calculation results indicate the pathway transition on the tip‐like FeN4 sites, promoting the dissociation of O−O bond via side‐on adsorption model. The adsorbed OH* can be facilely released on the curved surface and accelerate the oxygen reduction reaction (ORR) kinetics. The obtained T−Fe SAC nanoreactor exhibits excellent ORR activities (E1/2=0.91 V vs. RHE) and remarkable stability, exceeding those of…

Abstract MXene (Ti 3 C 2 T x ) is renowned for its exceptional conductivity and hydrophilicity; however, the low yield of monolayers hinders its industrial scalability. Herein, we present a strategy to substantially enhance the monolayer yield by disrupting the hydrogen‐bonding cage confinement of multilayer MXene using high‐temperature ultrasound, challenging the conventional belief that monolayer MXene can only be prepared at lower temperatures. At approximately 70 °C, the weakened hydrogen bonding between the oxygen‐containing terminal groups of multilayer MXene and surrounding water molecules weakens the hydrogen‐bond cage confinement. This enables ultrasonic cavitation to generate more microbubbles that penetrate the interlayers of multilayer MXene, resulting in gentle and thorough delamination into larger monolayer nanosheets. Achieving up to a 95 % yield in just tens of minutes, these nanosheets exhibit properties comparable to those produced by traditional ice‐bath methods. Furthermore, the high‐concentration MXene ink produced on a large scale using this high‐yield approach…

Abstract Flexible and high‐performance aqueous zinc‐ion batteries (ZIBs), coupled with low cost and safe, are considered as one of the most promising energy storage candidates for wearable electronics. Hydrogel electrolytes present a compelling alternative to liquid electrolytes due to their remarkable flexibility and clear advantages in mitigating parasitic side reactions. However, hydrogel electrolytes suffer from poor mechanical properties and interfacial chemistry, which limits them to suppressed performance levels in flexible ZIBs, especially under harsh mechanical strains. Herein, a bio‐inspired multifunctional hydrogel electrolyte network (polyacrylamide (PAM)/trehalose) with improved mechanical and adhesive properties was developed via a simple trehalose network‐repairing strategy to stabilize the interfacial chemistry for dendrite‐free and long‐life flexible ZIBs. As a result, the trehalose‐modified PAM hydrogel exhibits a superior strength and stretchability up to 100 kPa and 5338 %, respectively, as well as strong adhesive properties to various substrates. Also, the…

Abstract Conversion‐type electrode materials have gained massive research attention in sodium‐ion batteries (SIBs), but their limited reversibility hampers practical use. Herein, we report a bifunctional nanoreactor to boost highly reversible sodium‐ion storage, wherein a record‐high reversible degree of 85.65 % is achieved for MoS 2 anodes. Composed of nitrogen‐doped carbon‐supported single atom Mn (NC‐SAMn), this bifunctional nanoreactor concurrently confines active materials spatially and catalyzes reaction kinetics. In situ/ex situ characterizations including spectroscopy, microscopy, and electrochemistry, combined with theoretical simulations containing density functional theory and molecular dynamics, confirm that the NC‐SAMn nanoreactors facilitate the electron/ion transfer, promote the distribution and interconnection of discharging products (Na 2 S/Mo), and reduce the Na 2 S decomposition barrier. As a result, the nanoreactor‐promoted MoS 2 anodes exhibit ultra‐stable cycling with a capacity retention of 99.86 % after 200 cycles in the full cell. This work demonstrates the…

Abstract Graphite has been serving as the key anode material of rechargeable Li‐ion batteries, yet is difficultly charged within a quarter hour while maintaining stable electrochemistry. In addition to a defective edge structure that prevents fast Li‐ion entry, the high‐rate performance of graphite could be hampered by co‐intercalation and parasitic reduction of solvent molecules at anode/electrolyte interface. Conventional surface modification by pitch‐derived carbon barely isolates the solvent and electrons, and usually lead to inadequate rate capability to meet practical fast‐charge requirements. Here we show that, by applying a MoO x −MoN x layer onto graphite surface, the interface allows fast Li‐ion diffusion yet blocks solvent access and electron leakage. By regulating interfacial mass and charge transfer, the modified graphite anode delivers a reversible capacity of 340.3 mAh g −1 after 4000 cycles at 6 C, showing promises in building 10‐min‐rechargeable batteries with a long operation life.

Abstract The development of novel materials for highly efficient and selective photocatalysis is crucial for their practical applications. Herein, we employ the host‐guest chemistry of porphyrin‐based metallacages to regulate the generation of reactive oxygen species and further use them for the selective photocatalytic oxidation of benzyl alcohols. Upon irradiation, the sole metallacage ( 6 ) can generate singlet oxygen ( 1 O 2 ) effectively via excited energy transfer, while its complex with C 70 ( 6 ⊃C 70 ) opens a pathway for electron transfer to promote the formation of superoxide anion (O 2 ⋅ − ), producing both 1 O 2 and O 2 ⋅ − . The addition of 4,4′‐bipyridine (BPY) to complex 6 ⊃C 70 forms a more stable complex ( 6 ⊃BPY) via the coordination of the Zn‐porphyrin faces of 6 and BPY, which drives fullerenes out of the cavities and restores the ability of 1 O 2 generation. Therefore, benzyl alcohols are oxidized into benzyl aldehydes upon irradiation in the presence of 6 or 6 ⊃BPY, while they are oxidized into benzoic acids when 6 ⊃C 70 is employed as the photosensitizing…

Abstract Alloying‐type antimony (Sb) with high theoretical capacity is a promising anode candidate for both lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs). Given the larger radius of Na+ (1.02 Å) than Li+ (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…

Abstract Metal‐organic frameworks (MOFs) have emerged as promising oxygen evolution reaction (OER) electrocatalysts. Chemically bonded MOFs on supports are desirable yet lacking in routine synthesis, as they may allow variable structural evolution and the underlying structure‐activity relationship to be disclosed. Herein, direct MOF synthesis is achieved by an organic acid‐etching strategy (AES). Using π‐conjugated ferrocene (Fc) dicarboxylic acid as the etching agent and organic ligand, a series of MFc‐MOF (M=Ni, Co, Fe, Zn) nanosheets are synthesized on the metal supports. The crystal structure is studied using X‐ray diffraction and low‐dose transmission electron microscopy, which is quasi‐lattice‐matched with that of the metal, enabling in situ MOF growth. Operando Raman and attenuated total reflectance Fourier transform infrared spectroscopy disclose that the NiFc‐MOF features dynamic structural rebuilding during OER. The reconstructed one showing optimized electronic structures with an upshifted total d‐band center, high M−O bonding state occupancy, and localized electrons on…

Abstract Aqueous zinc‐ion batteries (ZIBs) hold immense potential for large‐scale energy storage, but their practical implementation faces significant challenges related to the zinc anode, including dendrite formation, corrosion, and hydrogen evolution. This study addresses these challenges by introducing diethylenetriamine pentaacetate sodium salt (DTPA‐Na) as a novel electrolyte additive. DTPA‐Na exhibits a unique dual functionality, enabling the formation of a robust, multi‐layered solid electrolyte interphase (SEI) on the zinc anode and a stable cathode electrolyte interphase (CEI) on the MnOOH cathode. The engineered SEI effectively suppresses interfacial side reactions, facilitates uniform zinc deposition, and mitigates dendrite growth, while the CEI inhibits MnOOH dissolution and detrimental cathode side reactions. This synergistic SEI/CEI engineering approach significantly enhances ZIB performance, achieving remarkable cycling stability and self‐discharge inhibition, as evidenced by the extended lifespan of Zn||Zn symmetrical cells (4400 hours at 0.5 mA/cm 2 ) and the…

Abstract The instability of the solid electrolyte interface (SEI) is a critical challenge for the zinc metal anodes, leading to an erratic electrode/electrolyte interface and hydrogen evolution reaction (HER), ultimately resulting in anode failure. This study uncovers that the fluorine species dissolution is the root cause of SEI instability. To effectively suppress the F − dissolution, an introduction of a low‐polarity molecule, 1,4‐thioxane (TX), is proposed, which reinforces the stability of the fluorine‐rich SEI. Moreover, the TX molecule has a strong affinity for coordinating with Zn 2+ and adsorbing at the electrode/electrolyte interface, thereby diminishing the activity of local water and consequently impeding SEI dissolution. The robust fluorine‐rich SEI layer promotes the high durability of the zinc anode in repeated plating/stripping cycles, while concurrently suppressing HER and enhancing Coulombic efficiency. Notably, the symmetric cell with TX demonstrates exceptional electrochemical performance, sustaining over 500 hours at 20 mA cm −2 with 10 mAh cm −2 . Furthermore,…

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 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(CF 3 SO 3 ) 2 ‐0.2 M acrylamide‐0.2 M ZnSO 4 is proposed. A robust polymer (polyacrylamide)‐inorganic (Zn 4 SO 4 (OH) 6 .xH 2 O) hybrid SEI is in situ constructed on Zn anodes through controllable polymerization of acrylamide and coprecipitation of SO 4 2− with Zn 2+ 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||NH 4 V 4 O…

Abstract The electrolytes for lithium metal batteries (LMBs) are plagued by a low Li+ transference number (T+) of conventional lithium salts and inability to form a stable solid electrolyte interphase (SEI). Here, we synthesized a self‐folded lithium salt, lithium 2‐[2‐(2‐methoxy ethoxy)ethoxy]ethanesulfonyl(trifluoromethanesulfonyl) imide (LiETFSI), and comparatively studied with its structure analogue, lithium 1,1,1‐trifluoro‐N‐[2‐[2‐(2‐methoxyethoxy)ethoxy)]ethyl]methanesulfonamide (LiFEA). The special anion chemistry imparts the following new characteristics: i) In both LiFEA and LiETFSI, the ethylene oxide moiety efficiently captures Li+, resulting in a self‐folded structure and high T+ around 0.8. ii) For LiFEA, a Li−N bond (2.069 Å) is revealed by single crystal X‐ray diffraction, indicating that the FEA anion possesses a high donor number (DN) and thus an intensive interphase “self‐cleaning” function for an ultra‐thin and compact SEI. iii) Starting from LiFEA, an electron‐withdrawing sulfone group is introduced near the N atom. The distance of Li−N is tuned from 2.069 Å in…

Abstract All‐polymer solar cells (all‐PSCs) have been regarded as one of the most promising candidates for commercial applications owing to their outstanding advantages such as mechanical flexibility, light weight and stable film morphology. However, compared to large amount of new‐emerging excellent polymer acceptors, the development of high‐performance polymer donor lags behind. Herein, a new D‐π‐A type polymer donor, namely QQ1, was developed based on dithienoquinoxalineimide (DTQI) as the A unit, benzodithiophene with thiophene‐conjugated side chains (BDTT) as the D unit, and alkyl‐thiophene as the π‐bridge, respectively. QQ1 not only possesses a strong dipole moment, but also shows a wide band gap of 1.80 eV and a deep HOMO energy level of −5.47 eV, even without halogen substituents that are commonly indispensable for high‐performance polymer donors. When blended with a classic polymer acceptor PY‐IT, the QQ1‐based all‐PSC delivers an outstanding PCE of 18.81 %. After the introduction of F‐BTA3 as the third component, a record PCE of 19.20 % was obtained, the highest value…

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 Electrochemical nitrate reduction reaction (NO 3 − RR) has promising prospects for green synthesis of ammonia and environmental remediation. However, the performance of catalysts at high current density usually suffers from the high energy barrier for the nitrate (NO 3 − ) to nitrite (NO 2 − ) and the competitive hydrogen evolution. Herein, we proposed a two‐step relay mechanism through spontaneous redox reaction followed electrochemical reaction by introducing low‐valence Fe species into Ni 2 P nanosheets to significantly enhance the NO 3 − RR performance at industrial current density. The existence of low‐valence Fe species bypasses the NO 3 − to NO 2 − step through the spontaneous redox with NO 3 − to produce NO 2 − and Fe 2 O 3 , regulates the electronic structure of Ni 2 P to reduce the barrier of NO 2 − to NH 3 , thirdly prohibits the hydrogen evolution by consuming the excess active hydrogen through reduction of Fe 2 O 3 to recover low‐valence Fe species. The triple regulations via Fe redox during the two‐step relay reactions guarantee the Fe‐Ni 2 P@NF high ammonia…

Abstract Photocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal‐covalent organic frameworks (MCOFs) with both small‐sized metal clusters and nitrogen‐rich ligands, named COF‐Cu3TG. Based on our design, small‐sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen‐rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single‐atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N2‐Ru‐N2 electron bridge (Ru‐SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g−1 h−1. Through theoretical calculation and EXAFS, the existence position and action mechanism…

Abstract The direct production of hydrogen peroxide (H 2 O 2 ) through photocatalytic reaction via H 2 O and O 2 is considered as an ideal approach. However, the efficiency of H 2 O 2 generation is generally limited by insufficient charge and mass transfer. Covalent organic framework (COFs) offer a promising platform as metal‐free photocatalyst for H 2 O 2 production due to their potential for rational design at the molecular level. Herein, we integrated the multipolar structures and carboxyl groups into COFs to enhance the efficiency of photocatalytic H 2 O 2 production in pure water without any sacrificial agents. The introduction of octupolar and quadrupolar structures, along with an increase of molecular planarity, created efficient oxygen reduction reaction (ORR) sites. Meanwhile, carboxyl groups could not only boost O 2 and H 2 O 2 movement via enhancement of pore hydrophilicity, but also promote proton conduction, enabling the conversion to H 2 O 2 from ⋅O 2 − , which is the crucial intermediate product in H 2 O 2 photocatalysis. Overall, we demonstrate that TACOF‐1‐COOH,…

Abstract Due to their remarkable features of lightweight, high strength, stiffness, high‐temperature resistance, and corrosion resistance, carbon fiber reinforced polymers (CFRPs) are extensively used in sports equipment, vehicles, aircraft, windmill blades, and other sectors. The urging need to develop a resource‐saving and environmentally responsible society requires the recycling of CFRPs. Traditional CFRPs, on the other hand, are difficult to recycle due to the permanent covalent crosslinking of polymer matrices. The combination of covalent adaptable networks (CANs) with carbon fibers (CFs) marks a new development path for closed‐loop recyclable CFRPs and polymer resins. In this review, we summarize the most recent developments of closed‐loop recyclable CFRPs from the unique paradigm of dynamic crosslinking polymers, CANs. These sophisticated materials with diverse functions, oriented towards CFs recycling and resin sustainability, are further categorized into several active domains of dynamic covalent bonds, including ester bonds, imine bonds, disulfide bonds, boronic ester…

Abstract The interface of perovskite solar cells (PSCs) plays an important role in transferring and collecting charges. Interface defects are important factors affecting the efficiency and stability of PSCs. Here, the buried interface between SnO2 and the perovskite layer is bridged by two‐dimensional (2D) MBene, which improves charge transfer. MBene can deposit additional electrons on the surface of SnO2, passivate its surface defects and facilitate the charge collection. Moreover, the dipole moment formed at the interface increases the electron transfer ability in the PSCs. MBene also regulates the growth of perovskite crystals, improves the quality of perovskite films, and reduces its grain boundary defects. As a result, PSCs based on FA0.2MA0.8PbI3 and (FAPbI3)0.95(MAPbBr3)0.05 get the enhanced efficiencies of 22.34 % and 24.32 % with negligible hysteresis. Furthermore, the optimized device exhibits better stability. This work opens up the application of MBene materials in PSCs, reveals a deeper understanding of the mechanism behind using 2D materials as an interface…

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 Two‐dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in‐plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π–π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn−N 3 units that can bridge nitrogen (N)‐doped carbon layers with polymeric carbon nitride nanosheets (C 3 N 4 −Zn−N(C)) to address this challenge. The symmetry‐breaking Zn−N 3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C 3 N 4 photocatalyst and the N‐doped carbon co‐catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn−N 3 bonding bridges. As a result, the designed C 3 N 4 −Zn−N(C) catalyst exhibits dramatically enhanced H 2 O 2 photosynthesis…

Abstract Electrocatalytic nitrate reduction to ammonia (NO 3 RR) is very attractive for nitrate removal and ammonia production in industrial processes. However, the nitrate reduction reaction is characterized by intense hydrogen competition at strong reduction potentials, which greatly limits the Faraday efficiency at strong reduction potentials. Herein, we reported an Au x Cu single‐atom alloy aerogels (Au x Cu SAAs) with three‐dimensional network structure with significant nitrate reduction performance of Faraday efficiency (FE) higher than 90 % over a wide potential range (0 ~ −1 V RHE ). The FE of the catalyst was close to 100 % at a high reduction potential of −0.8 V RHE , accompanying with NH 3 yield reaching 6.21 mmol h 1 cm 2 . More importantly, the catalyst maintained a long‐term operation over 400 h at 400 mA cm 2 for the NO 3 RR using a continuous flow system in a H‐cell. Experimental and theoretical analysis demonstrate that the catalyst can lower the energy barrier for the hydrogenation reaction of *NO 2 , leading to a rapid consumption of the generated *H, facilitate…

Abstract A novel Ir−Mn dual‐atom electrocatalyst is synthesized by a facile ion‐exchange method by incorporating Ir in SrMnO 3 , which yields an extremely high activity and stability for the oxygen evolution reaction (OER). The ion exchange process occurs in a self‐limitation way, which favors the formation of Ir−Mn dual‐atom in the IrMnO 9 unit. The incorporation of Ir modulates the electronic structure of both Ir and Mn, thereby resulting in a shorter distance of the Ir−Mn dual‐atom (2.41 Å) than the Mn−Mn dual‐atom (2.49 Å). The modulated Ir−Mn dual‐atom enables the same spin direction O (↑) of the adsorbed *O intermediates, thus facilitating the direct coupling of the two adsorbed *O intermediates to release O 2 via the oxygen‐oxygen radical coupling mechanism. Electrochemical tests reveal that the Ir‐SrMnO 3 exhibits a superior OER's activity with a low overpotential of 207 mV at 10 mA cm −2 and achieves a mass specific activity of 1100 A g Ir −1 at 1.5 V. The proton‐exchange‐membrane water electrolyzer with the Ir‐SrMnO 3 catalyst exhibits a low electrolysis voltage of 1.63 V…

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 H 2 O 2 . However, Cu‐CTU‐based MOFs are not able to photocatalyzed the formation of H 2 O 2 , while the alteration of metal nodes from Cu‐CTU to Ag‐CTU dramatically enhances the photocatalytic performance for H 2 O 2 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 H 2 O 2 production through molecular engineering.

Abstract Solid polymer electrolytes are promising electrolytes for safe and high‐energy‐density lithium metal batteries. However, traditional ether‐based polymer electrolytes are limited by their low lithium‐ion conductivity and narrow electrochemical window because of the well‐defined and intimated Li + ‐oxygen binding topologies in the solvation structure. Herein, we proposed a new strategy to reduce the Li + ‐polymer interaction and strengthen the anion‐polymer interaction by combining strong Li + ‐O (ether) interactions, weak Li + ‐O (ester) interactions with steric hindrance in polymer electrolytes. In this way, a polymer electrolyte with a high lithium ion transference number (0.80) and anion‐rich solvation structure is obtained. This polymer electrolyte possesses a wide electrochemical window (5.5 V versus Li/Li + ) and compatibility with both Li metal anode and high‐voltage NCM cathode. Li||LiNi 0.5 Co 0.2 Mn 0.3 O 2 full cells with middle‐high active material areal loading (~7.5 mg cm −2 ) can stably cycle at 4.5 V. This work provides new insight into the design of polymer…

Abstract The practical application of the electrocatalytic CO 2 reduction reaction (CO 2 RR) to form formic acid fuel is hindered by the limited activation of CO 2 molecules and the lack of universal feasibility across different pH levels. Herein, we report a doping‐engineered bismuth sulfide pre‐catalyst (BiS‐1) that S is partially retained after electrochemical reconstruction into metallic Bi for CO 2 RR to formate/formic acid with ultrahigh performance across a wide pH range. The best BiS‐1 maintains a Faraday efficiency (FE) of ~95 % at 2000 mA cm −2 in a flow cell under neutral and alkaline solutions. Furthermore, the BiS‐1 catalyst shows unprecedentedly high FE (~95 %) with current densities from 100 to 1300 mA cm −2 under acidic solutions. Notably, the current density can reach 700 mA cm −2 while maintaining a FE of above 90 % in a membrane electrode assembly electrolyzer and operate stably for 150 h at 200 mA cm −2 . In situ spectra and density functional theory calculations reveals that the S doping modulates the electronic structure of Bi and effectively promotes the…

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 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 Environmentally friendly crosslinked polymer networks feature degradable covalent or non‐covalent bonds, with many of them manifesting dynamic characteristics. These attributes enable convenient degradation, facile reprocessibility, and self‐healing capabilities. However, the inherent instability of these crosslinking bonds often compromises the mechanical properties of polymer networks, limiting their practical applications. In this context, environmentally friendly dual‐crosslinking polymer networks (denoted EF‐DCPNs) have emerged as promising alternatives to address this challenge. These materials effectively balance the need for high mechanical properties with the ability to degrade, recycle, and/or self‐heal. Despite their promising potential, investigations into EF‐DCPNs remain in their nascent stages, and several gaps and limitations persist. This Review provides a comprehensive overview of the synthesis, properties, and applications of recent progress in EF‐DCPNs. Firstly, synthetic routes to a rich variety of EF‐DCPNs possessing two distinct types of dynamic bonds…

Abstract Covalent organic frameworks (COFs) provide a molecular platform for designing a novel class of functional materials with well‐defined structures. A crucial structural parameter is the linkage, which dictates how knot and linker units are connected to form two‐dimensional polymers and layer frameworks, shaping ordered π‐array and porous architectures. However, the roles of linkage in the development of ordered π electronic structures and functions remain fundamental yet unresolved issues. Here we report the designed synthesis of COFs featuring four representative linkages: hydrazone, imine, azine, and C=C bonds, to elucidate their impacts on the evolution of π electronic structures and functions. Our observations revealed that the hydrazone linkage provides a non‐conjugated connection, while imine and azine allow partial π conjugation, and the C=C bond permits full π‐conjugation. Importantly, the linkage profoundly influences the control of π electronic structures and functions, unraveling its pivotal role in determining key electronic properties such as band gap, frontier…

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 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||Na3V2(PO4)3 yields an extended lifespan over 250…

Abstract 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 Despite ongoing challenges, achieving further breakthroughs in the development of gel polymer electrolytes with a wide temperature range, excellent liquid retention capability and enhanced anode compatibility in flexible zinc‐air batteries (FZABs) remains a significant objective. This study presents a significant advancement in the development of choline chloride/ethylene glycol‐polyvinyl alcohol (ChCl/EG‐PVA) eutectogel electrolyte, tailored for high‐performance operation across a wide temperature range. Systematic in‐situ and ex‐situ characterizations and theoretical simulations confirm the formation of robust hydrogen bonding and denser polymer cross‐linked networks within the prepared eutectogel, leading to enhanced liquid retention ability (93.7 % after 96 h exposure to air) and ion transport capacity (ionic conductivity of 171.3 mS cm −1 ). Additionally, the zincophilicity nature of the choline cation in eutectogel effectively suppresses dendrites growth. The assembled FZAB utilizing this eutectogel electrolyte achieves a peak power density of 109.3 mW cm −2 and a…

Abstract Precisely controlling the microstructure of supported metal catalysts and regulating metal‐support interactions at the atomic level are essential for achieving highly efficient heterogeneous catalysts. Strong metal‐support interaction (SMSI) not only stabilizes metal nanoparticles and improves their resistance to sintering but also modulates the electrical interaction between metal species and the support, optimizing the catalytic activity and selectivity. Therefore, understating the formation mechanism of SMSI and its dynamic evolution during the chemical reaction at the atomic scale is crucial for guiding the structural design and performance optimization of supported metal catalysts. Recent advancements in in situ transmission electron microscopy (TEM) have shed new light on these complex phenomena, providing deeper insights into the SMSI dynamics. Here, the research progress of in situ TEM investigation on SMSI in heterogeneous catalysis is systematically reviewed, focusing on the formation dynamics, structural evolution during the catalytic reactions, and regulation…

Abstract Catalytic removal of alkynes is essential in industry for producing polymer‐grade alkenes from steam cracking processes. Non‐noble Ni‐based catalysts hold promise as effective alternatives to industrial Pd‐based catalysts but suffer from low activity. Here we report embedding of single‐atom Pd onto the NiGa intermetallic surface with replacing Ga atoms via a well‐defined synthesis strategy to design Pd1−NiGa catalyst for alkyne semi‐hydrogenation. The fabricated Pd1Ni2Ga1 ensemble sites deliver remarkably higher specific mass activity under superb alkene selectivity of >96 % than the state‐of‐the‐art catalysts under industry‐relevant conditions. Integrated experimental and computational studies reveal that the single‐atom Pd synergizes with the neighbouring Ni sites to facilitate the σ‐adsorption of alkyne and dissociation of hydrogen while suppress the alkene adsorption. Such synergistic effects confer the single‐atom Pd on the NiGa intermetallic with a Midas touch for alkyne semi‐hydrogenation, providing an effective strategy for stimulating low active Ni‐based catalysts…

Abstract Covalent organic framework (COF) has attracted increasing interest in photocatalytic CO 2 reduction, but it remains a challenge to achieve high conversion efficiency owing to the insufficient active site and fast charge recombination. Rationally optimizing the electronic structures of COF to regulate the local charge of active sites precisely is the key point to improving catalytic performance. Herein, intercalated single Co sites coordinated by imine‐N motifs have been designed by using trinuclear copper‐based imine‐COFs with distinct electronic moieties via a molecular engineering strategy. It is confirmed that the charge delivery property and local charge distribution of these heterometallic frameworks can be profoundly influenced by electronic structures. Among these featured structures with mixed‐state copper clusters, Co/Cu 3 ‐TPA‐COF stands out for an exceptional photocatalytic CO 2 reduction activity and tunable syngas (CO/H 2 ) ratio by changing various bipyridines. Experimental and theoretical results indicate that interlayer Co‐imine N motifs on the donor 1…

Abstract Lithium‐ion batteries play an integral role in various aspects of daily life, yet there is a pressing need to enhance their safety and cycling stability. In this study, we have successfully developed a highly secure and flexible solid‐state polymer electrolyte (SPE) through the in situ polymerization of allyl acetoacetate (AAA) monomers. This SPE constructed an efficient Li+ transport channel inside and effectively improved the solid‐solid interface contact of solid‐state batteries to reduce interfacial impedance. Furthermore, it exhibited excellent thermal stability, an ionic conductivity of 3.82×10−4 S cm−1 at room temperature (RT), and a Li+ transport number (tLi+) of 0.66. The numerous oxygen vacancies on layered inorganic SiO2 created an excellent environment for TFSI− immobilization. Free Li+ migrated rapidly at the C=O equivalence site with the poly(allyl acetoacetate) (PAAA) matrix. Consequently, when cycled at 0.5C and RT, it displayed an initial discharge specific capacity of 140.6 mAh g−1 with a discharge specific capacity retention rate of 70 % even after 500…

Abstract Current potassium‐ion batteries (PIBs) are limited in safety and lifetime owing to the lack of suitable electrolyte solutions. To address these issues, herein, we report an innovative non‐flammable electrolyte design strategy that leverages an optimal moderate solvation phosphate‐based solvent which strikes a balance between solvation capability and salt dissociation ability, leading to superior electrochemical performance. The formulated electrolyte simultaneously exhibits the advantages of low salt concentration (only 0.6 M), low viscosity, high ionic conductivity, high oxidative stability, and safety. Our electrolyte also promotes the formation of self‐limiting inorganic‐rich interphases at the anode surface, alongside robust cathode‐electrolyte interphase on iron‐based Prussian blue analogues, mitigating electrode/electrolyte side reactions and preventing Fe dissolution. Notably, the PIBs employing our electrolyte exhibit exceptional durability, with 80 % capacity retention after 2,000 cycles at high‐voltage of 4.2 V in a coin cell. Impressively, in a larger scale pouch…

Abstract The electrocatalytic CO2 reduction reaction (CO2RR) is a sustainable route for converting CO2 into value‐added fuels and feedstocks, advancing a carbon‐neutral economy. The electrolyte critically influences CO2 utilization, reaction rate and product selectivity. While typically conducted in neutral/alkaline aqueous electrolytes, the CO2RR 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 (C2+) products, and poor electrocatalyst stability persist. The effective regulation of the reaction environment at the cathode is essential to favor the CO2RR over the competitive hydrogen evolution reaction (HER) and improve long‐term stability. This review examines progress in the acidic CO2RR, focusing on reaction environment regulation strategies such as electrocatalyst design, electrode modification and electrolyte engineering to promote the CO2RR. Insights into the reaction mechanisms via in…

Abstract RuO2 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 RuO6 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 RuSnOx electrocatalyst exhibited excellent OER activity in 0.1 M HClO4 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 Sodium‐ion batteries (SIBs) suffer from sluggish kinetics, large volume change, and limited specific capacity due to the large radius of Na + . These issues can be solved through using covalent organic frameworks (COFs) as electrodes. Herein, an azatriangulenetrione‐containing COF (denoted as CityU‐33) was designed and synthesized as an electrode material for SIBs. Due to its inherent abundance of multiple redox‐active sites and fast intercalation kinetics, CityU‐33 delivered a high discharge capacity of 410.4 mAh g −1 at 0.1 A g −1 and showed remarkable long‐term cycling stability, where a discharge capacity of 288 mAh g −1 at 0.2 A g −1 with 97 % retention over 2000 cycles was achieved, making it the top COF electrode material for SIBs.

Abstract Carbon dots (CDs) have rapidly emerged as a new family of carbon‐based nanomaterials since their initial discovery two decades ago. Numerous appealing properties, such as precursor and synthesis process flexibility, tunable photoluminescence, and good biocompatibility, have enabled their widespread applications in sensing, catalysis, energy, and biomedical fields. As the field expands, notable efforts have recently focused on mechanistically elucidating the structural formation and optical behavior of CDs. However, the absence of “clean” CDs presents a major obstacle to achieving a solid understanding of these aspects. Often, the claimed CDs are, in fact, a mixture of small molecules, oligomers, nano‐sized aggregates, or even microparticles. Such coexistence of impurities markedly impacts the physicochemical properties of resulting CD‐based mixtures, hampering the resolution of key mechanistic questions. Here, we aim to address this fundamental shortcoming of the field, going beyond the customary focus of the existing reviews that predominantly cover synthesis, optical…

Abstract The characteristics of the soft component and the ionic‐electronic nature in all‐inorganic CsPbI3‐xBrx perovskite typically lead to a significant number of halide vacancy defects and ions migration, resulting in a reduction in both photovoltaic efficiency and stability. Herein, we present a tailored approach in which both anion‐fixation and undercoordinated‐Pb passivation are achieved in situ during crystallization by employing a molecule derived from aniline, specifically 2‐methoxy‐5‐trifluoromethylaniline (MFA), to address the above challenges. The incorporation of MFA into the perovskite film results in a pronounced inhibition of ion migration, a significant reduction in trap density, an enhancement in grain size, an extension of charge carrier lifetime, and a more favorable alignment of energy levels. These advantageous characteristics contribute to achieving a champion power conversion efficiency (PCE) of 22.14 % for the MFA‐based CsPbI3‐xBrx perovskite solar cells (PSCs), representing the highest efficiency reported thus far for this type of inorganic metal halide…

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 The cycling performance of zinc‐ion batteries is greatly affected by dendrite formation and side reactions on zinc anode, particularly in scenarios involving high depth of discharge (DOD) and low negative/positive capacity (N/P) ratios in full cells. Herein, drawing upon principles of host–guest interaction chemistry, we investigate the impact of molecular structure of electrolyte additives, specifically the −COOH and −OH groups, on the zinc negative electrode through molecular design. Our findings reveal that molecules containing these groups exhibit strong adsorption onto zinc anode surfaces and chelate with Zn 2+ , forming a H 2 O‐poor inner Helmholtz plane. This effectively suppresses side reactions and promotes dendrite‐free zinc deposition of exposed (002) facets, enhancing stability and reversibility of an average coulombic efficiency of 99.89 % with the introduction of Lactobionic acid (LA) additive. Under harsh conditions of 92 % DOD, Zn//Zn cells exhibit stable cycling at challenging current densities of 15 mA ⋅ cm −2 . Even at a low N/P ratio of 1.3, Zn//NH 4 V 4…

Abstract The alkaline oxygen evolution reaction (OER) is a promising avenue for producing clean fuels and storing intermittent energy. However, challenges such as excessive OH− consumption and strong adsorption of oxygen‐containing intermediates hinder the development of alkaline OER. In this study, we propose a cooperative strategy by leveraging both nano‐scale and atomically local electric fields for alkaline OER, demonstrated through the synthesis of Mn single atom doped CoP nanoneedles (Mn SA‐CoP NNs). Finite element method simulations and density functional theory calculations predict that the nano‐scale local electric field enriches OH− around the catalyst surface, while the atomically local electric field improves *O desorption. Experimental validation using in situ attenuated total reflection infrared and Raman spectroscopy confirms the effectiveness of the nano‐scale and atomically electric fields. Mn SA‐CoP NNs exhibit an ultra‐low overpotential of 189 mV at 10 mA cm−2 and stable operation over 100 hours at ~100 mA cm−2 during alkaline OER. This innovative strategy…

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 Diluents have been extensively employed to overcome the disadvantages of high viscosity and sluggish kinetics of high‐concentration electrolytes, but generally do not change the pristine solvation structure. Herein, a weakly coordinating diluent, hexafluoroisopropyl methyl ether (HFME), is applied to regulate the coordination of Na + with diglyme and anion and form a diluent‐participated solvate. This unique solvation structure promotes the accelerated decomposition of anions and diluents, with the construction of robust inorganic‐rich electrode‐electrolyte interphases. In addition, the introduction of HFME reduces the desolvation energy of Na + , improves ionic conductivity, strengthens the antioxidant, and enhances the safety of the electrolyte. As a result, the assembled Na||Na symmetric cell achieves a stable cycle of over 1800 h. The cell of Na||P’2‐Na 0.67 MnO 2 delivers a high capacity retention of 87.3 % with a high average Coulombic efficiency of 99.7 % after 350 cycles. This work provides valuable insights into solvation chemistry for advanced electrolyte…

Abstract Acting as a passive protective layer, solid‐electrolyte interphase (SEI) plays a crucial role in maintaining the stability of the Li‐metal anode. Derived from the reductive decomposition of electrolytes (e.g., anion and solvent), the SEI construction presents as an interfacial process accompanied by the dynamic de‐solvation process during Li‐metal plating. However, typical electrolyte engineering and related SEI modification strategies always ignore the dynamic evolution of electrolyte configuration at the Li/electrolyte interface, which essentially determines the SEI architecture. Herein, by employing advanced electrochemical in situ FT‐IR and MRI technologies, we directly visualize the dynamic variations of solvation environments involving Li + ‐solvent/anion. Remarkably, a weakened Li + ‐solvent interaction and anion‐lean interfacial electrolyte configuration have been synchronously revealed, which is difficult for the fabrication of anion‐derived SEI layer. Moreover, as a simple electrochemical regulation strategy, pulse protocol was introduced to effectively restore…

Abstract Hybrid nanomaterials have found use in many biomedical applications. This article provides a comprehensive review of the principles, techniques, and recent advancements in the design and fabrication of hybrid nanomaterials for biomedicine. We begin with an introduction to the general concept of material hybridization, followed by a discussion of how this approach leads to materials with additional functionality and enhanced performance. We then highlight hybrid nanomaterials in the forms of nanostructures, nanocomposites, metal–organic frameworks, and biohybrids, including their fabrication methods. We also showcase the use of hybrid nanomaterials to advance biomedical engineering in the context of nanomedicine, regenerative medicine, diagnostics, theranostics, and biomanufacturing. Finally, we offer perspectives on challenges and opportunities.

Abstract Ethylene (C2H4) purification and propylene (C3H6) recovery are highly relevant in polymer synthesis, yet developing physisorbents for these industrial separation faces the challenges of merging easy scalability, economic feasibility, high moisture stability with great separation efficiency. Herein, we reported a robust and scalable MOF (MAC‐4) for simultaneous recovery of C3H6 and C2H4. Through creating nonpolar pores decorated by accessible N/O sites, MAC‐4 displays top‐tier uptakes and selectivities for C2H6 and C3H6 over C2H4 at ambient conditions. Molecular modelling combined with infrared spectroscopy revealed that C2H6 and C3H6 molecules were trapped in the framework with stronger contacts relative to C2H4. Breakthrough experiments demonstrated exceptional separation performance for binary C2H6/C2H4 and C3H6/C2H4 as well as ternary C3H6/C2H6/C2H4 mixtures, simultaneously affording record productivities of 27.4 and 36.2 L kg−1 for high‐purity C2H4 (≥99.9 %) and C3H6 (≥99.5 %). MAC‐4 was facilely prepared at deckgram‐scale under reflux condition within 3 hours, making…

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 Aluminum−sulfur (Al−S) batteries are promising energy storage devices due to their high theoretical capacity, low cost, and high safety. However, the high viscosity and inferior ion transport of conventionally used ionic liquid electrolytes (ILEs) limit the kinetics of Al−S batteries, especially at sub‐zero temperatures. Herein, locally concentrated ionic liquid electrolytes (LCILE) formed via diluting the ILEs with non‐solvating 1,2‐difluorobenzene (dFBn) co‐solvent are proposed for wide‐temperature‐range Al−S batteries. The addition of dFBn effectively promotes the fluidity and ionic conductivity without affecting the AlCl4−/Al2Cl7− equilibrium, which preserves the reversible stripping/plating of aluminum and further promotes the overall kinetics of Al−S batteries. As a result, Al−S cells employing the LCILE exhibit higher specific capacity, better cyclability, and lower polarization with respect to the neat ILE in a wide temperature range from −20 to 40 °C. For instance, Al−S batteries employing the LCILE sustain a remarkable capacity of 507 mAh g−1 after 300 cycles at…