The 100 most-cited articles in Angewandte Chemie, 2023

Abstract Two‐dimensional (2D) transition metal dichalcogenides (TMDs), a rising star in the post‐graphene era, are fundamentally and technologically intriguing for photocatalysis. Their extraordinary electronic, optical, and chemical properties endow them as promising materials for effectively harvesting light and catalyzing the redox reaction in photocatalysis. Here, we present a tutorial‐style review of the field of 2D TMDs for photocatalysis to educate researchers (especially the new‐comers), which begins with a brief introduction of the fundamentals of 2D TMDs and photocatalysis along with the synthesis of this type of material, then look deeply into the merits of 2D TMDs as co‐catalysts and active photocatalysts, followed by an overview of the challenges and corresponding strategies of 2D TMDs for photocatalysis, and finally look ahead this topic.

Abstract The performance of aqueous Zn ion batteries (AZIBs) is highly dependent on inner Helmholtz plane (IHP) chemistry. Notorious parasitic reactions containing hydrogen evolution reactions (HER) and Zn dendrites both originate from abundant free H 2 O and random Zn deposition inside active IHP. Here, we report a universal high donor number (DN) additive pyridine (Py) with only 1 vol. % addition (Py‐to‐H 2 O volume ratio), for regulating molecule distribution inside IHP. Density functional theory (DFT) calculations and molecular dynamics (MD) simulation verify that incorporated Py additive could tailor Zn 2+ solvation sheath and exclude H 2 O molecules from IHP effectively, which is in favor of preventing H 2 O decomposition. Consequently, even at extreme conditions such as high depth of discharge (DOD) of 80 %, the symmetric cell based on Py additive can sustain approximately 500 h long‐term stability. This efficient strategy with high DN additives furnishes a promising direction for designing novel electrolytes and promoting the practical application of AZIBs, despite…

Abstract Benefiting from the excellent structural tunability, robust framework, ultrahigh porosity, and rich active sites, covalent organic frameworks (COFs) are widely recognized as promising photocatalysts in chemical conversions, and emerged in the hydrogen peroxide (H 2 O 2 ) photosynthesis in 2020. H 2 O 2 , serving as an environmental‐friendly oxidant and a promising liquid fuel, has attracted increasing researchers to explore its potential. Over the past few years, numerous COFs‐based photocatalysts are developed with encouraging achievements in H 2 O 2 production, whereas no comprehensive review articles exist to summarize this specific and significant area. Herein we provide a systematic overview of the advances and challenges of COFs in photocatalytic H 2 O 2 production. We first introduce the priorities of COFs in H 2 O 2 photosynthesis. Then, various strategies to improve COFs photocatalytic efficiency are discussed. The perspective and outlook for future advances of COFs in this emerging field are finally offered. This timely review will pave the way for the development…

Abstract This work reports that a low‐temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface‐active sites while maintaining the crystal morphology. All the experiments demonstrate that the new photocatalyst nano MIL‐125(Ti)‐250 obtained by thermal calcination strategy has abundant Ti3+ induced by oxygen vacancies and high specific surface area. This facilitates the adsorption and activation of N2 molecules on the active sites in the photocatalytic nitrogen fixation. The photocatalytic NH3 yield over MIL‐125(Ti)‐250 is enhanced to 156.9 μmol g−1 h−1, over twice higher than that of the parent MIL‐125(Ti) (76.2 μmol g−1 h−1). Combined with density function theory (DFT), it shows that the N2 adsorption pattern on the active sites tends to be from “end‐on” to “side‐on” mode, which is thermodynamically favourable. Moreover, the electrochemical tests demonstrate that the high atomic ratio of Ti3+/Ti4+ can enhance carrier separation, which also promotes the efficiency of photocatalytic N2 fixation. This work may offer new…

Abstract We demonstrate the great feasibility of MBenes as a new class of tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO3RR). As a proof of concept, FeB2is first employed as a model MBene catalyst for the NO3RR, showing a maximum NH3‐Faradaic efficiency of 96.8 % with a corresponding NH3yield of 25.5 mg h−1 cm−2at −0.6 V vs. RHE. Mechanistic studies reveal that the exceptional NO3RR activity of FeB2arises from the tandem catalysis mechanism, that is, B sites activate NO3−to form intermediates, while Fe sites dissociate H2O and increase *H supply on B sites to promote the intermediate hydrogenation and enhance the NO3−‐to‐NH3conversion.

Abstract Efficient bifunctional electrocatalysts for hydrogen and oxygen evolution reactions are key to water electrolysis. Herein, we report a built‐in electric field (BEF) strategy to fabricate heterogeneous nickel phosphide‐cobalt nanowire arrays grown on carbon fiber paper (Ni2P‐CoCH/CFP) with large work function difference (ΔΦ) as bifunctional electrocatalysts for overall water splitting. Impressively, Ni2P‐CoCH/CFP exhibits a remarkable catalytic activity for hydrogen and oxygen evolution reactions to obtain 10 mA cm−2, respectively. Moreover, the assembled lab‐scale electrolyzer driven by an AAA battery delivers excellent stability after 50 h electrocatalysis with a 100 % faradic efficiency. Computational calculations combining with experiments reveal the interface‐induced electric field effect facilitates asymmetrical charge distributions, thereby regulating the adsorption/desorption of the intermediates during reactions. This work offers an avenue to rationally design high‐performance heterogeneous electrocatalysts.

Abstract Crystallography modulation of zinc (Zn) metal anode is promising to promote Zn reversibility in aqueous electrolytes, but efficiently constructing Zn with specific crystallographic texture remains challenging. Herein, we report a current‐controlled electrodeposition strategy to texture the Zn electrodeposits in conventional aqueous electrolytes. Using the electrolytic cell with low‐cost Zn(CH 3 COO) 2 electrolyte and Cu substrate as a model system, the texture of as‐deposited Zn gradually transforms from (101) to (002) crystal plane as increasing the current density from 20 to 80 mA cm −2 . Moreover, the high current accelerates the Zn nucleation rate with abundant nuclei, enabling uniform deposition. The (002) texture permits stronger resistance to dendrite growth and interfacial side reactions than the (101) texture. The resultant (002)‐textured Zn electrode achieves deep cycling stability and supports the stable operation of full batteries with conventional V/Mn‐based oxide cathodes.

Abstract Zinc (Zn) metal anode suffers from uncontrollable Zn dendrites and parasitic side reactions at the interface, which restrict the practical application of aqueous rechargeable zinc batteries (ARZBs). Herein, an amphoteric cellulose‐based double‐network is introduced as hydrogel electrolyte to overcome these obstacles. On one hand, the amphoteric groups build anion/cation transport channels to regulate electro‐deposition behavior on Zn (002) crystal plane enabled by homogenizing Zn2+ions flux. On the other hand, the strong bonding between negatively charged carboxyl groups and Zn2+ions promote the desolvation process of [Zn(H2O)6]2+to eliminate side reactions. Based on the above two functions, the hydrogel electrolyte enables an ultra‐stable cycling with a cumulative capacity of 7 Ah cm−2at 20 mA cm−2/20 mAh cm−2for Zn||Zn cell. This work provides significant concepts for developing hydrogel electrolytes to realize stable anode for high‐performance ARZBs.

Abstract Highly reversible plating/stripping in aqueous electrolytes is one of the critical processes determining the performance of Zn‐ion batteries, but it is severely impeded by the parasitic side reaction and dendrite growth. Herein, a novel electrolyte engineering strategy is first proposed based on the usage of 100 mM xylitol additive, which inhibits hydrogen evolution reaction and accelerates cations migration by expelling active H2O molecules and weakening electrostatic interaction through oriented reconstruction of hydrogen bonds. Concomitantly, xylitol molecules are preferentially adsorbed by Zn surface, which provides a shielding buffer layer to retard the sedimentation and suppress the planar diffusion of Zn2+ ions. Zn2+ transference number and cycling lifespan of Zn∥Zn cells have been significantly elevated, overwhelmingly larger than bare ZnSO4. The cell coupled with a NaV3O8 cathode still behaves much better than the additive‐free device in terms of capacity retention.

Abstract Problems of zinc anode including dendrite and hydrogen evolution seriously degrade the performance of zinc batteries. Solid electrolyte interphase (SEI), which plays a key role in achieving high reversibility of lithium anode in aprotic organic solvent, is also beneficial to performance improvement of zinc anode in aqueous electrolyte. However, various studies about interphase for zinc electrode is quite fragmented, and lack of deep understanding on root causes or general design rules for SEI construction. And water molecules with high reactivity brings serious challenge to the effective SEI construction. Here, we reviewed the brief development history of zinc batteries firstly, then summarized the approaches to construct SEI in aqueous electrolyte. Furthermore, the formation mechanisms behind approaches are systematically analyzed, together with discussion on the SEI components and evaluation on electrochemical performance of zinc anode with various types of SEI. Meanwhile, the challenge between lab and industrialization are also discussed.

Abstract In photosynthesis, solar energy is harvested by photosensitizers, and then, the excited electrons transfer via a Z‐Scheme mode to enzymatic catalytic centers to trigger redox reactions. Herein, we constructed a core–shell Z‐scheme heterojunction of semiconductor@single‐atom catalysts (SACs). The oxygen‐vacancy‐rich ZnO core and single‐atom Co−N4 sites supported on nitrogen‐rich carbon shell (SA‐Co‐CN) act as the photosensitizer and the enzyme‐mimicking active centers, respectively. Driven by built‐in electric field across the heterojunction, photoexcited electrons could rapidly (2 ps) transfer from the n‐type ZnO core to the p‐type SA‐Co‐CN shell, finally boosting the catalytic performance of the surface‐exposed single‐atom Co−N4 sites for peroxymonosulfate (PMS) activation under light irradiation. The synergies between photocatalysis and heterogeneous Fenton‐like reaction lead to phenomenally enhanced production of various reactive oxygen species for rapid degradation of various microcontaminants in water. Experimental and theoretical results validate that the interfacial…

Abstract Photocatalytic water splitting and carbon dioxide (CO 2 ) reduction provide promising solutions to global energy and environmental issues. In recent years, metal‐organic frameworks (MOFs), a class of crystalline porous solids featuring well‐defined and tailorable structures as well as high surface areas, have captured great interest toward photocatalytic water splitting and CO 2 reduction. In this review, the semiconductor‐like behavior of MOFs is first discussed. We then summarize the recent advances in photocatalytic water splitting and CO 2 reduction over MOF‐based materials and focus on the unique advantage of MOFs for clarifying the structure‐property relationship in photocatalysis. In addition, some representative characterization techniques have been presented to unveil the photocatalytic kinetics and reaction intermediates in MOF‐based systems. Finally, the challenges, and perspectives for future directions are proposed.

Abstract In the evolving field of electrocatalysis, thermal treatment of nano‐electrocatalysts has become an essential strategy for performance enhancement. This review systematically investigates the impact of various thermal treatments on the catalytic potential of nano‐electrocatalysts. The focus encompasses an in‐depth analysis of the changes induced in structural, morphological, and compositional properties, as well as alterations in electro‐active surface area, surface chemistry, and crystal defects. By providing a comprehensive comparison of commonly used thermal techniques, such as annealing, calcination, sintering, pyrolysis, hydrothermal, and solvothermal methods, this review serves as a scientific guide for selecting the right thermal technique and favorable temperature to tailor the nano‐electrocatalysts for optimal electrocatalysis. The resultant modifications in catalytic activity are explored across key electrochemical reactions such as electrochemical (bio)sensing, catalytic degradation, oxygen reduction reaction, hydrogen evolution reaction, overall water splitting,…

Abstract Highly efficient hydrogen evolution reaction (HER) electrocatalyst will determine the mass distributions of hydrogen‐powered clean technologies, while still faces grand challenges. In this work, a synergistic ligand modulation plus Co doping strategy is applied to 1T−MoS2 catalyst via CoMo‐metal‐organic frameworks precursors, boosting the HER catalytic activity and durability of 1T−MoS2. Confirmed by Cs corrected transmission electron microscope and X‐ray absorption spectroscopy, the polydentate 1,2‐bis(4‐pyridyl)ethane ligand can stably link with two‐dimensional 1T−MoS2 layers through cobalt sites to expand interlayer spacing of MoS2 (Co−1T−MoS2‐bpe), which promotes active site exposure, accelerates water dissociation, and optimizes the adsorption and desorption of H in alkaline HER processes. Theoretical calculations indicate the promotions in the electronic structure of 1T−MoS2 originate in the formation of three‐dimensional metal‐organic constructs by linking π‐conjugated ligand, which weakens the hybridization between Mo‐3d and S‐2p orbitals, and in turn makes S‐2p…

Abstract A highly selective and durable oxygen evolution reaction (OER) electrocatalyst is the bottleneck for direct seawater splitting because of side reactions primarily caused by chloride ions (Cl − ). Most studies about OER catalysts in seawater focus on the repulsion of the Cl − to reduce its negative effects. Herein, we demonstrate that the absorption of Cl − on the specific site of a popular OER electrocatalyst, nickel‐iron layered double hydroxide (NiFe LDH), does not have a significant negative impact; rather, it is beneficial for its activity and stability enhancement in natural seawater. A set of in situ characterization techniques reveals that the adsorption of Cl − on the desired Fe site suppresses Fe leaching, and creates more OER‐active Ni sites, improving the catalyst's long‐term stability and activity simultaneously. Therefore, we achieve direct alkaline seawater electrolysis for the very first time on a commercial‐scale alkaline electrolyser (AE, 120 cm 2 electrode area) using the NiFe LDH anode. The new alkaline seawater electrolyser exhibits a reduction in…

Abstract Modulating the microenvironment of single‐atom catalysts (SACs) is critical to optimizing catalytic activity. Herein, we innovatively propose a strategy to improve the local reaction environment of Ru single atoms by precisely switching the crystallinity of the support from high crystalline and low crystalline, which significantly improves the hydrogen evolution reaction (HER) activity. The Ru single‐atom catalyst anchored on low‐crystalline nickel hydroxide (Ru−LC−Ni(OH)2) reconstructs the distribution balance of the interfacial ions due to the activation effect of metal dangling bonds on the support. Single‐site Ru with a low oxidation state induces the aggregation of hydronium ions (H3O+), leading to the formation of a local acidic microenvironment in alkaline media, breaking the pH‐dependent HER activity. As a comparison, the Ru single‐atom catalyst anchored on high‐crystalline nickel hydroxide (Ru−HC−Ni(OH)2) exhibits a sluggish Volmer step and a conventional local reaction environment. As expected, Ru−LC−Ni(OH)2 requires low overpotentials of 9 and 136 mV at 10 and…

Abstract Covalent organic frameworks (COFs) have attracted considerable attention as adsorbents for capturing and separating gold from electronic wastes. To enhance the binding capture efficiency, constructing hydrogen‐bond nanotraps along the pore walls was one of the most widely adopted approaches. However, the development of absorbing skeletons was ignored due to the weak binding ability of the gold salts (Au). Herein, we demonstrated skeleton engineering to construct highly efficiently absorbs for Au capture. The strong electronic donating feature of diarylamine units enhanced the electronic density of binding sites (imine‐linkage) and thus resulted in high capacities over 1750 mg g−1 for all three COFs. Moreover, the absorbing performance was further improved via the ionization of diarylamine units. The ionic COF achieved 90 % of the maximal adsorption capacity, 1.63 times of that from the charge‐neutral COF within ten minutes, and showed remarkable uptakes of 1834 mg g−1, exceptional selectivity (97.45 %) and cycling stability. The theoretical calculation revealed the binding…

Abstract Recent years have seen the emergence of capacitive deionization (CDI) as a promising desalination technique for converting sea and wastewater into potable water, due to its energy efficiency and eco‐friendly nature. However, its low salt removal capacity and parasitic reactions have limited its effectiveness. As a result, the development of porous carbon nanomaterials as electrode materials have been explored, while taking into account of material characteristics such as morphology, wettability, high conductivity, chemical robustness, cyclic stability, specific surface area, and ease of production. To tackle the parasitic reaction issue, membrane capacitive deionization (mCDI) was proposed which utilizes ion‐exchange membranes coupled to the electrode. Fabrication techniques along with the experimental parameters used to evaluate the desalination performance of different materials are discussed in this review to provide an overview of improvements made for CDI and mCDI desalination purposes

Abstract The oxygen reduction reaction (ORR) on transition single‐atom catalysts (SACs) is sustainable in energy‐conversion devices. However, the atomically controllable fabrication of single‐atom sites and the sluggish kinetics of ORR have remained challenging. Here, we accelerate the kinetics of acid ORR through a direct O−O cleavage pathway through using a bi‐functional ligand‐assisted strategy to pre‐control the distance of hetero‐metal atoms. Concretely, the as‐synthesized Fe−Zn diatomic pairs on carbon substrates exhibited an outstanding ORR performance with the ultrahigh half‐wave potential of 0.86 V vs. RHE in acid electrolyte. Experimental evidence and density functional theory calculations confirmed that the Fe−Zn diatomic pairs with a specific distance range of around 3 Å, which is the key to their ultrahigh activity, average the interaction between hetero‐diatomic active sites and oxygen molecules. This work offers new insight into atomically controllable SACs synthesis and addresses the limitations of the ORR dissociative mechanism.

Abstract Rational design of low‐cost and efficient transition‐metal catalysts for low‐temperature CO2 activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO2 methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO2 catalyst affords an excellent low‐temperature performance hitherto, with a CO2 conversion of 84.0 %, CH4 selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g−1 h−1 for 106 h, reflecting one of the best CO2 methanation performance to date on Ni‐based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re‐constructing monoclinic‐ZrO2 supported Ni species with abundant oxygen vacancies can facilitate CO2 activation, owing to the enhanced local electron density of Ni induced by the strong metal‐support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO2 emission abatement and beyond.

Abstract The positive liquid crystals, 4′‐heptyl‐4‐biphenylcarbonitrile (7CB), are used to functionalize carbon nanotubes (LC‐CNT), which can be aligned in the liquid crystalline polyimide (LC‐PI) matrix under an alternating electric field to fabricate the thermally conductive LC‐CNT/LC‐PI composite films. The efficient establishment of thermal conduction pathways in thermally conductive LC‐CNT/LC‐PI composite films with a low amount of LC‐CNT is achieved through the oriented alignment of LC‐CNT within the LC‐PI matrix. When the mass fraction of LC‐CNT is 15 wt %, the in‐plane thermal conductivity coefficient (λ∥) and the through‐plane thermal conductivity coefficient (λ⊥) of the LC‐CNT/LC‐PI composite films reach 4.02 W/(m ⋅ K) and 0.55 W/(m⋅K), which are 90.5 % and 71.9 % higher than those of the intrinsically thermally conductive LC‐PI films respectively, also 28.8 % and 5.8 % higher than those of the CNT/LC‐PI composite films respectively. Meanwhile, the thermally conductive LC‐CNT/LC‐PI composite films also possess excellent mechanical and heat resistance properties. The…

Abstract For zinc‐ion batteries (ZIBs), the non‐uniform Zn plating/stripping results in a high polarization and low Coulombic efficiency (CE), hindering the large‐scale application of ZIBs. Here, inspired by biomass seaweed plants, an anionic polyelectrolyte alginate acid (SA) was used to initiate the in situ formation of the high‐performance solid electrolyte interphase (SEI) layer on the Zn anode. Attribute to the anionic groups of −COO−, the affinity of Zn2+ ions to alginate acid induces a well‐aligned accelerating channel for uniform plating. This SEI regulates the desolvation structure of Zn2+ and facilitates the formation of compact Zn (002) crystal planes. Even under high depth of discharge conditions (DOD), the SA‐coated Zn anode still maintains a stable Zn stripping/plating behavior with a low potential difference (0.114 V). According to the classical nucleation theory, the nucleation energy for SA‐coated Zn is 97 % less than that of bare Zn, resulting in a faster nucleation rate. The Zn||Cu cell assembled with the SA‐coated electrode exhibits an outstanding average CE of…

Abstract Covalent organic framework (COF) membranes featuring uniform topological structures and devisable functions, show huge potential in water purification and molecular separation. Nevertheless, the inability of uniform COF membranes to be produced on an industrial scale and their nonenvironmentally friendly fabrication method are the bottleneck preventing their industrial applications. Herein, we report a new green and industrially adaptable scraping‐assisted interfacial polymerization (SAIP) technique to fabricate scalable and uniform TpPa COF membranes. The process used non‐toxic and low‐volatility ionic liquids (ILs) as organic phase instead of conventional organic solvents for interfacial synthesis of TpPa COF layer on a support membrane, which can simultaneously achieve the purposes of (i) improving the greenness of membrane‐forming process and (ii) fabricating a robust membrane that can function beyond the conventional membranes. This approach yields a large‐area, continuous COF membrane (19×25 cm2) with a thickness of 78 nm within a brief period of 2 minutes. The…

Abstract Pursuing high power density lithium metal battery with high safety is essential for developing next‐generation energy‐storage devices, but uncontrollable electrolyte degradation and the consequence formed unstable solid‐electrolyte interface (SEI) make the task really challenging. Herein, an ionic liquid (IL) confined MOF/Polymer 3D‐porous membrane was constructed for boosting in situ electrochemical transformations of Janus‐heterarchical LiF/Li 3 N‐rich SEI films on the nanofibers. Such a 3D‐Janus SEI‐incorporated into the separator offers fast Li + transport routes, showing superior room‐temperature ionic conductivity of 8.17×10 −4 S cm −1 and Li + transfer number of 0.82. The cryo‐TEM was employed to visually monitor the in situ formed LiF and Li 3 N nanocrystals in SEI and the deposition of Li dendrites, which is greatly benefit to the theoretical simulation and kinetic analysis of the structural evolution during the battery charge and discharge process. In particular, this membrane with high thermal stability and mechanical strength used in solid‐state Li||LiFePO 4 and…

Abstract The insufficient exciton (e−‐h+ pair) separation/transfer and sluggish two‐electron water oxidation are two main factors limiting the H2O2 photosynthetic efficiency of covalent organic frameworks (COFs) photocatalysts. Herein, we present an alternative strategy to simultaneously facilitate exciton separation/transfer and reduce the energy barrier of two‐electron water oxidation in COFs via a dicyano functionalization. The in situ characterization and theoretical calculations reveal that the dicyano functionalization improves the amount of charge transfer channels between donor and acceptor units from two in COF‐0CN without cyano functionalization to three in COF‐1CN with mono‐cyano functionalization and four in COF‐2CN with dicyano functionalization, leading to the highest separation/transfer efficiency in COF‐2CN. More importantly, the dicyano group activates the neighbouring C atom to produce the key *OH intermediate for effectively reducing the energy barrier of rate‐determining two‐electron water oxidation in H2O2 photosynthesis. The simultaneously enhanced exciton…

Abstract Singlet oxygen (1O2) is an excellent reactive oxygen species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to the huge dilemma in synthesizing single‐site type catalysts, the control and regulation of 1O2 generation in AOPs is still challenging and the underlying mechanism remains largely obscure. Here, taking advantage of the well‐defined and flexibly tunable sites of covalent organic frameworks (COFs), we report the first achievement in precisely regulating ROSs generation in peroxymonosulfate (PMS)‐based AOPs by site engineering of COFs. Remarkably, COFs with bipyridine units (BPY‐COFs) facilitate PMS activation via a nonradical pathway with 100 % 1O2, whereas biphenyl‐based COFs (BPD‐COFs) with almost identical structures activate PMS to produce radicals (⋅OH and SO4⋅−). The BPY‐COFs/PMS system delivers boosted performance for selective degradation of target pollutants from water, which is ca. 9.4 times that of its BPD‐COFs counterpart, surpassing most reported PMS‐based AOPs systems. Mechanism…

Abstract Solar‐driven CO2 reduction integrated with C−C/C−X bond‐forming organic synthesis represents a substantially untapped opportunity to simultaneously tackle carbon neutrality and create an atom‐/redox‐economical chemical synthesis. Herein, we demonstrate the first cooperative photoredox catalysis of efficient and tunable CO2 reduction to syngas, paired with direct alkylation/arylation of unactivated allylic sp3 C−H bonds for accessing allylic C−C products, over SiO2‐supported single Ni atoms‐decorated CdS quantum dots (QDs). Our protocol not only bypasses additional oxidant/reductant and pre‐functionalization of organic substrates, affording a broad of allylic C−C products with moderate to excellent yields, but also produces syngas with tunable CO/H2 ratios (1 : 2–5 : 1). Such win‐win coupling catalysis highlights the high atom‐, step‐ and redox‐economy, and good durability, illuminating the tantalizing possibility of a renewable sunlight‐driven chemical feedstocks manufacturing industry.

Abstract Utilizing weak interactions to effectively recover and separate precious metals in solution is of great importance but the practice remains a challenge. Herein, we report a novel strategy to achieve precise recognition and separation of gold by regulating the hydrogen‐bond (H‐bond) nanotrap within the pore of covalent organic frameworks (COFs). It is found that both COF‐HNU25 and COF‐HNU26 can efficiently capture AuIII with fast kinetics, high selectivity, and uptake capacity. In particular, the COF‐HNU25 with the high density of H‐bond nanotraps exhibits an excellent gold uptake capacity of 1725 mg g−1, which is significantly higher than that (219 mg g−1) of its isostructural COF (COF‐42) without H‐bond nanostrap in the pores. Importantly, the uptake capacity is strongly correlated to the number of H‐bonds between phenolic OH in the COF and [AuCl4]− in water, and multiple H‐bond interactions are the key driving force for the excellent gold recovery and reusability of the adsorbent.

Abstract Herein, we successfully construct bifunctional electrocatalysts by synthesizing atomically dispersed Fe−Se atom pairs supported on N‐doped carbon (Fe−Se/NC). The obtained Fe−Se/NC shows a noteworthy bifunctional oxygen catalytic performance with a low potential difference of 0.698 V, far superior to that of reported Fe‐based single‐atom catalysts. The theoretical calculations reveal that p‐d orbital hybridization around the Fe−Se atom pairs leads to remarkably asymmetrical polarized charge distributions. Fe−Se/NC based solid‐state rechargeable Zn‐air batteries (ZABs−Fe−Se/NC) present stable charge/discharge of 200 h (1090 cycles) at 20 mA cm−2 at 25 °C, which is 6.9 times of ZABs−Pt/C+Ir/C. At extremely low temperature of −40 °C, ZABs−Fe−Se/NC displays an ultra‐robust cycling performance of 741 h (4041 cycles) at 1 mA cm−2, which is about 11.7 times of ZABs−Pt/C+Ir/C. More importantly, ZABs−Fe−Se/NC could be operated for 133 h (725 cycles) even at 5 mA cm−2 at −40 °C.

Abstract Seawater electrolysis is an attractive way of making H2 in coastal areas, and NiFe‐based materials are among the top options for alkaline seawater oxidation (ASO). However, ample Cl− in seawater can severely corrode catalytic sites and lead to limited lifespans. Herein, we report that in situ carbon oxyanion self‐transformation (COST) from oxalate to carbonate on a monolithic NiFe oxalate micropillar electrode allows safeguard of high‐valence metal reaction sites in ASO. In situ/ex situ studies show that spontaneous, timely, and appropriate COST safeguards active sites against Cl− attack during ASO even at an ampere‐level current density (j). Our NiFe catalyst shows efficient and stable ASO performance, which requires an overpotential as low as 349 mV to attain a j of 1 A cm−2. Moreover, the NiFe catalyst with protective surface CO32− exhibits a slight activity degradation after 600 h of electrolysis under 1 A cm−2 in alkaline seawater. This work reports effective catalyst surface design concepts at the level of oxyanion self‐transformation, acting as a momentous step…

Abstract Cyclic peptides are fascinating molecules abundantly found in nature and exploited as molecular format for drug development as well as other applications, ranging from research tools to food additives. Advances in peptide technologies made over many years through improved methods for synthesis and drug development have resulted in a steady stream of new drugs, with an average of around one cyclic peptide drug approved per year. Powerful technologies for screening random peptide libraries, and de novo generating ligands, have enabled the development of cyclic peptide drugs independent of naturally derived molecules and now offer virtually unlimited development opportunities. In this review, we feature therapeutically relevant cyclic peptides derived from nature and discuss the unique properties of cyclic peptides, the enormous technological advances in peptide ligand development in recent years, and current challenges and opportunities for developing cyclic peptides that address unmet medical needs.

Abstract Extraction and recovery of lithium from reserves play a critical role in the sustainable development of energy due to the explosive growth of the lithium‐battery market. However, the low efficiency of extraction and recovery seriously threatens the sustainability of lithium supply. In this contribution, we fabricate a novel mechanically robust fluorine‐rich hydrogel, showing highly efficient Li+ extraction from Li‐containing solutions. The hydrogel was facilely fabricated by simple one‐pot polymerization of supramolecular nanosheets of fluorinated monomers, acrylic acid and a small amount of chemical crosslinkers. The hydrogel exhibits a remarkable lithium adsorption capacity (Qm Li+=122.3 mg g−1) and can be reused. Moreover, it can exclusively extract lithium ions from multiple co‐existing metal ions. Notably, the separation of Li+/Na+ in actual wastewater is achieved with a surprising separation factor of 153.72. The detailed characterizations as well as calculation showed that the specific coordination of Li−F plays a central role for both of the striking recovery…

Abstract The construction of high‐activity and low‐cost electrocatalysts is critical for efficient hydrogen production by water electrolysis. Herein, we developed an advanced electrocatalyst by anchoring well‐dispersed Ir nanoparticles on nickel metal‐organic framework (MOF) Ni‐NDC (NDC: 2,6‐naphthalenedicarboxylic) nanosheets. Benefiting from the strong synergy between Ir and MOF through interfacial Ni−O−Ir bonds, the synthesized Ir@Ni‐NDC showed exceptional electrocatalytic performance for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and overall water splitting in a wide pH range, superior to commercial benchmarks and most reported electrocatalysts. Theoretical calculations revealed that the charge redistribution of Ni−O−Ir bridge induced the optimization of H 2 O, OH* and H* adsorption, thus leading to the accelerated electrochemical kinetics for HER and OER. This work provides a new clue to exploit bifunctional electrocatalysts for pH‐universal overall water splitting.

Abstract Since the insight to fuse Fenton chemistry and nanomedicine into cancer therapy, great signs of progress have been made in the field of chemodynamic therapy (CDT). However, the exact mechanism of CDT is obscured by the unique tumor chemical environment and inevitable nanoparticle‐cell interactions, thus impeding further development. In this Scientific Perspective, the significance of CDT is clarified, the complex mechanism is deconstructed into primitive chemical and biological interactions, and the mechanism research directions based on the chemical kinetics and biological signaling pathways are discussed in detail. Moreover, beneficial outlooks are presented to enlighten the evolution of next‐generation CDT. Hopefully, this Scientific Perspective can inspire new ideas and advances for CDT and provide a reference for breaking down the interdisciplinary barriers in the field of nanomedicine.

Abstract Organic fluorophores are indispensable tools in cells, tissue and in vivo imaging, and have enabled much progress in the wide range of biological and biomedical fields. However, many available dyes suffer from insufficient performances, such as short absorption and emission wavelength, low brightness, poor stability, small Stokes shift, and unsuitable permeability, restricting their application in advanced imaging technology and complex imaging. Over the past two decades, many efforts have been made to improve these performances of fluorophores. Starting with the luminescence principle of fluorophores, this review clarifies the mechanisms of the insufficient performance for traditional fluorophores to a certain extent, systematically summarizes the modified approaches of optimizing properties, highlights the typical applications of the improved fluorophores in imaging and sensing, and indicates existing problems and challenges in this area. This progress not only proves the significance of improving fluorophores properties, but also provide a theoretical guidance for the…

Abstract While recent work demonstrates the advantages of weakly solvating solvents in enhancing the cyclability of LMBs, both new designs and design strategies for high performance weakly solvating solvent, especially physicochemical properties, are still lacking. Here, we propose a molecular design to tune the solvating power and physicochemical properties of non‐fluorinated ether solvent. The resulting cyclopentylmethyl ether (CPME) have a weak solvating power and wide liquid‐phase temperature range. By optimizing the salt concentration, the CE is further promoted to 99.4 %. Besides, the improved electrochemical performance of Li−S battery in CPME‐based electrolytes is obtained at −20 °C. The Li||LFP (17.6 mg cm−2) battery with developed electrolyte maintains >90 % of the original capacity over 400 cycles. Our design concept for solvent molecule provides a promising pathway to non‐fluorinated electrolytes with weakly solvating power and wide temperature window for high‐energy‐density LMBs.

Abstract Carbon quantum dots (CQDs) feature bright and tunable photoluminescence, solution processability, and low toxicity, showing great potential in optoelectronics. However, the large‐scale synthesis of CQDs with near‐unity photoluminescence quantum yield (PLQY) has not been achieved so far. In this study, we perform radical‐assisted synthesis of hexagon‐shaped CQDs (H‐CQDs) delivering near‐unity PLQY (96 %). Experimental and theoretical analyses revealed that the large vertically oriented transition dipole moment of H‐CQDs originating from high symmetry results in nearly 100 % PLQY. The H‐CQDs also exhibited a high electron mobility of up to 0.07 cm2 V−1 s−1. These properties enable the H‐CQD‐based light‐emitting diodes with a high external quantum efficiency of 4.6 % and a record maximum brightness of over 11 000 cd m−2. This study represents a significant advance that CQDs‐based electroluminescent device can be utilized for potential display and lighting applications.

Abstract The electrochemical effect of isotope (EEI) of water is introduced in the Zn‐ion batteries (ZIBs) electrolyte to deal with the challenge of severe side reactions and massive gas production. Due to the low diffusion and strong coordination of ions in D 2 O, the possibility of side reactions is decreased, resulting in a broader electrochemically stable potential window, less pH change, and less zinc hydroxide sulfate (ZHS) generation during cycling. Moreover, we demonstrate that D 2 O eliminates the different ZHS phases generated by the change of bound water during cycling because of the consistently low local ion and molecule concentration, resulting in a stable interface between the electrode and electrolyte. The full cells with D 2 O‐based electrolyte demonstrated more stable cycling performance which displayed ∼100 % reversible efficiencies after 1,000 cycles with a wide voltage window of 0.8–2.0 V and 3,000 cycles with a normal voltage window of 0.8–1.9 V at a current density of 2 A g −1 .

Abstract Heteroatom doping has emerged as a highly effective strategy to enhance the activity of metal‐based electrocatalysts toward the oxygen evolution reaction (OER). It is widely accepted that the doping does not switch the OER mechanism from the adsorbate evolution mechanism (AEM) to the lattice‐oxygen‐mediated mechanism (LOM), and the enhanced activity is attributed to the optimized binding energies toward oxygen intermediates. However, this seems inconsistent with the fact that the overpotential of doped OER electrocatalysts (<300 mV) is considerably smaller than the limit of AEM (>370 mV). To determine the origin of this inconsistency, we select phosphorus (P)‐doped nickel‐iron mixed oxides as the model electrocatalysts and observe that the doping enhances the covalency of the metal‐oxygen bonds to drive the OER pathway transition from the AEM to the LOM, thereby breaking the adsorption linear relation between *OH and *OOH in the AEM. Consequently, the obtained P‐doped oxides display a small overpotential of 237 mV at 10 mA cm−2. Beyond P, the similar pathway transition is…

Abstract The practical applications of two‐dimensional (2D) transition‐metal borides (MBenes) have been severely hindered by the lack of accessible MBenes because of the difficulties in the selective etching of traditional ternary MAB phases with orthorhombic symmetry (ort‐MAB). Here, we discover a family of ternary hexagonal MAB (h‐MAB) phases and 2D hexagonal MBenes (h‐MBenes) by ab initio predictions and experiments. Calculations suggest that the ternary h‐MAB phases are more suitable precursors for MBenes than the ort‐MAB phases. Based on the prediction, we report the experimental synthesis of h‐MBene HfBO by selective removal of In from h‐MAB Hf2InB2. The synthesized 2D HfBO delivered a specific capacity of 420 mAh g−1 as an anode material in lithium‐ion batteries, demonstrating the potential for energy‐storage applications. The discovery of this h‐MBene HfBO added a new member to the growing family of 2D materials and provided opportunities for a wide range of novel applications.

Abstract Designing novel single‐atom catalysts (SACs) supports to modulate the electronic structure is crucial to optimize the catalytic activity, but rather challenging. Herein, a general strategy is proposed to utilize the metalloid properties of supports to trap and stabilize single‐atoms with low‐valence states. A series of single‐atoms supported on the surface of tungsten carbide (M‐WC x , M=Ru, Ir, Pd) are rationally developed through a facile pyrolysis method. Benefiting from the metalloid properties of WC x , the single‐atoms exhibit weak coordination with surface W and C atoms, resulting in the formation of low‐valence active centers similar to metals. The unique metal‐metal interaction effectively stabilizes the low‐valence single atoms on the WC x surface and improves the electronic orbital energy level distribution of the active sites. As expected, the representative Ru‐WC x exhibits superior mass activities of 7.84 and 62.52 A mg Ru −1 for the hydrogen oxidation and evolution reactions (HOR/HER), respectively. In‐depth mechanistic analysis demonstrates that an ideal…

Abstract Dual‐atom catalysts (DACs) have been a new frontier in heterogeneous catalysis due to their unique intrinsic properties. The synergy between dual atoms provides flexible active sites, promising to enhance performance and even catalyze more complex reactions. However, precisely regulating active site structure and uncovering dual‐atom metal interaction remain grand challenges. In this review, we clarify the significance of the inter‐metal interaction of DACs based on the understanding of active center structures. Three diatomic configurations are elaborated, including isolated dual single‐atom, N/O‐bridged dual‐atom, and direct dual‐metal bonding interaction. Subsequently, the up‐to‐date progress in heterogeneous oxidation reactions, hydrogenation/dehydrogenation reactions, electrocatalytic reactions, and photocatalytic reactions are summarized. The structure‐activity relationship between DACs and catalytic performance is then discussed at an atomic level. Finally, the challenges and future directions to engineer the structure of DACs are discussed. This review will offer…

Abstract Amongst various Fenton‐like single‐atom catalysts (SACs), the zinc (Zn)‐related SACs have been barely reported due to the fully occupied 3d10configuration of Zn2+being inactive for the Fenton‐like reaction. Herein, the inert element Zn is turned into an active single‐atom catalyst (SA−Zn−NC) for Fenton‐like chemistry by forming an atomic Zn−N4coordination structure. The SA−Zn−NC shows admirable Fenton‐like activity in organic pollutant remediation, including self‐oxidation and catalytic degradation by superoxide radical (O2⋅−) and singlet oxygen (1O2). Experimental and theoretical results unveiled that the single‐atomic Zn−N4site with electron acquisition can transfer electrons donated by electron‐rich pollutants and low‐concentration PMS toward dissolved oxygen (DO) to actuate DO reduction into O2⋅−and successive conversion into1O2. This work inspires an exploration of efficient and stable Fenton‐like SACs for sustainable and resource‐saving environmental applications.

Abstract Metallic conductive 1T phase molybdenum sulfide (MoS 2 ) has been identified as promising anode for sodium ion (Na + ) batteries, but its metastable feature makes it difficult to obtain and its restacking during the charge/discharge processing result in part capacity reversibility. Herein, a synergetic effect of atomic‐interface engineering is employed for constructing 2H‐MoS 2 layers assembled on single atomically dispersed Fe−N−C (SA Fe−N−C) anode material that boosts its reversible capacity. The work‐function‐driven‐electron transfer occurs from SA Fe−N−C to 2H‐MoS 2 via the Fe−S bonds, which enhances the adsorption of Na + by 2H‐MoS 2 , and lays the foundation for the sodiation process. A phase transfer from 2H to 1T/2H MoS 2 with the ferromagnetic spin‐polarization of SA Fe−N−C occurs during the sodiation/desodiation process, which significantly enhances the Na + storage kinetics, and thus the 1T/2H MoS 2 /SA Fe−N−C display a high electronic conductivity and a fast Na + diffusion rate.

Abstract The electrochemical conversion of nitrate pollutants into value‐added ammonia is a feasible way to achieve artificial nitrogen cycle. However, the development of electrocatalytic nitrate‐to‐ammonia reduction reaction (NO 3 − RR) has been hampered by high overpotential and low Faradaic efficiency. Here we develop an iron single‐atom catalyst coordinated with nitrogen and phosphorus on hollow carbon polyhedron (denoted as Fe−N/P−C) as a NO 3 − RR electrocatalyst. Owing to the tuning effect of phosphorus atoms on breaking local charge symmetry of the single‐Fe‐atom catalyst, it facilitates the adsorption of nitrate ions and enrichment of some key reaction intermediates during the NO 3 − RR process. The Fe−N/P−C catalyst exhibits 90.3 % ammonia Faradaic efficiency with a yield rate of 17980 μg h −1 mg cat −1 , greatly outperforming the reported Fe‐based catalysts. Furthermore, operando SR‐FTIR spectroscopy measurements reveal the reaction pathway based on key intermediates observed under different applied potentials and reaction durations. Density functional theory calculations…

Abstract The keto‐switched photocatalysis of covalent organic frameworks (COFs) for efficient H2 evolution was reported for the first time by engineering, at a molecular level, the local structure and component of the skeletal building blocks. A series of imine‐linked BT‐COFs were synthesized by the Schiff‐base reaction of 1, 3, 5‐benzenetrialdehyde with diamines to demonstrate the structural reconstruction of enol to keto configurations by alkaline catalysis. The keto groups of the skeletal building blocks served as active injectors, where hot π‐electrons were provided to Pt nanoparticles (NPs) across a polyvinylpyrrolidone (PVP) insulting layer. The characterization results, together with density functional theory calculations, indicated clearly that the formation of keto‐injectors not only made the conduction band level more negative, but also led to an inhomogeneous charge distribution in the donor‐acceptor molecular building blocks to form a strong intramolecular built‐in electric field. As a result, visible‐light photocatalysis of TP‐COFs‐1 with one keto group in the skeletal…

Abstract Thermally activated delayed fluorescence (TADF) materials have attracted great potential in the field of organic light‐emitting diodes (OLEDs). Among thousands of TADF materials, highly twisted TADF emitters have become a hotspot in recent years. Compared with traditional TADF materials, highly twisted TADF emitters tend to show multi‐channel charge‐transfer characters and form rigid molecular structures. This is advantageous for TADF materials, as non‐radiative decay processes can be suppressed to facilitate efficient exciton utilization. Accordingly, OLEDs with excellent device performances have also been reported. In this Review, we have summarized recent progress in highly twisted TADF materials and related devices, and give an overview of the molecular design strategies, photophysical studies, and the performances of OLED devices. In addition, the challenges and perspectives of highly twisted TADF molecules and the related OLEDs are also discussed.

Abstract Nanozymes, nanomaterials with enzyme‐mimicking activity, have attracted tremendous interest in recent years owing to their ability to replace natural enzymes in various biomedical applications, such as biosensing, therapeutics, drug delivery, and bioimaging. In particular, the nanozymes capable of regulating the cellular redox status by mimicking the antioxidant enzymes in mammalian cells are of great therapeutic significance in oxidative‐stress‐mediated disorders. As the distinction of physiological oxidative stress (oxidative eustress) and pathological oxidative stress (oxidative distress) occurs at a fine borderline, it is a great challenge to design nanozymes that can differentially sense the two extremes in cells, tissues and organs and mediate appropriate redox chemical reactions. In this Review, we summarize the advances in the development of redox‐active nanozymes and their biomedical applications. We primarily highlight the therapeutic significance of the antioxidant and prooxidant nanozymes in various disease model systems, such as cancer, neurodegeneration, and…

Abstract Alkaline polymer electrolytes (APEs) are essential materials for alkaline energy conversion devices such as anion exchange membrane fuel cells (AEMFCs) and water electrolyzers (AEMWEs). Here, we report a series of branched poly(aryl‐co‐aryl piperidinium) with different branching agents (triptycene: highly‐rigid, three‐dimensional structure; triphenylbenzene: planar, two‐dimensional structure) for high‐performance APEs. Among them, triptycene branched APEs showed excellent hydroxide conductivity (193.5 mS cm−1@80 °C), alkaline stability, mechanical properties, and dimensional stability due to the formation of branched network structures, and increased free volume. AEMFCs based on triptycene‐branched APEs reached promising peak power densities of 2.503 and 1.705 W cm−2 at 75/100 % and 30/30 % (anode/cathode) relative humidity, respectively. In addition, the fuel cells can run stably at a current density of 0.6 A cm−2 for 500 h with a low voltage decay rate of 46 μV h−1. Importantly, the related AEMWE achieved unprecedented current densities of 16 A cm−2 and 14.17 A cm−2 (@2…

Abstract Rational design of efficient, stable, and inexpensive bifunctional electrocatalysts for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) is a key challenge to realize green hydrogen production via electrolytic water splitting. Herein, Ru nanoparticles and FeNi alloy heterojunction catalyst (Ru−FeNi@NLC) encapsulated via lignin‐derived carbon was prepared by self‐assembly precipitation and in situ pyrolysis. The designed catalyst displays excellent performance at 10 mA cm −2 with low overpotentials of 36 mV for HER and 198 mV for OER, and only needs 1.48 V for overall water splitting. Results and DFT calculations show the unique N‐doped lignin‐derived carbon layer and Ru−FeNi heterojunction contribute to optimized electronic structure for enhancing electron transfer, balanced free energy of reactants and intermediates in the sorption/desorption process, and significantly reduced reaction energy barrier for the HER and OER rate‐determining steps, thus improved reaction kinetics. This work provides a new in situ pyrolysis doping strategy based on…

Abstract Rational engineering active sites and vantage defects of catalysts are promising but grand challenging task to enhance photoreduction CO2 to high value‐added C2 products. In this study, we designed an N,S‐codoped Fe‐based MIL‐88B catalyst with well‐defined bipyramidal hexagonal prism morphology via a facile and effective process, which was synthesized by addition of appropriate 1,2‐benzisothiazolin‐3‐one (BIT) and acetic acid to the reaction solution. Under simulated solar irradiation, the designed catalyst exhibits high C2H4 evolution yield of 17.7 μmol g−1⋅h, which has been rarely achieved in photocatalytic CO2 reduction process. The synergistic effect of Fe‐N coordinated sites and reasonable defects in the N,S‐codoped photocatalyst can accelerate the migration of photogenerated carriers, resulting in high electron density, and this in turn helps to facilitate the formation and dimerization of C−C coupling intermediates for C2H4 effectively.

Abstract Electrochemical reduction of nitrate waste is promising for environmental remediation and ammonia preparation. This process includes multiple hydrogenation steps, and thus the active hydrogen behavior on the surface of the catalyst is crucial. The crystal phase referred to the atomic arrangements in crystals has a great effect on active hydrogen, but the influence of the crystal phase on nitrate reduction is still unclear. Herein, enzyme‐mimicking MoS 2 in different crystal phases (1T and 2H) are used as models. The Faradaic efficiency of ammonia reaches ≈90 % over 1T‐MoS 2 , obviously outperforming that of 2H‐MoS 2 (27.31 %). In situ Raman spectra and theoretical calculations reveal that 1T‐MoS 2 produces more active hydrogen on edge S sites at a more positive potential and conducts an effortless pathway from nitrate to ammonia instead of multiple energetically demanding hydrogenation steps (such as *HNO to *HNOH) performed on 2H‐MoS 2 .

Abstract Understanding the nature of single‐atom catalytic sites and identifying their spectroscopic fingerprints are essential prerequisites for the rational design of target catalysts. Here, we apply correlated in situ X‐ray absorption and infrared spectroscopy to probe the edge‐site‐specific chemistry of Co−N−C electrocatalyst during the oxygen reduction reaction (ORR) operation. The unique edge‐hosted architecture affords single‐atom Co site remarkable structural flexibility with adapted dynamic oxo adsorption and valence state shuttling between Co (2−δ)+ and Co 2+ , in contrast to the rigid in‐plane embedded Co 1 −N x counterpart. Theoretical calculations demonstrate that the synergistic interplay of in situ reconstructed Co 1 −N 2 ‐oxo with peripheral oxygen groups gives a rise to the near‐optimal adsorption of *OOH intermediate and substantially increases the activation barrier for its dissociation, accounting for a robust acidic ORR activity and 2e − selectivity for H 2 O 2 production.

Abstract The slow water dissociation process in alkaline electrolyte severely limits the kinetics of HER. The orientation of H 2 O is well known to affect the dissociation process, but H 2 O orientation is hard to control because of its random distribution. Herein, an atomically asymmetric local electric field was designed by IrRu dizygotic single‐atom sites (IrRu DSACs) to tune the H 2 O adsorption configuration and orientation, thus optimizing its dissociation process. The electric field intensity of IrRu DSACs is over 4.00×10 10 N/C. The ab initio molecular dynamics simulations combined with in situ Raman spectroscopy analysis on the adsorption behavior of H 2 O show that the M−H bond length (M=active site) is shortened at the interface due to the strong local electric field gradient and the optimized water orientation promotes the dissociation process of interfacial water. This work provides a new way to explore the role of single atomic sites in alkaline hydrogen evolution reaction.

Abstract Transition‐metal‐based oxyhydroxides are efficient catalysts in biomass electrooxidation towards fossil‐fuel‐free production of valuable chemicals. However, identification of active sites remains elusive. Herein, using cobalt oxyhydroxide (CoOOH) as the archetype and the electrocatalyzed glucose oxidation reaction (GOR) as the model reaction, we track dynamic transformation of the electronic and atomic structure of the catalyst using a suite of operando and ex situ techniques. We reveal that two types of reducible Co3+‐oxo species are afforded for the GOR, including adsorbed hydroxyl on Co3+ ion (μ1‐OH−Co3+) and di‐Co3+‐bridged lattice oxygen (μ2‐O−Co3+). Moreover, theoretical calculations unveil that μ1‐OH−Co3+ is responsible for oxygenation, while μ2‐O−Co3+ mainly contributes to dehydrogenation, both as key oxidative steps in glucose‐to‐formate transformation. This work provides a framework for mechanistic understanding of the complex near‐surface chemistry of metal oxyhydroxides in biomass electrorefining.

Abstract Solid‐state lithium‐metal batteries are considered as the next generation of high‐energy‐density batteries. However, their solid electrolytes suffer from low ionic conductivity, poor interface performance, and high production costs, restricting their commercial application. Herein, a low‐cost cellulose acetate‐based quasi‐solid composite polymer electrolyte (C‐CLA QPE) was developed with a high Li+ transference number ( ) of 0.85 and excellent interface stability. The prepared LiFePO4 (LFP)|C‐CLA QPE|Li batteries exhibited excellent cycle performance with a capacity retention of 97.7 % after 1200 cycles at 1 C and 25 °C. The experimental results and Density Function Theory (DFT) simulation revealed that the partially esterified side groups in the CLA matrix contribute to the migration of Li+ and enhance electrochemical stability. This work provides a promising strategy for fabricating cost‐effective, stable polymer electrolytes for solid‐state lithium batteries.

Abstract Nanozymes aim to mimic the highly evolved active centers of natural enzymes. Despite progress in nanozyme engineering, their catalytic performance is much less favorable compared with natural enzymes. This study shows that precise control over the atomic configuration of the active centers of Co single‐atom nanozymes (SAzymes) enables the rational regulation of their catalase‐like performance guided by theorical calculations. The constructed Co‐N3PS SAzyme exhibits an excellent catalase‐like activity and kinetics, exceeding the representative controls of Co‐based SAzymes with different atomic configurations. Moreover, we developed an ordered structure‐oriented coordination design strategy for rationally engineering SAzymes and established a correlation between the structure and enzyme‐like performance. This work demonstrates that precise control over the active centers of SAzymes is an efficient strategy to mimic the highly evolved active sites of natural enzymes.

Abstract Synergy engineering is an important way to enhance the kinetic activity of oxygen‐evolution‐reaction (OER) electrocatalysts. Here, we fabricated NiFe amorphous nanoreactor (NiFe‐ANR) oxide as OER electrocatalysts via a mild self‐catalytic reaction. Firstly, the amorphousness helps transform NiFe‐ANR into highly active hydroxyhydroxides, and its many fine‐grain boundaries increase active sites. More importantly, as proved by experiments and finite element analysis, the nanoreactor structure alters the spatial curvature and the mass transfer over the catalyst, thereby enriching OH− in the catalyst surface and inner part. Thus, the catalyst with the structure of amorphous nanoreactors gained excellent activity, far superior to the NiFe catalyst with the structure of crystalline nanoreactor or amorphous non‐nanoreactor. This work provides new insights into the applications and mechanisms of amorphousness and nanoreactors, embodying the “1+1>2” synergy of crystalline state and morphology.

Abstract Manganese‐rich layered oxide cathodes of sodium‐ion batteries (SIBs) are extremely promising for large‐scale energy storage owing to their high capacities and cost effectiveness, while the Jahn–Teller (J–T) distortion and low operating potential of Mn redox largely hinder their practical applications. Herein, we reveal that annealing in argon rather than conventional air is a universal strategy to comprehensively upgrade the Na‐storage performance of Mn‐based oxide cathodes. Bulk oxygen vacancies are introduced via this method, leading to reduced Mn valence, lowered Mn 3 d‐ orbital energy level, and formation of the new‐concept Mn domains. As a result, the energy density of the model P2‐Na 0.75 Mg 0.25 Mn 0.75 O 2 cathode increases by ≈50 % benefiting from the improved specific capacity and operating potential of Mn redox. The Mn domains can disrupt the cooperative J–T distortion, greatly promoting the cycling stability. This exciting finding opens a new avenue towards high‐performance Mn‐based oxide cathodes for SIBs.

Abstract 3,4,9,10‐Perylenetetracarboxylic dianhydride (PDI) is one of the best n‐type organic semiconductors and an ideal light‐driven catalyst for lignin depolymerization. However, the charge localization effect and the excessively strong intermolecular aggregation trend in PDI result in rapid electron‐hole (e − −h + ) recombination, which limits photocatalytic performance. Herein, polymeric carbon nitride/polyhedral oligomeric silsesquioxane PDI (p‐CN/P‐PDI) S‐scheme heterojunction photocatalyst was prepared by the solvent evaporation‐deposition method for C−C bond selective cleavage of lignin β‐O‐4 model. Based on the material characterization results, the synergic role of polyhedral oligomeric silsesquioxane (POSS) and S‐scheme heterojunction maintains appropriate aggregation domains, achieves better solar light utilization, faster charge‐transfer efficiency, and greater redox capacity. Notably, the 3 % p‐CN/P‐PDI heterostructure exhibits a remarkable enhancement in cleavage conversion efficiency, achieving approximately 16.42 and 2.57 times higher conversion rates compared to…

Abstract The great success of controlled radical polymerizations has encouraged researchers to develop more facile and robust approaches for surface‐initiated polymerizations (SIPs) to fabricate polymer brushes, even for non‐experts. In recent years, external‐stimuli‐mediated radical polymerization methods have come to the fore as SIPs because of their less rigorous synthetic procedures and high controllability, which expand the opportunities for synthesizing macromolecules with desired chemical compositions and structures, as well as tailor‐made polymers and bioconjugates that show broad applicability and physiological compatibility. This review discusses the latest developments in surface‐initiated polymerization methods, in particular, external‐stimuli mediated atom transfer radical polymerization (ATRP), photo‐induced polymerizations, and reversible addition‐fragmentation chain transfer (RAFT) polymerization, as well as other methods and their combination for the application in surface grafting. The implementation of these methods is of great interest due to their unique…

Abstract Ammonium‐ion batteries (AIBs) have recently attracted increasing attention in the field of aqueous batteries owing to their high safety and fast diffusion kinetics. The NH4+storage mechanism is quite different from that of spherical metal ions (e.g. Li+, Na+, K+, Mg2+, and Zn2+) because of the formation of hydrogen bonds between NH4+and host materials. Although many materials have been proposed as electrode materials for AIBs, their performances hardly meet the requirement of future electrochemical energy storage devices. It is thus urgent to design and exploit advanced materials for AIBs. This review highlights the state‐of‐the‐art research on AIBs. The insights into the basic configuration, operating mechanism and recent progress of electrode materials and corresponding electrolytes for AIBs have been comprehensively outlined. The electrode materials are classified and compared according to different NH4+storage behaviour in the structure. The challenges, design strategies and perspectives are also discussed for the future development of AIBs.

Abstract All‐solid‐state batteries (ASSBs) with inorganic solid electrolytes (SEs) have attracted significant interest as next‐generation energy storage. Halides such as Li3YCl6are promising candidates for SE because they combine high oxidation stability and deformability. However, the ionic conductivities of halide SEs are not as high as those of other SEs, especially sulfides. Here, we discover new lithium‐metal‐oxy‐halide materials, LiMOCl4(M=Nb, Ta). They exhibit extremely high ionic conductivities of 10.4 mS cm−1forM=Nb and 12.4 mS cm−1forM=Ta, respectively, even in cold‐pressed powder forms at room temperature, which are comparable to or surpass those of organic liquid electrolytes used in lithium‐ion batteries. Bulk‐type ASSB cells using the oxyhalides as the cathode SE demonstrate an outstanding rate capability with a capacity retention of 80 % at 5 C/0.1 C. We believe that the proposed oxyhalides are promising SE candidates for the practical applications of ASSBs.

Abstract Lithium–sulfur (Li−S) batteries are promising due to ultrahigh theoretical energy density. However, their cycling lifespan is crucially affected by the electrode kinetics of lithium polysulfides. Herein, the polysulfide solvation structure is correlated with polysulfide electrode kinetics towards long‐cycling Li−S batteries. The solvation structure derived from strong solvating power electrolyte induces fast anode kinetics and rapid anode failure, while that derived from weak solvating power electrolyte causes sluggish cathode kinetics and rapid capacity loss. By contrast, the solvation structure derived from medium solvating power electrolyte balances cathode and anode kinetics and improves the cycling performance of Li−S batteries. Li−S coin cells with ultra‐thin Li anodes and high‐S‐loading cathodes deliver 146 cycles and a 338 Wh kg−1 pouch cell undergoes stable 30 cycles. This work clarifies the relationship between polysulfide solvation structure and electrode kinetics and inspires rational electrolyte design for long‐cycling Li−S batteries.

Abstract Poly (triazine imide) (PTI/Li+Cl−), one of the crystalline versions of polymeric carbon nitrides, holds great promise for photocatalytic overall water splitting. In principle, the photocatalytic activity of PTI/Li+Cl− is closely related to the morphology, which could be reasonably tailored by the modulation of the polycondensation process. Herein, we demonstrate that the hexagonal prisms of PTI/Li+Cl− could be converted to hexagonal nanosheets by adjusting the binary eutectic salts from LiCl/KCl or NaCl/LiCl to ternary LiCl/KCl/NaCl. Results reveal that the extension of in‐plane conjugation is preferred, when the polymerisation was performed in the presence of ternary eutectic salts. The hexagonal nanosheets bears longer lifetimes of charge carriers than that of hexagonal prisms due to lower intensity of structure defects and shorter hopping distance of charge carriers along the stacking direction of triazine nanosheets. The optimized hexagonal nanosheets exhibits a record apparent quantum yield value of 25 % (λ=365 nm) for solar hydrogen production by one‐step excitation…

Abstract Carbonyl functional materials as additives are extensively applied to reduce the defects density of the perovskite film. However, there is still a lack of comprehensive understanding for the effect of carbonyl additives to improve device performance. In this work, we systematically study the effect of carbonyl additive molecules on the passivation of defects in perovskite films. After a comprehensive investigation, the results confirm the importance of molecular dipole in amplifying the passivation effect of additive molecules. The additive with strong molecular dipole possesses the advantages of enhancing the efficiency and stability of perovskite solar cells (PSCs). After optimization, the companion efficiency of PSCs is 23.20 %, and it can maintain long‐term stability under harsh conditions. Additionally, a large‐area solar cell module‐modified DLBA was 20.18 % (14 cm 2 ). This work provides an important reference for the selection and designing of efficient carbonyl additives.

Abstract Single‐ion conductive electrolytes can largely eliminate electrode polarization, reduce the proportion of anion migration and inhibit side reactions in batteries. However, they usually suffer from insufficient ion conductivity due to the strong interaction between cations and cationic receptors. Here we report an ultrafast light‐responsive covalent organic frameworks (COF) with sulfonic acid groups modification as the acrylamide polymerization initiator. Benefiting from the reduced electrostatic interaction between Zn2+ and sulfonic acid groups through solvation effects, the as‐prepared COF‐based hydrogel electrolyte (TCOF‐S‐Gel) receives an ion conductivity of up to 27.2 mS/cm and Zn2+ transference number of up to 0.89. In addition, sufficient hydrogen bonds endow the single‐ion conductive TCOF‐S‐Gel electrolyte to have good water retention and superb mechanical properties. The assembled Zn||TCOF‐S‐Gel||MnO2 full zinc‐ion battery exhibits high discharge capacity (248 mAh/g at 1C), excellent rate capability (90 mAh/g at 10C) and superior cycling performance. These enviable…

Abstract Covalent organic frameworks (COFs), possessing pre‐designable structures and tailorable functionalities, are promising candidates for photocatalysis. Nevertheless, the most studied imine‐linked COFs (Im‐COFs) usually suffer from unsatisfactory stability and photocatalytic performance. To meet this challenge, a series of highly stable enaminone‐linked COFs (En‐COFs) have been synthesized and afford much improved visible‐light‐driven hydrogen production activities, ranging from 44 to 1078 times that of isoreticular Im‐COFs, with the only difference being the linkages (enaminone vs. imine) in their structures. The enhanced light‐harvesting ability, facilitated exciton dissociation and improved chemical stability account for the superior activity. Furthermore, quinoline‐linked COFs (Qu‐COFs) have been further obtained via the post‐modification of Im‐COFs. Compared with Im‐COFs, the photocatalytic activities of Qu‐COFs are significantly improved after modification, but still below those of the corresponding En‐COFs (3–107 times). The facile synthesis, excellent activity, and…

Abstract To date, the chemical conversion of organic pollutants into value‐added chemical feedstocks rather than CO 2 remains a major challenge. Herein, we successfully developed a coupled piezocatalytic and advanced oxidation processes (AOPs) system for achieving the conversion of various organic pollutants to CO. The CO product stems from the specific process in which organics are first oxidized to carbonate through peroxymonosulfate (PMS)‐based AOPs, and then the as‐obtained carbonate is converted into CO by piezoelectric reduction under ultrasonic (US) vibration by using a Co 3 S 4 /MoS 2 catalyst. Experiments and DFT calculations show that the introduction of Co 3 S 4 not only effectively promotes the transfer and utilization of piezoelectric electrons but also realizes highly selective conversion from carbonate to CO. The Co 3 S 4 /MoS 2 /PMS system has achieved selective generation of CO in actual complex wastewater treatment for the first time, indicating its potential practical applicability.

Abstract Nickel‐based catalysts have been regarded as one of the most promising electrocatalysts for urea oxidation reaction (UOR), however, their activity is largely limited by the inevitable self‐oxidation reaction of Ni species (NSOR) during the UOR. Here, we proposed an interface chemistry modulation strategy to trigger the occurrence of UOR before the NSOR via constructing a 2D/2D heterostructure that consists of ultrathin NiO anchored Ru−Co dual‐atom support (Ru‐Co DAS/NiO). Operando spectroscopic characterizations confirm this unique triggering mechanism on the surface of Ru‐Co DAS/NiO. Consequently, the fabricated catalyst exhibits outstanding UOR activity with a low potential of 1.288 V at 10 mA cm −2 and remarkable long‐term durability for more than 330 h operation. DFT calculations and spectroscopic characterizations demonstrate that the favorable electronic structure induced by this unique heterointerface endows the catalyst energetically more favorable for the UOR than the NSOR.

Abstract The electrochemical NO 3 − reduction and its coupling with CO 2 can provide novel and clean routes to synthesize NH 3 and urea, respectively. However, their practical application is still impeded by the lack of efficient catalysts with desirable Faradaic efficiency (FE) and yield rate. Herein, we report the synthesis of molybdenum oxide nanoclusters anchored on carbon black (MoO x /C) as electrocatalyst. It affords an outstanding FE of 98.14 % and NH 3 yield rate of 91.63 mg h −1 mg cat. −1 in NO 3 − reduction. Besides, the highest FE of 27.7 % with a maximum urea yield rate of 1431.5 μg h −1 mg cat. −1 toward urea is also achieved. The formation of electron‐rich MoO x nanoclusters with highly unsaturated metal sites in the MoO x /C heterostructure is beneficial for enhanced catalytic performance. Studies on the mechanism reveal that the stabilization of *NO and *CO 2 NOOH intermediates are critical for the NH 3 and urea synthesis, respectively.

Abstract Simultaneous optimization of the energy level of water dissociation, hydrogen and hydroxide desorption is the key to achieving fast kinetics for the alkaline hydrogen evolution reaction (HER). Herein, the well‐dispersed Ru clusters on the surface of amorphous/crystalline CeO2‐δ (Ru/ac‐CeO2‐δ) is demonstrated to be an excellent electrocatalyst for significantly boosting the alkaline HER kinetics owing to the presence of unique oxygen vacancy (VO) and Ru Lewis acid–base pairs (LABPs). The representative Ru/ac‐CeO2‐δ exhibits an outstanding mass activity of 7180 mA mgRu−1 that is approximately 9 times higher than that of commercial Pt/C at the potential of −0.1 V (V vs RHE) and an extremely low overpotential of 21.2 mV at a geometric current density of 10 mA cm−2. Experimental and theoretical studies reveal that the VO as Lewis acid sites facilitate the adsorption of H2O and cleavage of H‐OH bonds, meanwhile, the weak Lewis basic Ru clusters favor for the hydrogen desorption. Importantly, the desorption of OH from VO sites is accelerated via a water‐assisted proton exchange…

Abstract Smart fluorescent materials that can respond to environmental stimuli are of great importance in the fields of information encryption and anti‐counterfeiting. However, traditional fluorescent materials usually face problems such as lack of tunable fluorescence and insufficient surface‐adaptive adhesion, hindering their practical applications. Herein, inspired by the glowing sucker octopus, we present a novel strategy to fabricate a reversible fluorescent eutectogel with high transparency, adhesive and self‐healing performance for conformal information encryption and anti‐counterfeiting. Using anthracene as luminescent unit, the eutectogel exhibits photoswitchable fluorescence and can therefore be reversibly written/erased with patterns by non‐contact stimulation. Additionally, different from mechanically irreversible adhesion via glue, the eutectogel can adhere to various irregular substrates over a wide temperature range (−20 to 65 °C) and conformally deform more than 1000 times without peeling off. Furthermore, by exploiting surface‐adaptive adhesion, high transparency…

Abstract The deployment of lithium metal anode in solid‐state batteries with polymer electrolytes has been recognized as a promising approach to achieving high‐energy‐density technologies. However, the practical application of the polymer electrolytes is currently constrained by various challenges, including low ionic conductivity, inadequate electrochemical window, and poor interface stability. To address these issues, a novel eutectic‐based polymer electrolyte consisting of succinonitrile (SN) and poly (ethylene glycol) methyl ether acrylate (PEGMEA) is developed. The research results demonstrate that the interactions between SN and PEGMEA promote the dissociation of the lithium difluoro(oxalato) borate (LiDFOB) salt and increase the concentration of free Li+. The well‐designed eutectic‐based PAN1.2‐SPE (PEGMEA: SN=1: 1.2 mass ratio) exhibits high ionic conductivity of 1.30 mS cm−1 at 30 °C and superior interface stability with Li anode. The Li/Li symmetric cell based on PAN1.2‐SPE enables long‐term plating/stripping at 0.3 and 0.5 mA cm−2, and the Li/LiFePO4 cell achieves…

Abstract Stable Zn anodes with a high utilization efficiency pose a challenge due to notorious dendrite growth and severe side reactions. Therefore, electrolyte additives are developed to address these issues. However, the additives are always consumed by the electrochemical reactions over cycling, affecting the cycling stability. Here, hexamethylphosphoric triamide (HMPA) is reported as an electrolyte additive for achieving stable cycling of Zn anodes. HMPA reshapes the solvation structures and promotes anion decomposition, leading to the in situ formation of inorganic‐rich solid‐electrolyte‐interphase. More interestingly, this anion decomposition does not involve HMPA, preserving its long‐term impact on the electrolyte. Thus, the symmetric cells with HMPA in the electrolyte survive ≈500 h at 10 mA cm−2 for 10 mAh cm−2 or ≈200 h at 40 mA cm−2 for 10 mAh cm−2 with a Zn utilization rate of 85.6 %. The full cells of Zn||V2O5 exhibit a record‐high cumulative capacity even under a lean electrolyte condition (E/C ratio=12 μL mAh−1), a limited Zn supply (N/P ratio=1.8) and a high areal…

Abstract Rechargeable lithium batteries are one of the most appropriate energy storage systems in our electrified society, as virtually all portable electronic devices and electric vehicles today rely on the chemical energy stored in them. However, sub‐zero Celsius operation, especially below −20 °C, remains a huge challenge for lithium batteries and greatly limits their application in extreme environments. Slow Li+diffusion and charge transfer kinetics have been identified as two main origins of the poor performance of RLBs under low‐temperature conditions, both strongly associated with the liquid electrolyte that governs bulk and interfacial ion transport. In this review, we first analyze the low‐temperature kinetic behavior and failure mechanism of lithium batteries from an electrolyte standpoint. We next trace the history of low‐temperature electrolytes in the past 40 years (1983–2022), followed by a comprehensive summary of the research progress as well as introducing the state‐of‐the‐art characterization and computational methods for revealing their underlying mechanisms.…

Abstract Nickel‐rich (Ni≥90 %) layered cathodes are critical materials for achieving higher‐energy‐density and lower‐cost next‐generation Li‐ion batteries (LIBs). However, their bulk and interface structural instabilities significantly impair their electrochemical performance, thus hindering their widespread adoption in commercial LIBs. Exploiting Ti and Mo diffusion chemistry, we report one‐step calcination to synthesize bulk‐to‐surface modified LiNi 0.9 Co 0.09 Mo 0.01 O 2 (NCMo90) featuring a 5 nm Li 2 TiO 3 coating on the surface, a Mo‐rich Li + /Ni 2+ superlattice at the sub‐surface, and Ti‐doping in the bulk. Such a multi‐functional structure effectively maintains its structural integrity upon cycling. As a result, such NCMo90 exhibits a high initial capacity of 221 mAh g −1 at 0.1 C, excellent rate performance (184 mAh g −1 at 5 C), and high capacity retention of 94.0 % after 500 cycles. This work opens a new avenue to developing industry‐applicable Ni‐rich cathodes for next‐generation LIBs.

Abstract Oxygen vacancies‐enriched black TiO2 is one promising support for enhancing hydrogen evolution reaction (HER). Herein, oxygen vacancies enriched black TiO2 supported sub‐nanometer Pt clusters (Pt/TiO2‐OV) with metal support interactions is designed through solvent‐free microwave and following low‐temperature electroless approach for the first time. High‐temperature and strong reductants are not required and then can avoid the aggregation of decorated Pt species. Experimental and theoretical calculation verify that the created oxygen vacancies and Pt clusters exhibit synergistic effects for optimizing the reaction kinetics. Based on it, Pt/TiO2‐OV presents remarkable electrocatalytic performance with 18 mV to achieve 10 mA cm−2 coupled with small Tafel slope of 12 mV dec−1. This work provides quick synthetic strategy for preparing black titanium dioxide based nanomaterials.

Abstract The migration of ions is known to be associated with various detrimental phenomena, including current density‐voltage hysteresis, phase segregation, etc., which significantly limit the stability and performance of perovskite solar cells, impeding their progress toward commercial applications. To address these challenges, we propose incorporating a polymerizable organic small molecule monomer, N‐carbamoyl‐2‐propan‐2‐ylpent‐4‐enamide (Apronal), into the perovskite film to form a crosslinked polymer (P‐Apronal) through thermal crosslinking. The carbonyl and amino groups in Apronal effectively interact with shallow defects, such as uncoordinated Pb2+ and iodide vacancies, leading to the formation of high‐quality films with enhanced crystallinity and reduced lattice strain. Furthermore, the introduction of P‐Apronal improves energy level alignment, and facilitates charge carrier extraction and transport, resulting in a champion efficiency of 25.09 %. Importantly, P‐Apronal can effectively suppress the migration of I− ions and improve the long‐term stability of the devices. The…

Abstract Peroxymonosulfate (PMS) mediated radical and nonradical active substances can synergistically achieve the efficient elimination of antibiotic resistance genes (ARGs). However, enhancing interface electron cycling and optimizing the coupling of the oxygen‐containing intermediates to improve PMS activation kinetics remains a major challenge. Here, Co doped CeVO4 catalyst (Co−CVO) with asymmetric sites was constructed based on Ce 4f−O 2p−Co 3d gradient orbital coupling. The catalyst achieved approximately 2.51×105 copies/mL of extracellular ARGs (eARGs) removal within 15 minutes, exhibited ultrahigh degradation rate (k=1.24 min−1). The effective gradient 4f‐2p‐3d orbital coupling precisely regulates the electron distribution of Ce−O−Co active center microenvironment, while optimizing the electronic structure of Co 3d states (especially the occupancy of eg), promoting the adsorption of oxygen‐containing intermediates. The generated radical and nonradical generated by interfacial electron cycling enhanced by the reduction reaction of PMS at the Ce site and the oxidation reaction…

Abstract Eco‐friendly lead‐free organic–inorganic manganese halides (OIMHs) have attracted considerable attention in various optoelectronic applications because of their superior optical properties and flexible solution processibility. Herein, we report a novel pseudo‐2D layered OIMH (MTP)2MnBr4 (MTP: methyltriphenylphosphonium), which exhibits intense green emission under UV/blue or X‐ray excitation, with a near‐unity photoluminescence quantum yield, high resistance to thermal quenching (I150 °C=84.1 %) and good photochemical stability. These features enable (MTP)2MnBr4 as an efficient green phosphor for blue‐converted white light‐emitting diodes, demonstrating a commercial‐level luminous efficiency of 101 lm W−1 and a wide color gamut of 116 % NTSC. Moreover, these (MTP)2MnBr4 crystals showcase outstanding X‐ray scintillation properties, delivering a light yield of 67000 photon MeV−1, a detection limit of 82.4 nGy s−1, and a competitive spatial resolution of 6.2 lp mm−1 for X‐ray imaging. This work presents a new avenue for the exploration of eco‐friendly luminescent OIMHs towards…

Abstract Fe−N−C catalysts with single‐atom Fe−N4 configurations are highly needed owing to the high activity for oxygen reduction reaction (ORR). However, the limited intrinsic activity and dissatisfactory durability have significantly restrained the practical application of proton‐exchange membrane fuel cells (PEMFCs). Here, we demonstrate that constructing adjacent metal atomic clusters (ACs) is effective in boosting the ORR performance and stability of Fe−N4 catalysts. The integration of Fe−N4 configurations with highly uniform Co4 ACs on the N‐doped carbon substrate (Co4@/Fe1@NC) is realized through a “pre‐constrained” strategy using Co4 molecular clusters and Fe(acac)3 implanted carbon precursors. The as‐developed Co4@/Fe1@NC catalyst exhibits excellent ORR activity with a half‐wave potential (E1/2) of 0.835 V vs. RHE in acidic media and a high peak power density of 840 mW cm−2 in a H2−O2 fuel cell test. First‐principles calculations further clarify the ORR catalytic mechanism on the identified Fe−N4 that modified with Co4 ACs. This work provides a viable strategy for precisely…

Abstract Electrocatalytic CO 2 reduction reaction (CO 2 RR) in membrane electrode assembly (MEA) systems is a promising technology. Gaseous CO 2 can be directly transported to the cathode catalyst layer, leading to enhanced reaction rate. Meanwhile, there is no liquid electrolyte between the cathode and the anode, which can help to improve the energy efficiency of the whole system. The remarkable progress achieved recently points out the way to realize industrially relevant performance. In this review, we focus on the principles in MEA for CO 2 RR, focusing on gas diffusion electrodes and ion exchange membranes. Furthermore, anode processes beyond the oxidation of water are considered. Besides, the voltage distribution is scrutinized to identify the specific losses related to the individual components. We also summarize the progress on the generation of different reduced products together with the corresponding catalysts. Finally, the challenges and opportunities are highlighted for future research.

Abstract Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn2+, thus inhibiting hydrogen evolution and side reactions. The self‐assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm−2/1.0 mAh cm−2.

Abstract The separation of isomeric C4 paraffins is an important task in the petrochemical industry, while current adsorbents undergo a trade‐off relationship between selectivity and adsorption capacity. In this work, the pore aperture of a cage‐like Zn‐bzc (bzc=pyrazole‐4‐carboxylic acid) is tuned by the stepwise installation methyl groups on its narrow aperture to achieve both molecular‐sieving separation and high n‐C4H10 uptake. Notably, the resulting Zn‐bzc‐2CH3 (bzc‐2CH3=3,5‐dimethylpyrazole‐4‐carboxylic acid) can sensitively capture n‐C4H10 and exclude iso‐C4H10, affording molecular‐sieving for n‐C4H10/iso‐C4H10 separation and high n‐C4H10 adsorption capacity (54.3 cm3 g−1). Breakthrough tests prove n‐C4H10/iso‐C4H10 can be efficiently separated and high‐purity iso‐C4H10 (99.99 %) can be collected. Importantly, the hydrophobic microenvironment created by the introduced methyl groups greatly improves the stability of Zn‐bzc and significantly eliminates the negative effect of water vapor on gas separation under humid conditions, indicating Zn‐bzc‐2CH3 is a new benchmark…

Abstract Owing to outstanding performances, nickel‐based electrocatalysts are commonly used in electrochemical alcohol oxidation reactions (AORs), and the active phase is usually vacancy‐rich nickel oxide/hydroxide (NiOxHy) species. However, researchers are not aware of the catalytic role of atom vacancy in AORs. Here, we study vacancy‐induced catalytic mechanisms for AORs on NiOxHy species. As to AORs on oxygen‐vacancy‐poor β‐Ni(OH)2, the only redox mediator is electrooxidation‐induced electrophilic lattice oxygen species, which can only catalyze the dehydrogenation process (e.g., the electrooxidation of primary alcohol to carboxylic acid) instead of the C−C bond cleavage. Hence, vicinal diol electrooxidation reaction involving the C−C bond cleavage is not feasible with oxygen‐vacancy‐poor β‐Ni(OH)2. Only through oxygen vacancy‐induced adsorbed oxygen‐mediated mechanism, can oxygen‐vacancy‐rich NiOxHy species catalyze the electrooxidation of vicinal diol to carboxylic acid and formic acid accompanied with the C−C bond cleavage. Crucially, we examine how vacancies and…

Abstract Large scale production of green CH3OH obtained from CO2 and green H2 is a highly wanted process due to the role of CH3OH as H2/energy carrier and for producing chemicals. Starting with a short summary of the advantages of metal–organic frameworks (MOFs) as catalysts in liquid‐phase reactions, the present article highlights the opportunities that MOFs may offer also for some gas‐phase reactions, particularly for the selective CO2 hydrogenation to CH3OH. It is commented that there is a temperature compatibility window that combines the thermal stability of some MOFs with the temperature required in the CO2 hydrogenation to CH3OH that frequently ranges from 250 to 300 °C. The existing literature in this area is briefly organized according to the role of MOF as providing the active sites or as support of active metal nanoparticles (NPs). Emphasis is made to show how the flexibility in design and synthesis of MOFs can be used to enhance the catalytic activity by adjusting the composition of the nodes and the structure of the linkers. The influence of structural defects and…

Abstract Anion exchange membrane fuel cells (AEMFCs) and water electrolysis (AEMWE) show great application potential in the field of hydrogen energy conversion technology. However, scalable anion exchange membranes (AEMs) with desirable properties are still lacking, which greatly hampers the commercialization of this technology. Herein, we propose a series of novel multiblock AEMs based on ether‐free poly(biphenyl ammonium‐b‐biphenyl phenyl)s (PBPA‐b‐BPPs) that are suitable for use in high performance AEMFC and AEMWE systems because of their well‐formed microphase separation structures. The developed AEMs achieved outstanding OH− conductivity (162.2 mS cm−1 at 80 °C) with a low swelling ratio, good alkaline stability, and excellent mechanical durability (tensile strength >31 MPa and elongation at break >147 % after treatment in 2 M NaOH at 80 °C for 3750 h). A PBPA‐b‐BPP‐based AEMFC demonstrated a remarkable peak power density of 2.41 W cm−2 and in situ durability for 330 h under 0.6 A cm−2 at 70 °C. An AEMWE device showed a promising performance (6.25 A cm−2 at 2 V, 80 °C) and…

Abstract Electrocatalytic urea synthesis via coupling N 2 and CO 2 provides an effective route to mitigate energy crisis and close carbon footprint. However, the difficulty on breaking N≡N is the main reason that caused low efficiencies for both electrocatalytic NH 3 and urea synthesis, which is the bottleneck restricting their industrial applications. Herein, a new mechanism to overcome the inert of the nitrogen molecule was proposed by elongating N≡N instead of breaking N≡N to realize one‐step C−N coupling in the process for urea production. We constructed a Zn−Mn diatomic catalyst with axial chloride coordination, Zn−Mn sites display high tolerance to CO poisoning and the Faradaic efficiency can even be increased to 63.5 %, which is the highest value that has ever been reported. More importantly, negligible N≡N bond breakage effectively avoids the generation of ammonia as intermediates, therefore, the N‐selectivity in the co‐electrocatalytic system reaches100 % for urea synthesis. The previous cognition that electrocatalysts for urea synthesis must possess ammonia synthesis…

Abstract Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate‐determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS2‐WO3 to elevate the d‐band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS2‐WO3 exhibited a high NH3 yield of 62.38 μg h−1 mgcat−1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS2‐WO3 upshifted the d‐band center of W towards the Fermi level, leading to enhanced adsorption of −NH2 and −NH intermediates on the catalyst…

Abstract The dynamic restructuring of Cu surfaces in electroreduction conditions is of fundamental interest in electrocatalysis. We decode the structural dynamics of a Cu(111) electrode under reduction conditions by joint first‐principles calculations and operando electrochemical scanning tunneling microscopy (ECSTM) experiments. Combining global optimization and grand canonical density functional theory, we unravel the potential‐ and pH‐dependent restructuring of Cu(111) in acidic electrolyte. At reductive potential, Cu(111) is covered by a high density of H atoms and, below a threshold potential, Cu adatoms are formed on the surface in a (4×4) superstructure, a restructuring unfavorable in vacuum. The strong H adsorption is the driving force for the restructuring, itself induced by the electrode potential. On the restructured surface, barriers for hydrogen evolution reaction steps are low. Restructuring in electroreduction conditions creates highly active Cu adatom sites not present on Cu(111).

Abstract Lithium metal batteries hold great promise for promoting energy density and operating at low temperatures, yet they still suffer from insufficient Li compatibility and slow kinetic, especially at ultra‐low temperatures. Herein, we rationally design and synthesize a new amphiphilic solvent, 1,1,2,2‐tetrafluoro‐3‐methoxypropane, for use in battery electrolytes. The lithiophilic segment is readily to solvate Li + to induce self‐assembly of the electrolyte solution to form a peculiar core‐shell‐solvation structure. Such unique solvation structure not only largely improves the ionic conductivity to allow fast Li + transport and lower the desolvation energy to enable facile desolvation, but also leads to the formation of a highly robust and conductive inorganic SEI. The resulting electrolyte demonstrates high Li efficiency and superior cycling stability from room temperature to −40 °C at high current densities. Meanwhile, anode‐free high‐voltage cell retains 87 % capacity after 100 cycles.

Abstract Atmospheric water harvesting represents a promising technique to address water stress. Advanced adsorbents have been rationally designed to achieve high water uptake, yet their water sorption kinetics and regeneration temperature greatly limit water production efficiency. Herein, we demonstrated that 2D covalent organic frameworks (COFs), featuring hydrophobic skeleton, proper hydrophilic site density, and 1D open channels significantly lowered the water diffusion and desorption energy barrier. DHTA‐Pa COF showed a high water uptake of 0.48 g/g at 30 % R.H. with a remarkable adsorption rate of 0.72 L/Kg/h (298 K) and a desorption rate of 2.58 L/Kg/h (333 K). Moreover, more than 90 % adsorbed water could be released within 20 min at 313 K. This kinetic performance surpassed the reported porous materials and boosted the efficiency for multiple water extraction cycles. It may shed light on the material design strategy to achieve high daily water production with low‐energy input.

Abstract Electrochemical CO2 reduction reaction (CO2RR) over Cu catalysts exhibits enormous potential for efficiently converting CO2 to ethylene (C2H4). However, achieving high C2H4 selectivity remains a considerable challenge due to the propensity of Cu catalysts to undergo structural reconstruction during CO2RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating the reconstruction of a Cu‐based material to a pathway that facilitates CO2 reduction to C2H4 products. An excellent Faraday efficiency (FE) of 63.6 % on C2H4 with a current density of 497.2 mA cm−2 in flow cell was achieved, about 6.5 times higher than the pristine Cu catalyst which mainly produce CH4. The in situ X‐ray absorption spectroscopy and Raman studies reveal that the hydroxyl group in TA stabilizes Cuδ+ during the CO2RR. Furthermore, theoretical calculations demonstrate that the Cuδ+/Cu0 interfaces lower the activation energy barrier for *CO dimerization, and hydroxyl species stabilize the *COH intermediate via hydrogen bonding, thereby…

Abstract The large‐scale applicability of Zn‐metal anodes is severely impeded by the issues such as the dendrite growth, complicated hydrogen evolution, and uncontrollable passivation reaction. Herein, a negatively charged carboxylated double‐network hydrogel electrolyte (Gelatin/Sodium alginate‐acetate, denoted as Gel/SA‐acetate) has been developed to stabilize the interfacial electrochemistry, which restructures a type of Zn 2+ ion solvent sheath optimized via a chain‐liquid synergistic effect. New hydrogen bonds are reconstructed with water molecules by the zincophilic functional groups, and directional migration of hydrated Zn 2+ ions is therefore induced. Concomitantly, the robust chemical bonding of such hydrogel layers to the Zn slab exhibits a desirable anti‐catalytic effect, thereby greatly diminishing the water activity and eliminating side reactions. Subsequently, a symmetric cell using the Gel/SA‐acetate electrolyte demonstrates a reversible plating/stripping performance for 1580 h, and an asymmetric cell reaches a state‐of‐the‐art runtime of 5600 h with a high average…

Abstract The limited active sites and poor acid‐alkaline solution stability of metal–organic frameworks (MOFs), significantly limit their wider application. In this study, the acid property of tannic acid (TA) was used as an etchant to etch the surface‐active sites. Subsequently, the further chelation of the protonated TA with the exposed metal active site can effectively protect the metal ions. Meanwhile, the TA provided a large amount of phenolic hydroxyl groups, which can greatly improve the stability of imidazolate‐coordinated MOFs. The electrochemical test results indicated that the MOFs composite materials synthesized using this scheme had high specific capacitance and stability. And the mechanism of its electrochemical reaction process was explored through in situ X‐ray diffraction (XRD) and theoretical calculations. In addition, the same treatment was carried out through a series of carboxyl‐coordinated MOFs, which further confirmed the principle of this scheme to obtain a higher active site and stability. This paper explains the mechanism of functionalization of nano‐MOFs…

Abstract Transition metal oxides (TMOs) were one of the first photocatalysts used to produce hydrogen from water using solar energy. Despite the emergence of many other genres of photocatalysts over the years, TMO photocatalysts remain dominant due to their easy synthesis and unique physicochemical properties. Various strategies have been developed to enhance the photocatalytic activity of TMOs, but the solar‐to‐hydrogen (STH) conversion efficiency of TMO photocatalysts is still very low (<2 %), which is far below the targeted STH of 10 % for commercial viability. This article provides a comprehensive analysis of several widely used strategies, including oxygen defects control, doping, establishing interfacial junctions, and phase‐facet‐morphology engineering, that have been adopted to improve TMO photocatalysts. By critically evaluating these strategies and providing a roadmap for future research directions, this article serves as a valuable resource for researchers, students, and professionals seeking to develop efficient energy materials for green energy solutions.

Abstract To overcome the thermodynamic and kinetic impediments of the Sabatier CO 2 methanation reaction, the process must be operated under very high temperature and pressure conditions, to obtain an industrially viable conversion, rate, and selectivity. Herein, we report that these technologically relevant performance metrics have been achieved under much milder conditions using solar rather than thermal energy, where the methanation reaction is enabled by a novel nickel‐boron nitride catalyst. In this regard, an in situ generated HOB⋅⋅⋅B surface frustrated Lewis's pair is considered responsible for the high Sabatier conversion 87.68 %, reaction rate 2.03 mol g Ni −1 h −1 , and near 100 % selectivity, realized under ambient pressure conditions. This discovery bodes well for an opto‐chemical engineering strategy aimed at the development and implementation of a sustainable ‘Solar Sabatier’ methanation process.

Abstract Carbonate electrolytes have excellent chemical stability and high salt solubility, which are ideally practical choice for achieving high‐energy‐density sodium (Na) metal battery at room temperature. However, their application at ultra‐low temperature (−40 °C) is adversely affected by the instability of solid electrolyte interphase (SEI) formed by electrolyte decomposition and the difficulty of desolvation. Here, we designed a novel low‐temperature carbonate electrolyte by molecular engineering on solvation structure. The calculations and experimental results demonstrate that ethylene sulfate (ES) reduces the sodium ion desolvation energy and promotes the forming of more inorganic substances on the Na surface, which promote ion migration and inhibit dendrite growth. At −40 °C, the Na||Na symmetric battery exhibits a stable cycle of 1500 hours, and the Na||Na 3 V 2 (PO 4 ) 3 (NVP) battery achieves 88.2 % capacity retention after 200 cycles.

Abstract Pyrometallurgy technique is usually applied as a pretreatment to enhance the leaching efficiencies in the hydrometallurgy process for recovering valuable metals from spent lithium‐ion batteries. However, traditional pyrometallurgy processes are energy and time consuming. Here, we report a carbothermal shock (CTS) method for reducing LiNi 0.3 Co 0.2 Mn 0.5 O 2 (NCM325) cathode materials with uniform temperature distribution, high heating and cooling rates, high temperatures, and ultrafast reaction times. Li can be selectively leached through water leaching after CTS process with an efficiency of >90 %. Ni, Co, and Mn are recovered by dilute acid leaching with efficiencies >98 %. The CTS reduction strategy is feasible for various spent cathode materials, including NCM111, NCM523, NCM622, NCM811, LiCoO 2 , and LiMn 2 O 4 . The CTS process, with its low energy consumption and potential scale application, provides an efficient and environmentally friendly way for recovering spent lithium‐ion batteries.