The 100 most-cited articles in Angewandte Chemie International Edition, 2022

Nowadays, many chemical investigations are supported by routine calculations of molecular structures, reaction energies, barrier heights, and spectroscopic properties. The lion's share of these quantum-chemical calculations applies density functional theory (DFT) evaluated in atomic-orbital basis sets. This work provides best-practice guidance on the numerous methodological and technical aspects of DFT calculations in three parts: Firstly, we set the stage and introduce a step-by-step decision tree to choose a computational protocol that models the experiment as closely as possible. Secondly, we present a recommendation matrix to guide the choice of functional and basis set depending on the task at hand. A particular focus is on achieving an optimal balance between accuracy, robustness, and efficiency through multi-level approaches. Finally, we discuss selected representative examples to illustrate the recommended protocols and the effect of methodological choices.

In recent years, the increasing demand for high-capacity and safe energy storage has focused attention on zinc batteries featuring high voltage, high capacity, or both. Despite extensive research progress, achieving high-energy-density zinc batteries remains challenging and requires the synergistic regulation of multiple factors including reaction mechanisms, electrodes, and electrolytes. In this Review, we comprehensively summarize the rational design strategies of high-energy-density zinc batteries and critically analyze the positive effects and potential issues of these strategies in optimizing the electrochemistry, cathode materials, electrolytes, and device architecture. Finally, the challenges and perspectives for the further development of high-energy-density zinc batteries are outlined to guide research towards new-generation batteries for household appliances, low-speed electric vehicles, and large-scale energy storage systems.

Abstract Synthesizing H 2 O 2 from water and air via a photocatalytic approach is ideal for efficient production of this chemical at small‐scale. However, the poor activity and selectivity of the 2 e − water oxidation reaction (WOR) greatly restricts the efficiency of photocatalytic H 2 O 2 production. Herein we prepare a bipyridine‐based covalent organic framework photocatalyst (denoted as COF‐TfpBpy) for H 2 O 2 production from water and air. The solar‐to‐chemical conversion (SCC) efficiency at 298 K and 333 K is 0.57 % and 1.08 %, respectively, which are higher than the current reported highest value. The resulting H 2 O 2 solution is capable of degrading pollutants. A mechanistic study revealed that the excellent photocatalytic activity of COF‐TfpBpy is due to the protonation of bipyridine monomer, which promotes the rate‐determining reaction (2 e − WOR) and then enhances Yeager‐type oxygen adsorption to accelerate 2 e − one‐step oxygen reduction. This work demonstrates, for the first time, the COF‐catalyzed photosynthesis of H 2 O 2 from water and air; and paves the way for…

Abstract In this study, we propose a versatile method for synthesizing uniform three‐dimensional (3D) metal carbides, nitrides, and carbonitrides (MXenes)/metal–organic frameworks (MOFs) composites (Ti 3 C 2 T X /Cu‐BTC, Ti 3 C 2 T X /Fe,Co‐PBA, Ti 3 C 2 T X /ZIF‐8, and Ti 3 C 2 T X /ZIF‐67) that combine the advantages of MOFs and MXenes to enhance stability and improve conductivity. Subsequently, 3D hollow Ti 3 C 2 T X /ZIF‐67/CoV 2 O 6 composites with excellent electron‐ and ion‐transport properties derived from Ti 3 C 2 T X /ZIF‐67 were synthesized. The specific capacitance of the Ti 3 C 2 T X /ZIF‐67/CoV 2 O 6 electrode was 285.5 F g −1 , which is much higher than that of the ZIF‐67 and Ti 3 C 2 T X /ZIF‐67 electrode. This study opens a new avenue for the design and synthesis of MXene/MOF composites and complex hollow structures with tailorable structures and compositions for various applications.

Abstract Herein, a novel dual single‐atom catalyst comprising adjacent Fe‐N 4 and Mn‐N 4 sites on 2D ultrathin N‐doped carbon nanosheets with porous structure (FeMn‐DSAC) was constructed as the cathode for a flexible low‐temperature Zn‐air battery (ZAB). FeMn‐DSAC exhibits remarkable bifunctional activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Control experiments and density functional theory calculations reveal that the catalytic activity arises from the cooperative effect of the Fe/Mn dual‐sites aiding *OOH dissociation as well as the porous 2D nanosheet structure promoting active sits exposure and mass transfer during the reaction process. The excellent bifunctional activity of FeMn‐DSAC enables the ZAB to operate efficiently at ultra‐low temperature of −40 °C, delivering 30 mW cm −2 peak power density and retaining up to 86 % specific capacity from the room temperature counterpart.

Multifunctional wearable electronic devices based on natural materials are highly desirable for versatile applications of energy conversion, electronic skin and artificial intelligence. Herein, multifunctional wearable silver nanowire decorated leather (AgNW/leather) nanocomposites with hierarchical structures for integrated visual Joule heating, electromagnetic interference (EMI) shielding and piezoresistive sensing are fabricated via the facile vacuum-assisted filtration process. The AgNWs penetrate the micro-nanoporous structures in the corium side of leather constructing highly-efficient conductive networks. The resultant flexible and mechanically strong AgNW/leather nanocomposites exhibit extremely low sheet resistance of 0.8 Ω/sq, superior visual Joule heating temperatures up to 108 °C at low supplied voltage of 2.0 V due to efficient energy conversion, excellent EMI shielding effectiveness (EMI SE) of ≈55 dB and outstanding piezoresistive sensing ability in human motion detection. This work demonstrates the fabrication of multifunctional AgNW/leather nanocomposites for…

Abstract The electrochemical nitrate reduction reaction (NITRR) provides a promising solution for restoring the imbalance in the global nitrogen cycle while enabling a sustainable and decentralized route to source ammonia. Here, we demonstrate a novel electrocatalyst for NITRR consisting of Rh clusters and single‐atoms dispersed onto Cu nanowires (NWs), which delivers a partial current density of 162 mA cm −2 for NH 3 production and a Faradaic efficiency (FE) of 93 % at −0.2 V vs. RHE. The highest ammonia yield rate reached a record value of 1.27 mmol h −1 cm −2 . Detailed investigations by electron paramagnetic resonance, in situ infrared spectroscopy, differential electrochemical mass spectrometry and density functional theory modeling suggest that the high activity originates from the synergistic catalytic cooperation between Rh and Cu sites, whereby adsorbed hydrogen on Rh site transfers to vicinal *NO intermediate species adsorbed on Cu promoting the hydrogenation and ammonia formation.

Abstract Aqueous zinc‐ion batteries have drawn increasing attention due to the intrinsic safety, cost‐effectiveness and high energy density. However, parasitic reactions and non‐uniform dendrite growth on the Zn anode side impede their application. Herein, a multifunctional additive, ammonium dihydrogen phosphate (NHP), is introduced to regulate uniform zinc deposition and to suppress side reactions. The results show that the NH 4 + tends to be preferably absorbed on the Zn surface to form a “shielding effect” and blocks the direct contact of water with Zn. Moreover, NH 4 + and (H 2 PO 4 ) − jointly maintain pH values of the electrode‐electrolyte interface. Consequently, the NHP additive enables highly reversible Zn plating/stripping behaviors in Zn//Zn and Zn//Cu cells. Furthermore, the electrochemical performances of Zn//MnO 2 full cells and Zn//active carbon (AC) capacitors are improved. This work provides an efficient and general strategy for modifying Zn plating/stripping behaviors and suppressing side reactions in mild aqueous electrolyte.

Abstract The biomass‐derived alcohol oxidation reaction (BDAOR) holds great promise for sustainable production of chemicals. However, selective electrooxidation of alcohols to value‐added aldehyde compounds is still challenging. Herein, we report the electrocatalytic BDAORs to selectively produce aldehydes using single‐atom ruthenium on nickel oxide (Ru 1 ‐NiO) as a catalyst in the neutral medium. For electrooxidation of 5‐hydroxymethylfurfural (HMF), Ru 1 ‐NiO exhibits a low potential of 1.283 V at 10 mA cm −2 , and an optimal 2,5‐diformylfuran (DFF) selectivity of 90 %. Experimental studies reveal that the neutral electrolyte plays a critical role in achieving a high aldehyde selectivity, and the single‐atom Ru boosts HMF oxidation in the neutral medium by promoting water dissociation to afford OH*. Furthermore, Ru 1 ‐NiO can be extended to selective electrooxidation of a series of biomass‐derived alcohols to corresponding aldehydes, which are conventionally difficult to obtain in the alkaline medium.

The introduction of high-entropy into Prussian blue analogues (PBAs) has yet to attract attention in the field of lithium-sulfur battery materials. Herein, we systematically synthesize a library of PBAs from binary to high-entropy by a facile coprecipitation method. The coordination environment in PBAs is explored by X-ray absorption fine structure spectroscopy, which together with elemental mapping confirm the successful introduction of all metals. Importantly, electrochemical tests demonstrate that high-entropy PBA can serve as polysulfide immobilizer to inhibit shuttle effect and as catalyst to promote polysulfides conversion, thereby boosting its outstanding performance. Additionally, a variety of nanocubic metal oxides from binary to senary are fabricated by using PBAs as sacrificial precursors. We believe that a wide range of new materials obtained from our coprecipitation and pyrolysis methodology can promote further developments in research on PBA systems and sulfur hosts.

Abstract The S‐scheme heterojunction is flourishing in photocatalysis because it concurrently realizes separated charge carriers and sufficient redox ability. Steady‐state charge transfer has been confirmed by other methods. However, an essential part, the transfer dynamics in S‐scheme heterojunctions, is still missing. To compensate, a series of cadmium sulfide/pyrene‐alt‐difluorinated benzothiadiazole heterojunctions were constructed and the photophysical processes were investigated with femtosecond transient absorption spectroscopy. Encouragingly, an interfacial charge‐transfer signal was detected in the spectra of the heterojunction, which provides solid evidence for S‐scheme charge transfer to complement the results from well‐established methods. Furthermore, the lifetime for interfacial charge transfer was calculated to be ca. 78.6 ps. Moreover, the S‐scheme heterojunction photocatalysts exhibit higher photocatalytic conversion of 1,2‐diols and H2production rates than bare cadmium sulfide.

The electrochemical oxidation of small molecules to generate value-added products has gained enormous interest in recent years because of the advantages of benign operation conditions, high conversion efficiency and selectivity, the absence of external oxidizing agents, and eco-friendliness. Coupling the electrochemical oxidation of small molecules to replace oxygen evolution reaction (OER) at the anode and the hydrogen evolution reaction (HER) at the cathode in an electrolyzer would simultaneously realize the generation of high-value chemicals or pollutant degradation and the highly efficient production of hydrogen. This Minireview presents an introduction on small-molecule choice and design strategies of electrocatalysts as well as recent breakthroughs achieved in the highly efficient production of hydrogen. Finally, challenges and future orientations are highlighted.

Abstract A partially fluorinated, metal‐free, imine‐linked two‐dimensional triazine covalent organic framework (TF50‐COF) photocatalyst was developed. Fluorine (F)‐substituted and nonsubstituted units were integrated in equimolar amounts on the edge aromatic units, where they mediated two‐electron O2 photoreduction. F‐substitution created an abundance of Lewis acid sites, which regulated the electronic distribution of adjacent carbon atoms and provided highly active sites for O2 adsorption, and widened the visible‐light‐responsive range of the catalyst, while enhancing charge separation. Varying the proportion of F maximized the interlayer interactions of TF50‐COF, resulting in improved crystallinity with faster carrier transfer and robust photostability. The TF50‐COF catalyst demonstrates high selectivity and stability in O2 photoreduction into H2O2, with a high H2O2 yield rate of 1739 μmol h−1 g−1 and a remarkable apparent quantum efficiency of 5.1 % at 400 nm, exceeding the performance of previously reported nonmetal COF‐based photocatalysts.

Abstract The integration of Fe dopant and interfacial FeOOH into Ni‐MOFs [Fe‐doped‐(Ni‐MOFs)/FeOOH] to construct Fe−O−Ni−O−Fe bonding is demonstrated and the origin of remarkable electrocatalytic performance of Ni‐MOFs is elucidated. X‐ray absorption/photoelectron spectroscopy and theoretical calculation results indicate that Fe‐O−Ni−O−Fe bonding can facilitate the distorted coordinated structure of the Ni site with a short nickel–oxygen bond and low coordination number, and can promote the redistribution of Ni/Fe charge density to efficiently regulate the adsorption behavior of key intermediates with a near‐optimal d‐band center. Here the Fe‐doped‐(Ni‐MOFs)/FeOOH with interfacial Fe−O−Ni−O−Fe bonding shows superior catalytic performance for OER with a low overpotential of 210 mV at 15 mA cm−2 and excellent stability with ≈3 % attenuation after a 120 h cycle test. This study provides a novel strategy to design high‐performance Ni/Fe‐based electrocatalysts for OER in alkaline media.

Abstract Heteroatom‐doping in metal‐nitrogen‐carbon single‐atom catalysts (SACs) is considered a powerful strategy to promote the electrocatalytic CO 2 reduction reaction (CO 2 RR), but the origin of enhanced catalytic activity is still elusive. Here, we disclose that sulfur doping induces an obvious proton‐feeding effect for CO 2 RR. The model SAC catalyst with sulfur doping in the second‐shell of FeN 4 (Fe 1 −NSC) was verified by X‐ray absorption spectroscopy and aberration‐corrected scanning transmission electron microscopy. Fe 1 −NSC exhibits superior CO 2 RR performance compared to sulfur‐free FeN 4 and most reported Fe‐based SACs, with a maximum CO Faradaic efficiency of 98.6 % and turnover frequency of 1197 h −1 . Kinetic analysis and in situ characterizations confirm that sulfur doping accelerates H 2 O activation and feeds sufficient protons for promoting CO 2 conversion to *COOH, which is also corroborated by the theoretical results. This work deepens the understanding of the CO 2 RR mechanism based on SAC catalysts.

Abstract Simultaneous regulation of the coordination environment of single‐atom catalysts (SACs) and engineering architectures with efficient exposed active sites are efficient strategies for boosting peroxymonosulfate (PMS) activation. We isolated cobalt atoms with dual nitrogen and oxygen coordination (Co−N 3 O 1 ) on oxygen‐doped tubular carbon nitride (TCN) by pyrolyzing a hydrogen‐bonded cyanuric acid melamine–cobalt acetate precursor. The theoretically constructed Co−N 3 O 1 moiety on TCN exhibited an impressive mass activity of 7.61×10 5 min −1 mol −1 with high 1 O 2 selectivity. Theoretical calculations revealed that the cobalt single atoms occupied a dual nitrogen and oxygen coordination environment, and that PMS adsorption was promoted and energy barriers reduced for the key *O intermediate that produced 1 O 2 . The catalysts were attached to a widely used poly(vinylidene fluoride) microfiltration membrane to deliver an antibiotic wastewater treatment system with 97.5 % ciprofloxacin rejection over 10 hours, thereby revealing the suitability of the membrane for industrial…

Abstract Transition‐metal alloys are currently drawing increasing attention as promising electrocatalysts for the alkaline hydrogen evolution reaction (HER). However, traditional density‐functional‐theory‐derived d ‐band theory fails to describe the hydrogen adsorption energy (Δ G H ) on hollow sites. Herein, by studying the Δ G H for a series of Ni−M (M=Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, W) bimetallic alloys, an improved d ‐band center was provided and a potential NiCu electrocatalyst with a near‐optimal Δ G H was discovered. Moreover, oxygen atoms were introduced into Ni−M (O−NiM) to balance the adsorption/desorption of hydroxyl species. The tailored electrocatalytic sites for water dissociation can synergistically accelerate the multi‐step alkaline HER. The prepared O−NiCu shows the optimum HER activity with a low overpotential of 23 mV at 10 mA cm −2 . This work not only broadens the applicability of d ‐band theory, but also provides crucial understanding for designing efficient HER electrocatalysts.

Abstract Electrochemical reduction of nitrate pollutants to ammonia has emerged as an attractive alternative for ammonia synthesis. Currently, many strategies have been developed for enhancing nitrate reduction to ammonia (NRA) efficiency, but the influence of the degree of structural disorder is still unexplored. Here, carbon‐supported RuO2 nanosheets with adjustable crystallinity are synthesized by a facile molten salt method. The as‐synthesized amorphous RuO2 displays high ammonia Faradaic efficiency (97.46 %) and selectivity (96.42 %), greatly outperforming the crystalline counterparts. The disordered structure with abundant oxygen vacancies is revealed to modulate the d‐band center and hydrogen affinity, thus lowering the energy of the potential‐determining step (NH2*→NH3*).

Abstract The capacity of transition metal oxide cathode for Li‐ion batteries can be further enhanced by increasing the charging potential. However, these high voltage cathodes suffer from fast capacity decay because the large volume change of cathode breaks the active materials and cathode‐electrolyte interphase (CEI), resulting in electrolyte penetration into broken active materials and continuous side reactions between cathode and electrolytes. Herein, a robust LiF‐rich CEI was formed by potentiostatic reduction of fluorinated electrolyte at a low potential of 1.7 V. By taking LiCoO 2 as a model cathode, we demonstrate that the LiF‐rich CEI maintains the structural integrity and suppresses electrolyte penetration at a high cut‐off potential of 4.6 V. The LiCoO 2 with LiF‐rich CEI exhibited a capacity of 198 mAh g −1 at 0.5C and an enhanced capacity retention of 63.5 % over 400 cycles as compared to the LiF‐free LiCoO 2 with only 17.4 % of capacity retention.

Abstract Manipulating the active species and improving the structural stabilization of sulfur‐containing catalysts during the OER process remain a tremendous challenge. Herein, we constructed NiO/NiS 2 and Fe−NiO/NiS 2 as catalyst models to study the effect of Fe doping. As expected, Fe−NiO/NiS 2 exhibits a low overpotential of 270 mV at 10 mA cm −2 . The accumulation of hydroxyl groups on the surface of materials after Fe doping can promote the formation of highly active NiOOH at a lower OER potential. Moreover, we investigated the level of corrosion of M−S bonds and compared the stability variation of M−S bonds with Fe at different locations. Interestingly, Fe bonded with S in the bulk as the sacrificial agent can alleviate the oxidation corrosion of partial Ni−S bonds and thus endow Fe−NiO/NiS 2 long‐term durability. This work could motivate the community to focus more on resolving the corrosion of sulfur‐containing materials.

Abstract Photoreduction of CO 2 to C 2+ solar fuel is a promising carbon‐neutral technology for renewable energy. This strategy is challenged by its low productivity due to low efficiency in multielectron utilization and slow C−C coupling kinetics. This work reports a dual‐metal photocatalyst consisting of atomically dispersed indium and copper anchored on polymeric carbon nitride (InCu/PCN), on which the photoreduction of CO 2 delivered an excellent ethanol production rate of 28.5 μmol g −1 h −1 with a high selectivity of 92 %. Coupled experimental investigation and DFT calculations reveal the following mechanisms underpinning the high performance of this catalyst. Essentially, the In−Cu interaction enhances the charge separation by accelerating charge transfer from PCN to the metal sites. Indium also transfers electrons to neighboring copper via Cu−N−In bridges, increasing the electron density of copper active sites. Furthermore, In−Cu dual‐metal sites promote the adsorption of *CO intermediates and lower the energy barrier of C−C coupling.

Abstract Work function strongly impacts the surficial charge distribution, especially for metal‐support electrocatalysts when a built‐in electric field (BEF) is constructed. Therefore, studying the correlation between work function and BEF is crucial for understanding the intrinsic reaction mechanism. Herein, we present a Pt@CoOx electrocatalyst with a large work function difference (ΔΦ) and strong BEF, which shows outstanding hydrogen evolution activity in a neutral medium with a 4.5‐fold mass activity higher than 20 % Pt/C. Both experimental and theoretical results confirm the interfacial charge redistribution induced by the strong BEF, thus subtly optimizing hydrogen and hydroxide adsorption energy. This work not only provides fresh insights into the neutral hydrogen evolution mechanism but also proposes new design principles toward efficient electrocatalysts for hydrogen production in a neutral medium.

Abstract The best use of photogenerated electrons and holes is crucial to boosting photocatalytic activity. Herein, a bifunctional dual‐cocatalyst‐modified photocatalyst is constructed based on CdS/MoO2/MoS2 hollow spheres for hydrogen evolution coupled with selective pyruvic acid (PA) production from lactic acid (LA) oxidation. MoS2 and MoO2 are simultaneously obtained from the conversion of CdMoO4 in one step. In a photocatalytic process, the MoS2 and MoO2 function as the reduction and oxidation centers on which photogenerated electrons and holes accumulate and are used for hydrogen evolution reaction (HER) and PA synthesis, respectively. By monitoring the intermediates, a two‐step single‐electron route for PA production is proposed, initiated by the cleavage of the α‐C(sp3)−H bond in the LA. The conversion of LA and the selectivity of PA can reach ca. 29 % and 95 % after a five‐hour reaction, respectively.

Abstract Zn batteries are considered as potential candidates in future power sources, however suffer problems of rampant dendrite/by‐product on Zn anodes, torpid Zn 2+ transfer/diffusion and poor energy density. Inspired by the host‐guest interaction chemistry, an anion‐trap agent β‐cyclodextrin (β‐CD) is introduced into the Zn(ClO 4 ) 2 electrolyte to induce dominant Zn (002) deposition and improve Zn 2+ migration behaviors. The anion ClO 4 − is revealed to be trapped inside the cavity of β‐CD, impairing barriers for Zn 2+ migration and significantly elevating the Zn 2+ transference number to 0.878. Meanwhile, the β‐CD@ClO 4 − complex shows the function in preferential growth of the Zn (002), blocking the approach of dendrite growth. Above combined functions lead to substantial enhancement in long‐term stability and cell capacity, as proved by 10 times longer life of Zn||Zn symmetric cells and 57 % capacity increasement of Zn‐MnO 2 full cells (at 0.1 A g −1 ) compared with that of pure Zn(ClO 4 ) 2 electrolyte.

Abstract Electrochemical reduction of biomass‐derived 5‐hydroxymethylfurfural (HMF) represents an elegant route toward sustainable value‐added chemicals production that circumvents the use of fossil fuel and hydrogen. However, the reaction efficiency is hampered by the high voltage and low activity of electrodes (Cu, Bi, Pb). Herein, we report a Ru 1 Cu single‐atom alloy (SAA) catalyst with isolated Ru atoms on Cu nanowires that exhibits an electrochemical reduction of HMF to 2,5‐dihydroxymethylfuran (DHMF) with promoted productivity (0.47 vs. 0.08 mmol cm −2 h −1 ) and faradic efficiency (FE) (85.6 vs. 71.3 %) at −0.3 V (vs. RHE) compared with Cu counterpart. More importantly, the FE (87.5 %) is largely retained at high HMF concentration (100 mM). Kinetic studies by using combined electrochemical techniques suggest disparate mechanisms over Ru 1 Cu and Cu, revealing that single‐atom Ru promotes the dissociation of water to produce H* species that effectively react with HMF via an electrocatalytic hydrogenation (ECH) mechanism.

Polymer electrolyte membrane water electrolysis (PEMWE) has been regarded as a promising technology for renewable hydrogen production. However, acidic oxygen evolution reaction (OER) catalysts with long-term stability impose a grand challenge in its large-scale industrialization. In this review, critical factors that may lead to catalyst's instability in couple with potential solutions are comprehensively discussed, including mechanical peeling, substrate corrosion, active-site over-oxidation/dissolution, reconstruction, oxide crystal structure collapse through the lattice oxygen-participated reaction pathway, etc. Last but not least, personal prospects are provided in terms of rigorous stability evaluation criteria, in situ/operando characterizations, economic feasibility and practical electrolyzer consideration, highlighting the ternary relationship of structure evolution, industrial-relevant activity and stability to serve as a roadmap towards the ultimate application of PEMWE.

Carbazole-derived self-assembled monolayers (SAMs) are promising hole-selective materials for inverted perovskite solar cells (PSCs). However, they often possess small dipoles which prohibit them from effectively modulating the workfunction of ITO substrate, limiting the PSC photovoltage. Moreover, their properties can be drastically affected by even subtle structural modifications, undermining the final PSC performance. Here, we designed two carbazole-derived SAMs, CbzPh and CbzNaph through asymmetric or helical π-expansion for improved molecular dipole moment and strengthened π-π interaction. The helical π-expanded CbzNaph has the largest dipole, forming densely packed and ordered monolayer, facilitated by the highly ordered assembly observed in its π-scaffold's single crystal. These synergistically modulate the perovskite crystallization atop and tune the ITO workfunction. Consequently, the champion PSC employing CbzNaph showed an excellent 24.1 % efficiency and improved stability.

Abstract Zinc‐ion batteries (ZIB) present great potential in energy storage due to low cost and high safety. However, the poor stability, dendrite growth, and narrow electrochemical window limit their practical application. Herein, we develop a new eutectic electrolyte consisting of ethylene glycol (EG) and ZnCl 2 for dendrite‐free and long‐lifespan ZIBs. The EG molecules participate in the Zn 2+ solvation via coordination and hydrogen‐bond interactions. Optimizing the ZnCl 2 /EG molar ratio (1 : 4) can strengthen intermolecular interactions to form [ZnCl(EG)] + and [ZnCl(EG) 2 ] + cations. The dissociation–reduction of these complex cations enables the formation of a Cl‐rich organic–inorganic hybrid solid electrolyte interphase film on a Zn anode, realizing highly reversible Zn plating/stripping with long‐term stability of ≈3200 h. Furthermore, the polyaniline||Zn cell manifests decent cycling performance with ≈78 % capacity retention after 10 000 cycles, and the assembled pouch cell demonstrates high safety and stable capacity. This work opens an avenue for developing eutectic…

Abstract Aqueous zinc‐ion batteries (ZIBs) are promising for next‐generation energy storage. However, the reported electrode materials for ZIBs are facing shortcomings including low capacity and unsatisfactory cycling stability etc. Herein, hexaazatrinaphthalene‐quione (HATNQ) is reported for aqueous ZIBs. The HATNQ electrodes delivered an ultrahigh capacity (482.5 mAh g −1 at 0.2 A g −1 ) and outstanding cyclability of >10 000 cycles at 5 A g −1 . The capacity sets a new record for organic cathodes in aqueous ZIBs. The high performances are ascribed to the rich C=O and C=N groups that endowed HATNQ with a 2D layered supramolecular structure by multiple hydrogen bonds in plane with π–π interactions out‐of‐plane, leading to enhanced charge transfer, insolubility, and rapid ion transport for fast‐charge and ‐discharge batteries. Moreover, the 2D supramolecular structure boosted the storage of Zn 2+ /H + , particularly the storage of Zn 2+ , due to the more favorable O⋅⋅⋅Zn⋅⋅⋅N coordination in HATNQ.

Abstract The development of efficient electrocatalysts to generate key *NH 2 and *CO intermediates is crucial for ambient urea electrosynthesis with nitrate (NO 3 − ) and carbon dioxide (CO 2 ). Here we report a liquid‐phase laser irradiation method to fabricate symbiotic graphitic carbon encapsulated amorphous iron and iron oxide nanoparticles on carbon nanotubes (Fe(a)@C‐Fe 3 O 4 /CNTs). Fe(a)@C‐Fe 3 O 4 /CNTs exhibits superior electrocatalytic activity toward urea synthesis using NO 3 − and CO 2 , affording a urea yield of 1341.3±112.6 μg h −1 mg cat −1 and a faradic efficiency of 16.5±6.1 % at ambient conditions. Both experimental and theoretical results indicate that the formed Fe(a)@C and Fe 3 O 4 on CNTs provide dual active sites for the adsorption and activation of NO 3 − and CO 2 , thus generating key *NH 2 and *CO intermediates with lower energy barriers for urea formation. This work would be helpful for design and development of high‐efficiency dual‐site electrocatalysts for ambient urea synthesis.

Strong metal-support interactions (SMSI) represent a classic yet fast-growing area in catalysis research. The SMSI phenomenon results in the encapsulation and stabilization of metal nanoparticles (NPs) with the support material that significantly impacts the catalytic performance through regulation of the interfacial interactions. Engineering SMSI provides a promising approach to steer catalytic performance in various chemical processes, which serves as an effective tool to tackle energy and environmental challenges. Our Minireview covers characterization, theory, catalytic activity, dependence on the catalytic structure and inducing environment of SMSI phenomena. By providing an overview and outlook on the cutting-edge techniques in this multidisciplinary research field, we not only want to provide insights into the further exploitation of SMSI in catalysis, but we also hope to inspire rational designs and characterization in the broad field of material science and physical chemistry.

Abstract Solar‐driven overall water splitting is an ideal way to generate renewable energy while still challenging. For the first time, this work combined covalent organic frameworks (COFs) and piezoelectric material by covalent linkages to form Z‐scheme core@shell heterostructure for overall water splitting. Benefiting from the synergistic effect between the polarized electric field and photo‐generated charges, as well as the precise adjustment of shell thickness, the carrier separation and utilization efficiency is greatly improved. The optimal BiFeO 3 @TpPa‐1‐COF photocatalyst revealed hydrogen (H 2 ) and oxygen (O 2 ) production rates of 1416.4 and 708.2 μmol h −1 g −1 under the excitation of ultrasonication coupled with light irradiation, which is the best performance among various piezo‐ and COF‐based photocatalysts. This provides a new sight for the practical application of highly efficient photocatalytic overall water splitting.

Abstract The light‐driven CO 2 reduction to multi‐carbon products is especially meaningful, while the low efficiency of multi‐electron transfer and sluggish C−C coupling greatly hinder its development. Herein, we report a photocatalyst comprising of P and Cu dual sites anchored on graphitic carbon nitride (P/Cu SAs@CN), which achieves a high C 2 H 6 evolution rate of 616.6 μmol g −1 h −1 in reducing CO 2 to hydrocarbons. The detailed spectroscopic characterizations identify the formation of charge‐enriched Cu sites, where the isolated P atoms serve as hole capture sites during photocatalysis. Theoretical simulations combined with in situ FTIR measurement reveal a kinetically feasible process for the formation of C−C coupling intermediate (*OC−COH) and confirm the favorable production of C 2 H 6 on the P/Cu SAs@CN photocatalyst. This work offers new insights into the photocatalyst design with atomic precision toward highly efficient photocatalytic CO 2 conversion to high value‐added carbon products.

Abstract Covalent organic frameworks (COFs) are highly desirable for achieving high‐efficiency overall photosynthesis of hydrogen peroxide (H 2 O 2 ) via molecular design. However, precise construction of COFs toward overall photosynthetic H 2 O 2 remains a great challenge. Herein, we report the crystalline s ‐heptazine‐based COFs (HEP‐TAPT‐COF and HEP‐TAPB‐COF) with separated redox centers for efficient H 2 O 2 production from O 2 and pure water. The spatially and orderly separated active sites in HEP‐COFs can efficiently promote charge separation and enhance photocatalytic H 2 O 2 production. Compared with HEP‐TAPB‐COF, HEP‐TAPT‐COF exhibits higher H 2 O 2 production efficiency for integrating dual O 2 reduction active centers of s ‐heptazine and triazine moieties. Accordingly, HEP‐TAPT‐COF bearing dual O 2 reduction centers exhibits a remarkable solar‐to‐chemical energy efficiency of 0.65 % with a high apparent quantum efficiency of 15.35 % at 420 nm, surpassing previously reported COF‐based photocatalysts.

Abstract Theoretical calculations unveil that the formation of Os‐OsSe 2 heterostructures with neutralized work function (WF) perfectly balances the electronic state between strong (Os) and weak (OsSe 2 ) adsorbents and bidirectionally optimizes the hydrogen evolution reaction (HER) activity of Os sites, significantly reducing thermodynamic energy barrier and accelerating kinetics process. Then, heterostructural Os‐OsSe 2 is constructed for the first time by a molten salt method and confirmed by in‐depth structural characterization. Impressively, due to highly active sites endowed by the charge balance effect, Os‐OsSe 2 exhibits ultra‐low overpotentials for HER in both acidic (26 mV @ 10 mA cm −2 ) and alkaline (23 mV @ 10 mA cm −2 ) media, surpassing commercial Pt catalysts. Moreover, the solar‐to‐hydrogen device assembled with Os‐OsSe 2 further highlights its potential application prospects. Profoundly, this special heterostructure provides a new model for rational selection of heterocomponents.

Abstract Elaborate molecular design on cathodes is of great importance for rechargeable aqueous zinc–organic batteries’ performance elevation. Herein, we design a novel orthoquinone‐based covalent organic framework with an ordered channel structures (BT‐PTO COF) cathode for an ultrahigh performance aqueous zinc–organic battery. The ordered channel structure facilitates ions transfer and makes the COF follow a redox pseudocapacitance mechanism. Thus, it delivers a high reversible capacity of 225 mAh g−1 at 0.1 A g−1 and an exceptional long‐term cyclability (retention rate 98.0 % at 5 A g−1 (≈18 C) after 10 000 cycles). Moreover, a co‐insertion mechanism with Zn2+ first followed by two H+ is uncovered for the first time. Significantly, this co‐insertion behaviour evolves to more H+ insertion routes at high current density and gives the COF ultra‐fast kinetics thus it achieves unprecedented specific power of 184 kW kg−1(COF) and a high energy density of 92.4 Wh kg−1(COF). Our work reports a superior organic material for zinc batteries and provides a design idea for future…

Thermal conduction for electronic equipment has grown in importance in light of the burgeoning of 5G communication. It is imperatively desired to design highly thermally conductive fillers and polymer composite films with prominent Joule heating characteristics and extensive mechanical properties. In this work, "solvothermal & in situ growth" method is carried out to prepare "Fungal tree"-like hetero-structured silver nanowires@boron nitride nanosheet (AgNWs@BNNS) thermally conductive fillers. The thermally conductive AgNWs@BNNS/ANF composite films are obtained by the method of "suction filtration self-assembly and hot-pressing". When the mass fraction of AgNWs@BNNS is 50 wt%, AgNWs@BNNS/ANF composite film presents the optimal thermal conductivity coefficient of 9.44 W/(m ⋅ K) and excellent tensile strength of 136.6 MPa, good temperature-voltage response characteristics, superior electrical stability and reliability, which promise a wide application potential in 5G electronic devices.

Abstract The in‐depth understanding of local atomic environment–property relationships of p‐block metal single‐atom catalysts toward the 2 e− oxygen reduction reaction (ORR) has rarely been reported. Here, guided by first‐principles calculations, we develop a heteroatom‐modified In‐based metal–organic framework‐assisted approach to accurately synthesize an optimal catalyst, in which single In atoms are anchored by combined N,S‐dual first coordination and B second coordination supported by the hollow carbon rods (In SAs/NSBC). The In SAs/NSBC catalyst exhibits a high H2O2 selectivity of above 95 % in a wide range of pH. Furthermore, the In SAs/NSBC‐modified natural air diffusion electrode exhibits an unprecedented production rate of 6.49 mol peroxide gcatalyst−1 h−1 in 0.1 M KOH electrolyte and 6.71 mol peroxide gcatalyst−1 h−1 in 0.1 M PBS electrolyte. This strategy enables the design of next‐generation high‐performance single‐atom materials, and provides practical guidance for H2O2 electrosynthesis.

Abstract The global temperature increase must be limited to below 1.5 °C to alleviate the worst effects of climate change. Electrocatalytic CO 2 reduction (ECO 2 R) to generate chemicals and feedstocks is considered one of the most promising technologies to cut CO 2 emission at an industrial level. However, despite decades of studies, advances at the laboratory scale have not yet led to high industrial deployment rates. This Review discusses practical challenges in the industrial chain that hamper the scaling‐up deployment of the ECO 2 R technology. Faradaic efficiencies (FEs) of about 100 % and current densities above 200 mA cm −2 have been achieved for the ECO 2 R to CO/HCOOH, and the stability of the electrolysis system has been prolonged to 2000 h. For ECO 2 R to C 2 H 4 , the maximum FE is over 80 %, and the highest current density has reached the A cm −2 level. Thus, it is believed that ECO 2 R may have reached the stage for scale‐up. We aim to provide insights that can accelerate the development of the ECO 2 R technology.

Abstract The universal limit on the pH conditions is disturbing peroxymonosulfate (PMS)‐triggered high‐valent iron‐oxo systems in environmental applications. Here, we propose for the first time the construction of a neutral microenvironment on the surface of Zn−Fe layered double hydroxide (ZnFe‐LDH) by using the amphoteric properties of zinc hydroxide, which continuously generates ≡FeIV=O over a wide pH range of 3.0–11.0 in activating PMS. The ≡Zn(OH)2 moiety offers a neutral microenvironment at the phase interface, which mitigates the self‐decomposition of ≡FeIV=O by protons and the hydrolysis reaction of iron by hydroxyl groups, which is supported by the Mossbauer spectra, density functional theory calculations and designed experiments. Consequently, ZnFe‐LDH/PMS can satisfy the stability in long‐term experiments, selectivity under conditions with high salinity or natural organic matter and efficient treatment of actual wastewater.

Abstract The full reaction photosynthesis of H 2 O 2 that can combine water‐oxidation and oxygen‐reduction without sacrificial agents is highly demanded to maximize the light‐utilization and overcome the complex reaction‐process of anthraquinone‐oxidation. Here, a kind of oxidation‐reduction molecular junction covalent‐organic‐framework (TTF‐BT‐COF) has been synthesized through the covalent‐coupling of tetrathiafulvalene (photo‐oxidation site) and benzothiazole (photo‐reduction site), which presents visible‐light‐adsorption region, effective electron‐hole separation‐efficiency and photo‐redox sites that enables full reaction generation of H 2 O 2 . Specifically, a record‐high yield (TTF‐BT‐COF, ≈276 000 μM h −1 g −1 ) for H 2 O 2 photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation‐reduction molecular junction COFs for full reaction photosynthesis of H 2 O 2 , which might extend the scope of COFs in H 2 O 2 production.

Abstract Manipulating the coordination environment of the active center via anion modulation to reveal tailored activity and selectivity has been widely achieved, especially for carbon‐based single‐atom site catalysts (SACs). However, tuning ligand fields of the active center by single‐site metal cation regulation and identifying the effects on the resulting electronic configuration is seldom explored. Herein, we propose a single‐site Ru cation coordination strategy to engineer the electronic properties by constructing a Ru/LiCoO 2 SAC with atomically dispersed Ru−Co pair sites. Benefitting from the strong electronic coupling between Ru and Co sites, the catalyst possesses an enhanced electrical conductivity and achieves near‐optimal oxygen adsorption energies. Therefore, the optimized catalyst delivers superior oxygen evolution reaction (OER) activity with low overpotential, the high mass activity of 1000 A g oxide −1 at a small overpotential of 335 mV, and excellent long‐term stability. It also exhibits rapid kinetics with superior rate capability and outstanding durability in a…

Abstract Catalyst/support interaction plays a vital role in catalysis towards acidic oxygen evolution (OER), and the performance reinforcement is currently interpreted by either strain or electron donation effect. We herein report that these views are insufficient, where the dynamic evolution of the interface under potential bias must be considered. Taking Nb2O5−x supported iridium (Ir/Nb2O5−x) as a model catalyst, we uncovered the dynamic migration of oxygen species between IrOx and Nb2O5−x during OER. Direct spectroscopic evidence combined with theoretical computation suggests these migrations not only regulate the in situ Ir structure towards boosted activity, but also suppress its over‐oxidation via spontaneously delivering excessive oxygen from IrOx to Nb2O5−x. The optimized Ir/Nb2O5−x thus demonstrated exceptional performance in scalable water electrolyzers, i.e., only need 1.839 V to attain 3 A cm−2 (surpassing the DOE 2025 target), and no activity decay during a 2000 h test at 2 A cm−2.

Abstract Understanding the site interaction nature of single‐atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a site distance effect, which emphasizes how well the distance of the adjacent copper atoms (denoted as d Cu1−Cu1 ) matches with the reactant peroxydisulfate (PDS) molecular size to determine the Fenton‐like reaction reactivity on the carbon‐supported SACs. The optimized d Cu1−Cu1 in the range of 5–6 Å, which matches the molecular size of PDS, endows the catalyst with a nearly two times higher turnover frequency than that of d Cu1−Cu1 beyond this range, accordingly achieving record‐breaking kinetics for the oxidation of emerging organic contaminants. Further studies suggest that this site distance effect originates from the alteration of PDS adsorption to a dual‐site structure on Cu 1 −Cu 1 sites when d Cu1−Cu1 falls within 5–6 Å, significantly enhancing the interfacial charge transfer and consequently resulting in the most efficient catalyst for PDS activation so far.

Abstract Narrowband emissive organoboron emitters featuring the multi‐resonance (MR) effect have now become a critical material component for constructing high‐performance organic light‐emitting diodes (OLEDs) with pure emission colors. These MR organoboron emitters are capable of exhibiting high‐efficiency narrowband thermally activated delayed fluorescence (TADF) by allowing triplet‐to‐singlet reverse intersystem crossing (RISC). However, RISC involving spin‐flip exciton upconversion is generally the rate‐limiting step in the overall TADF; hence, a deeper understanding and precise control of the RISC dynamics are ongoing crucial challenges. Here, we introduce the first MR organoboron emitter ( CzBSe ) doped with a selenium atom, demonstrating a record‐high RISC rate exceeding 10 8 s −1 , which is even higher than its fluorescence radiation rate. Furthermore, the spin‐flip upconversion process in CzBSe can be accelerated by factors of ≈20000 and ≈800, compared to those of its oxygen‐ and sulfur‐doped homologs ( CzBO and CzBS ), respectively. Unlike CzBO and CzBS , the photophysical…

Directly splitting seawater to produce hydrogen provides a promising pathway for energy and environmental sustainability. However, current seawater splitting faces many challenges because of the sluggish kinetics, the presence of impurities, membrane contamination, and the competitive chloride oxidation reaction at the anode, which makes it more difficult than freshwater splitting. This Review firstly introduces the basic mechanisms of the anode and cathode reactions during seawater splitting. We critically analyze the primary principles for designing catalysts for seawater splitting in terms of both the hydrogen and oxygen evolution reactions, including with noble metal, noble metal free, and metal-free catalysts. Strategies to design effective catalysts, such as active site population, synergistic effect regulation, and surface engineering, are discussed. Furthermore, promises, perspectives, and challenges in developing seawater splitting technologies for clean hydrogen generation are summarized.

Biosensors are powerful tools for modern basic research and biomedical diagnostics. Their development requires substantial input from the chemical sciences. Sensors or probes with an optical readout, such as fluorescence, offer rapid, minimally invasive sensing of analytes with high spatial and temporal resolution. The near-infrared (NIR) region is beneficial because of the reduced background and scattering of biological samples (tissue transparency window) in this range. In this context, single-walled carbon nanotubes (SWCNTs) have emerged as versatile NIR fluorescent building blocks for biosensors. Here, we provide an overview of advances in SWCNT-based NIR fluorescent molecular sensors. We focus on chemical design strategies for diverse analytes and summarize insights into the photophysics and molecular recognition. Furthermore, different application areas are discussed-from chemical imaging of cellular systems and diagnostics to in vivo applications and perspectives for the future.

Abstract Selective CO2photoreduction to hydrocarbon fuels such as CH4is promising and sustainable for carbon‐neutral future. However, lack of proper binding strengths with reaction intermediates makes it still a challenge for photocatalytic CO2methanation with both high activity and selectivity. Here, low‐coordination single Au atoms (Au1‐S2) on ultrathin ZnIn2S4nanosheets was synthesized by a complex‐exchange route, enabling exceptional photocatalytic CO2reduction performance. Under visible light irradiation, Au1/ZnIn2S4catalyst exhibits a CH4yield of 275 μmol g−1 h−1with a selectivity as high as 77 %. As revealed by detailed characterizations and density functional theory calculations, Au1/ZnIn2S4with Au1‐S2structure not only display fast carrier transfer to underpin its superior activity, but also greatly reduce the energy barrier for protonation of *CO and stabilize the *CH3intermediate, thereby leading to the selective CH4generation from CO2photoreduction.

For lithium (Li) metal batteries, the decrease in operating temperature brings severe safety issues by more disordered Li deposition. Here, we demonstrate that the solvating power of solvent is closely related to the reversibility of the Li deposition/stripping process under low-temperature conditions. The electrolyte with weakly solvating power solvent shows lower desolvation energy, allowing for a uniform Li deposition morphology, as well as a high deposition/stripping efficiency (97.87 % at -40 °C). Based on a weakly solvating electrolyte, we further built a full cell by coupling the Li metal anode with a sulfurized polyacrylonitrile electrode at a low anode-to-cathode capacity ratio for steady cycling at -40 °C. Our results clarified the relationship between solvating power of solvent and Li deposition behavior at low temperatures.

Abstract Atmospheric water harvesting (AWH) is regarded as one of the promising strategies for freshwater production desirable to provide sustainable water for landlocked and arid regions. Hygroscopic materials have attracted widespread attention because of their water harvesting performance. However, the introduction of many inorganic salts often leads to aggregation and leakage issues in practical use. Here, polyzwitterionic hydrogels are developed as an effective AWH material platform. Via anti‐polyelectrolyte effects, the hygroscopic salt coordinated with polymer chains could capture moisture and enhance the swelling property, leading to a strong moisture sorption capacity. The hydrogel shows superior AWH performance (0.62 g g−1, 120 minutes for equilibrium at 30 % relative humidity) and produces 5.87 L kg−1 freshwater per day. It is anticipated that the polyzwitterionic hydrogels with unique salt‐responsive properties could provide new insights into the design and synthesis of next‐generation AWH materials.

The simultaneous presence of two active metal centres in diatomic catalysts (DACs) leads to the occurrence of specific interactions between active sites. Such interactions, referred to as long-range interactions (LRIs), play an important role in determining the rate and selectivity of a reaction. The optimal combination of metal centres must be determined to achieve the targeted efficiency. To date, various types of DACs have been synthesised and applied in electrochemistry. However, LRIs have not been systematically summarised. Herein, the regulation, mechanism, and electrocatalytic applications of LRIs are comprehensively summarised and discussed. In addition to the basic information above, the challenges, opportunities, and future development of LRIs in DACs are proposed in order to present an overall view and reference for future research.

Developing new strategies to advance the fundamental understanding of electrochemistry is crucial to mitigating multiple contemporary technological challenges. In this regard, magnetoelectrochemistry offers many strategic advantages in controlling and understanding electrochemical reactions that might be tricky to regulate in conventional electrochemical fields. However, the topic is highly interdisciplinary, combining concepts from electrochemistry, hydrodynamics, and magnetism with experimental outcomes that are sometimes unexpected. In this Review, we survey recent advances in using a magnetic field in different electrochemical applications organized by the effect of the generated forces on fundamental electrochemical principles and focus on how the magnetic field leads to the observed results. Finally, we discuss the challenges that remain to be addressed to establish robust applications capable of meeting present needs.

Transition metal complexes are well-known homogeneous electrocatalysts. In this regard, metal-organic frameworks (MOFs) can be considered as an ensemble of transition metal complexes ordered in a periodic arrangement. In addition, MOFs have several additional positive structural features that make them suitable for electrocatalysis, including large surface area, high porosity, and high content of accessible transition metal with exchangeable coordination positions. The present review describes the current state in the use of MOFs as electrocatalysts, both as host of electroactive guests and their direct electrocatalytic activity, particularly in the case of bimetallic MOFs. The field of MOF-derived materials is purposely not covered, focusing on the direct use of MOFs or its composites as electrocatalysts. Special attention has been paid to present strategies to overcome their poor electrical conductivity and limited stability.

Abstract Transition metal‐based electrocatalysts will undergo surface reconstruction to form active oxyhydroxide‐based hybrids, which are regarded as the “true‐catalysts” for the oxygen evolution reaction (OER). Much effort has been devoted to understanding the surface reconstruction, but little on identifying the origin of the enhanced performance derived from the substrate effect. Herein, we report the electrochemical synthesis of amorphous CoOOH layers on the surface of various cobalt sulfides (CoSα), and identify that the reduced intermolecular energy gap (Δinter) between the valence band maximum (VBM) of CoOOH and the conduction band minimum (CBM) of CoSα can accelerate the formation of OER‐active high‐valent Co4+ species. The combination of electrochemical and in situ spectroscopic approaches, including cyclic voltammetry (CV), operando electron paramagnetic resonance (EPR) and Raman, reveals that Co species in the CoOOH/Co9S8 are more readily oxidized to CoO2/Co9S8 than in CoOOH and other CoOOH/CoSα. This work provides a new design principle for transition metal‐based OER…

Abstract Prussian blue analogs (PBAs) are promising candidates for aqueous Zn‐ion batteries due to their unique open‐framework structures. However, they suffer from limited capacity and severe capacity decay originating from insufficient redox sites and structural instability. Herein, Cu‐substituted Mn‐PBA double‐shelled nanoboxes (CuMn‐PBA DSNBs) prepared by tannic acid etching and cation exchange approaches are demonstrated for efficient Zn ion storage. The unique hollow structures can expose abundant active sites and alleviate the volume change during the cycling test. Moreover, partial Cu substitution and induced Mn vacancies might inhibit the Jahn–Teller distortions of Mn‐N6 octahedra, thus contributing to the prolonged lifespan. As a result, CuMn‐PBA DSNBs exhibit high reversible capacity, decent rate performance and superior cycling stability for 2000 cycles. Furthermore, ex situ characterizations reveal that the charge storage mechanism of CuMn‐PBA DSNBs mainly involves the reversible redox reactions of transition metals and Zn2+ ion insertion/extraction processes.

Abstract Single‐atom active‐site catalysts have attracted significant attention in the field of photocatalytic CO2conversion. However, designing active sites for CO2reduction and H2O oxidation simultaneously on a photocatalyst and combining the corresponding half‐reaction in a photocatalytic system is still difficult. Here, we synthesized a bimetallic single‐atom active‐site photocatalyst with two compatible active centers of Mn and Co on carbon nitride (Mn1Co1/CN). Our experimental results and density functional theory calculations showed that the active center of Mn promotes H2O oxidation by accumulating photogenerated holes. In addition, the active center of Co promotes CO2activation by increasing the bond length and bond angle of CO2molecules. Benefiting from the synergistic effect of the atomic active centers, the synthesized Mn1Co1/CN exhibited a CO production rate of 47 μmol g−1 h−1, which is significantly higher than that of the corresponding single‐metal active‐site photocatalyst.

Abstract Sodium‐ion batteries capable of operating at rate and temperature extremes are highly desirable, but elusive due to the dynamics and thermodynamics limitations. Herein, a strategy of electrode–electrolyte interfacial chemistry modulation is proposed. The commercial hard carbon demonstrates superior rate performance with 212 mAh g −1 at an ultra‐high current density of 5 A g −1 in the electrolyte with weak ion solvation/desolvation, which is much higher than those in common electrolytes (nearly no capacity in carbonate‐based electrolytes). Even at −20 °C, a high capacity of 175 mAh g −1 (74 % of its room‐temperature capacity) can be maintained at 2 A g −1 . Such an electrode retains 90 % of its initial capacity after 1000 cycles. As proven, weak ion solvation/desolvation of tetrahydrofuran greatly facilitates fast‐ion diffusion at the SEI/electrolyte interface and homogeneous SEI with well‐distributed NaF and organic components ensures fast Na + diffusion through the SEI layer and a stable interface.

Abstract Ruthenium (Ru) has been theoretically considered a viable alkaline hydrogen evolution reaction electrocatalyst due to its fast water dissociation kinetics. However, its strong affinity to the adsorbed hydroxyl (OH ad ) blocks the active sites, resulting in unsatisfactory performance during the practical HER process. Here, we first reported a competitive adsorption strategy for the construction of SnO 2 nanoparticles doped with Ru single‐atoms supported on carbon (Ru SAs‐SnO 2 /C) via atomic galvanic replacement. SnO 2 was introduced to regulate the strong interaction between Ru and OH ad by the competitive adsorption of OH ad between Ru and SnO 2 , which alleviated the poisoning of Ru sites. As a consequence, the Ru SAs‐SnO 2 /C exhibited a low overpotential at 10 mA cm −2 (10 mV) and a low Tafel slope of 25 mV dec −1 . This approach provides a new avenue to modulate the adsorption strength of active sites and intermediates, which paves the way for the development of highly active electrocatalysts.

When it comes to using solar energy to promote catalytic reactions, photocatalysis technology is the first choice. However, sunlight can not only be directly converted into chemical energy through a photocatalytic process, it can also be converted through different energy-transfer pathways. Using sunlight as the energy source, photocatalytic reactions can proceed independently, and can also be coupled with other catalytic technologies to enhance the overall catalytic efficiency. Therefore, sunlight-driven catalytic reactions are diverse, and need to be given a specific definition. We propose a timely perspective for catalytic reactions driven by sunlight and give them a specific definition, namely "solar energy catalysis". The concept of different types of solar energy catalysis, such as photocatalysis, photothermal catalysis, solar cell powered electrocatalysis, and pyroelectric catalysis, are highlighted. Finally, their limitations and future research directions are discussed.

Abstract Interfacial solar vapor generation (SVG) is regarded as a promising and sustainable strategy for clean water production. While many materials have demonstrated excellent evaporation rates under one sun, it remains challenging to design solar evaporators without compromising SVG performance in high‐salinity brines (≥10 wt %). Herein, polyzwitterionic hydrogels (PZHs) are proposed as a novel platform for high‐salinity solar desalination. Taking advantage of the unique anti‐polyelectrolyte effects, PZHs can trap salt ions from the brine water to form a more hydrated polymer network, leading to enhanced SVG performance. PZHs exhibit an exceptional solar evaporation rate of 4.14 kg m −2 h −1 in 10 wt % brine, which is ≈20 % higher than that in pure water. It is anticipated that salt‐responsive PZHs may provide insights for the design of next‐generation solar desalination systems.

Abstract Multi‐resonance TADF (MR‐TADF) emitters are promising for high‐resolution OLEDs, but the concurrent optimization of excited‐state dynamics and color purity remains a tough challenge. Herein, three deep‐blue MR‐TADF compounds (BN1–BN3) featuring gradually enlarged ring‐fused structures and increased rigidity are accessed by lithium‐free borylation in high yields from the same precursor, with all the emitters possessing CIEy coordinates below 0.08. Structure–property investigations demonstrate a strategic improvement of the oscillator strength (fosc) and acceleration of the reverse intersystem crossing (RISC) process by extending the π‐skeleton, where BN3 realizes a maximum external quantum efficiency (EQE) of 37.6 % and reduced roll‐off, thus showing the best efficiency reported for deep‐blue TADF OLEDs. The internal regulation of the efficiency and color purity of these compounds validate the general effectiveness to achieve advanced deep‐blue narrowband emitters with higher‐order boron/nitrogen‐based MR motifs.

Abstract The development of two divergent and complementary Lewis acid catalyzed additions of bicyclobutanes to imines is described. Microscale high‐throughput experimentation was integral to the discovery and optimization of both reactions. N ‐arylimines undergo formal (3+2) cycloaddition with bicyclobutanes to yield azabicyclo[2.1.1]hexanes in a single step; in contrast, N ‐alkylimines undergo an addition/elimination sequence to generate cyclobutenyl methanamine products with high diastereoselectivity. These new products contain a variety of synthetic handles for further elaboration, including many functional groups relevant to pharmaceutical synthesis. The divergent reactivity observed is attributed to differences in basicity and nucleophilicity of the nitrogen atom in a common carbocation intermediate, leading to either nucleophilic attack ( N ‐aryl) or E1 elimination ( N ‐alkyl).

Abstract Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast‐charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn 2+ ‐ion diffusion. Moreover, steady‐state Zn metal plating/stripping with Coulombic efficiency above 99 % is achieved at 10–100 mA cm −2 in a reasonably high concentration (3 M) ZnSO 4 electrolyte. Significantly, a long‐term cycling‐stable Zn metal electrode is realized with a depth of discharge of 66.7 % under 50 mA cm −2 in both Zn||Zn symmetrical cells and MnO 2 ||Zn full cells.

Self-assembled monolayers (SAMs) have been widely employed as an effective way to modify interfaces of electronic/optoelectronic devices. To achieve a good control of the growth and molecular functionality of SAMs, we develop a co-assembled monolayer (co-SAM) for obtaining efficient hole selection and suppressed recombination at the hole-selective interface in inverted perovskite solar cells (PSCs). By engineering the position of methoxy substituents, an aligned energy level and favorable dipole moment can be obtained in our newly synthesized SAM, ((2,7-dimethoxy-9H-carbazol-9-yl) methyl) phosphonic acid (DC-PA). An alkyl ammonium containing SAM is co-assembled to further optimize the surface functionalization and interaction with perovskite layer on top. A champion device with an excellent power conversion efficiency (PCE) of 23.59 % and improved device stability are achieved. This work demonstrates the advantage of using co-SAM in improving performance and stability of PSCs.

Abstract The complexity of chemical compounds in lithium‐ion batteries (LIBs) results in great difficulties in the extraction of multiple transition metals, which have similar physicochemical characteristics. Here, we propose a novel strategy for selective extraction of nickel, cobalt, and manganese from spent LiNi x Co y Mn 1− x − y O 2 (NCM) cathode through the regulation of coordination environment. Depending on adjusting the composition of ligand in transition metal complexes, a tandem leaching and separation system is designed and finally enables nickel, cobalt, and manganese to enrich in the form of NiO, Co 3 O 4 , and Mn 3 O 4 with high recovery yields of 99.1 %, 95.1 %, and 95.3 %, respectively. We further confirm that the combination of different transition metals with well‐designed ligands is the key to good selectivity. Through our work, fine‐tuning the coordination environment of metal ions is proved to have great prospects in the battery recycling industry.

Advanced electrocatalysts for complete oxidation of ethylene glycol (EG) in direct EG fuel cells are strongly desired owing to the higher energy efficiency. Herein, Pd-PdSe heterostructural nanosheets (Pd-PdSe HNSs) have been successfully fabricated via a one-step approach. These Pd-PdSe HNSs feature unique electronic and geometrical structures, in which unconventional p-d hybridization interactions and tensile strain effect co-exist. Compared with commercial Pd/C and Pd NSs catalysts, Pd-PdSe HNSs display 5.5 (6.6) and 2.5 (2.6) fold enhancement of specific (mass) activity for the EG oxidation reaction (EGOR). Especially, the optimum C1 pathway selectivity of Pd-PdSe HNSs reaches 44.3 %, illustrating the superior C-C bond cleavage ability. Electrochemical in situ FTIR spectroscopy and theoretical calculations demonstrate that the extraordinary p-d hybridization interaction and tensile strain effect could effectively reduce the activation energy of C-C bond breaking and accelerate CO* oxidation, boosting the complete oxidation of EG and improving the catalytic performance.

Single-junction organic solar cells (OSCs) have made significant progress in recent years. Innovations in material design and device optimization have improved the power conversion efficiencies to over 19 %. In this Minireview, based on recent advances, we discuss molecular design strategies to tune the absorption spectrum, energy level, and intermolecular aggregation as well as highlight the role of molecular electrostatic potential in decreasing energy loss. Then, we introduce the latest progress in four types of OSCs composed of different donor:acceptor combinations: polymer donor:small-molecule acceptor, all-polymer, all-small-molecule, and small-molecule donor:polymer acceptor. Finally, the challenges of OSCs in practical applications, including material cost, stability, and multi-function integration, are discussed.

Abstract Nanocatalytic therapy, involving the nanozyme‐triggered production of reactive oxygen species (ROS) in the tumor microenvironment (TME), has demonstrated potential in tumor therapy, but nanozymes still face challenges of activity and specificity that compromise the therapeutic efficacy. Herein, we report a strategy based on a single‐atom nanozyme to initiate cascade enzymatic reactions in the TME for tumor‐specific treatment. The cobalt‐single‐atom nanozyme, with Co−N coordination on N‐doped porous carbon (Co‐SAs@NC), displays catalase‐like activity that decomposes cellular endogenous H 2 O 2 to produce O 2 , and subsequent oxidase‐like activity that converts O 2 into cytotoxic superoxide radicals to efficiently kill tumor cells. By incorporation with doxorubicin, the therapy achieves a significantly enhanced antitumor effect in vivo. Our findings show that cascade TME‐specific catalytic therapy combined with chemotherapy is a promising strategy for efficient tumor therapy.

Abstract Despite the fact that high‐valent nickel‐based oxides exhibit promising catalytic activity for the urea oxidation reaction (UOR), the fundamental questions concerning the origin of the high performance and the structure–activity correlations remain to be elucidated. Here, we unveil the underlying enhanced mechanism of UOR by employing a series of prepared cation‐vacancy controllable LiNiO 2 (LNO) model catalysts. Impressively, the optimized layered LNO‐2 exhibits an extremely low overpotential at 10 mA cm −2 along with excellent stability after the 160 h test. Operando characterisations combined with the theoretical analysis reveal the activated lattice oxygen in layered LiNiO 2 with moderate cation vacancies triggers charge disproportion of the Ni site to form Ni 4+ species, facilitating deprotonation in a lattice oxygen involved catalytic process.

Abstract Uncontrolled dendrites growth and serious parasitic reactions in aqueous electrolytes, greatly hinder the practical application of aqueous zinc‐ion battery. On the basis of in situ‐chemical construction and performance‐improving mechanism, multifunctional fluoroethylene carbonate (FEC) is introduced into aqueous electrolyte to construct a high‐quality and ZnF 2 ‐riched inorganic/organic hybrid SEI (ZHS) layer on Zn metal anode (ZMA) surface. Notably, FEC additive can regulate the solvated structure of Zn 2+ to reduce H 2 O molecules reactivity. Additionally, the ZHS layer with strong Zn 2+ affinity can avoid dendrites formation and hinder the direct contact between the electrolyte and anode. Therefore, the dendrites growth, Zn corrosion, and H 2 evolution reaction on ZMA in FEC‐included ZnSO 4 electrolyte are highly suppressed. Thus, ZMA in such electrolyte realize a long cycle life over 1000 h and deliver a stable coulombic efficiency of 99.1 % after 500 cycles.

Monotonous luminescence has always been a major factor limiting the application of organic room-temperature phosphorescence (RTP) materials. Enhancing and regulating the intermolecular interactions between the host and guest is an effective strategy to achieve excellent phosphorescence performance. In this study, intermolecular halogen bonding (CN⋅⋅⋅Br) was introduced into the host-guest RTP system. The interaction promoted intersystem crossing and stabilized the triplet excitons, thus helping to achieve strong phosphorescence emission. In addition, the weak intermolecular interaction of halogen bonding is sensitive to external stimuli such as heat, mechanical force, and X-rays. Therefore, the triplet excitons were easily quenched and colorimetric multi-stimuli responsive behaviors were realized, which greatly enriched the luminescence functionality of the RTP materials. This method provides a new platform for the future design of responsive RTP materials based on weak intermolecular interactions between the host and guest molecules.

Abstract Developing efficient piezocatalytic systems for two‐electron water splitting (TEWS) with producing H 2 and H 2 O 2 shows great promise to meet the industrial demand. Herein, Ag single atoms (SAs) and clusters are co‐anchored on carbon nitride (Ag SA+C −CN) to serve as the multifunctional sites for efficient TEWS. The Ag SAs enhance the in‐plane piezoelectric polarization of CN that is intimately modulated by the atomic coordination induced charge redistribution, and Ag clusters afford strong interfacial electric field to remarkably promote the out‐of‐plane migration of piezoelectrons from CN. Moreover, Ag SA+C −CN yields a larger piezoresistive effect that elevates carrier mobility under strain. Consequently, a superior H 2 and H 2 O 2 evolution rate of 7.90 mmol g −1 h −1 and 5.84 mmol g −1 h −1 is delivered by Ag SA+C −CN, respectively, far exceeding that of the previously reported piezocatalysts. This work not only presents the SAs decoration as an available polarization enhancement strategy, but also sheds light on the superiority of multi‐sites engineering in…

Abstract Regulating the distribution of reactive oxygen species generated from H 2 O 2 activation is the prerequisite to ensuring the efficient and safe use of H 2 O 2 in the chemistry and life science fields. Herein, we demonstrate that constructing a dual Cu−Fe site through the self‐assembly of single‐atomic‐layered Cu 5 nanoclusters onto a FeS 2 surface achieves selective H 2 O 2 activation with high efficiency. Unlike its unitary Cu or Fe counterpart, the dual Cu−Fe sites residing at the perimeter zone of the Cu 5 /FeS 2 interface facilitate H 2 O 2 adsorption and barrierless decomposition into ⋅OH via forming a bridging Cu‐O‐O‐Fe complex. The robust in situ formation of ⋅OH governed by this atomic‐layered catalyst enables the effective oxidation of several refractory toxic pollutants across a broad pH range, including alachlor, sulfadimidine, p‐nitrobenzoic acid, p‐chlorophenol, p‐chloronitrobenzene. This work highlights the concept of building a dual catalytic site in manipulating selective H 2 O 2 activation on the surface molecular level towards efficient environmental…

Abstract Development of effective and stable catalysts for CO2 hydrogenation into ethanol remains a challenge. Herein, we report that Rh1/CeTiOx single‐atom catalyst constructed by embedding monoatomic Rh onto Ti‐doped CeO2 support has shown a super high ethanol selectivity (≈99.1 %), record‐breaking turnover frequency (493.1 h−1), and outstanding stability. Synergistic effects of Ti‐doption and monoatomic Rh contribute to this excellent catalytic performance by firstly facilitating oxygen vacancies formation to generate oxygen‐vacancy‐Rh Lewis‐acid‐base pairs, which favor CO2 adsorption and activation, cleavage of C−O bonds in CHxOH* and COOH* into CHx* and CO* species, subsequent C−C coupling and hydrogenation into ethanol, and secondly generating strong Rh−O bond by Ti‐doping‐induced crystal reconstruction, which contributes to striking stability. This work highlights the importance of support elaborating regulation for single‐atom catalyst design to substantially improve the catalytic performance.

Abstract Single atom catalysts (SACs) have been widely studied in the field of CO 2 electroreduction, but industrial‐level current density and near‐unity product selectivity are still difficult to achieve. Herein, a diatomic site catalysts (DASCs) consisting of Co‐Cu hetero‐diatomic pairs is synthesized. The CoCu DASC exhibits excellent selectivity with the maximum CO Faradaic efficiency of 99.1 %. The CO selectivity can maintain above 95 % over a wide current density range from 100 mA cm −2 to 500 mA cm −2 . The maximum CO partial current density can reach to 483 mA cm −2 in flow cell, far exceed industrial‐level current density requirements (>200 mA cm −2 ). Theoretical calculation reveals that the synergistic catalysis of the Co‐Cu bimetallic sites reduce the activation energy and promote the formation of intermediate *COOH. This work shows that the introduction of another metal atom into SACs can significantly affect the electronic structure and then enhance the catalytic activity of SACs.

Abstract As hot topics in the chemical conversion of CO2, the photo‐/electrocatalytic reduction of CO2and use of CO2as a supporter for energy storage have shown great potential for the utilization of CO2. However, many obstacles still exist on the road to realizing highly efficient chemical CO2conversion, such as inefficient uptake/activation of CO2and mass transport in catalysts. Covalent organic frameworks (COFs), as a kind of porous material, have been widely explored as catalysts for the chemical conversion of CO2owing to their unique features. In particular, COF‐based functional materials containing diverse active sites (such as single metal sites, metal nanoparticles, and metal oxides) offer great potential for realizing CO2conversion and energy storage. This Minireview discusses recent breakthroughs in the basic knowledge, mechanisms, and pathways of chemical CO2conversion strategies that use COF‐based functional catalysts. In addition, the challenges and prospects of COF‐based functional catalysts for the efficient utilization of CO2are also introduced.

Abstract The rampant dendrites and hydrogen evolution reaction (HER) resulting from the turbulent interfacial evolution at the anode/electrolyte are the main culprits of short lifespan and low Coulombic efficiency of Zn metal batteries. In this work, a versatile protective coating with excellent zincophilic and amphoteric features is constructed on the surface of Zn metal (ZP@Zn) as dendrite‐free anodes. This kind of protective coating possesses the advantages of reversible proton storage and rapid desolvation kinetics, thereby mitigating the HER and facilitating homogeneous nucleation concomitantly. Furthermore, the space charge polarization effect promotes charge redistribution to achieve uniform Zn deposition. Accordingly, the ZP@Zn symmetric cell manifests excellent reversibility at an ultrahigh cumulative plating capacity of 4700 mAh cm−2and stable cycling at 80 % depth of discharge (DOD). The ZP@Zn//V6O13pouch cell also reveals superior cycling stability with a high capacity of 326.6 mAh g−1.

Abstract Covalent organic frameworks (COF) possess a robust and porous crystalline structure, making them an appealing candidate for energy storage. Herein, we report an exfoliated polyimide COF composite (P‐COF@SWCNT) prepared by an in situ condensation of anhydride and amine on the single‐walled carbon nanotubes as advanced anode for potassium‐ion batteries (PIBs). Numerous active sites exposed on the exfoliated frameworks and the various open pathways promote the highly efficient ion diffusion in the P‐COF@SWCNT while preventing irreversible dissolution in the electrolyte. During the charging/discharging process, K+ is engaged in the carbonyls of imide group and naphthalene rings through the enolization and π‐K+ effect, which is demonstrated by the DFT calculation and XPS, ex‐situ FTIR, Raman. As a result, the prepared P‐COF@SWCNT anode enables an incredibly high reversible specific capacity of 438 mA h g−1 at 0.05 A g−1 and extended stability. The structural advantage of P‐COF@SWCNT enables more insights into the design and versatility of COF as an electrode.

Abstract Metal–organic frameworks (MOFs) have been intensively studied as a class of semiconductor‐like materials in photocatalysis. However, band bending, which plays a crucial role in semiconductor photocatalysis, has not yet been demonstrated in MOF photocatalysts. Herein, a representative MOF, MIL‐125‐NH2, is integrated with the metal oxides (MoO3 and V2O5) that feature appropriate work functions and energy levels to afford the corresponding MOF composites. Surface photovoltage results demonstrate band bending in the MOF composites, which gives rise to the built‐in electric field of MIL‐125‐NH2, boosting the charge separation. As a result, the MOF composites present 56 and 42 times higher activities, respectively, compared to the pristine MOF for photocatalytic H2 production. Upon depositing Pt onto the MOF, ∼6 times higher activity is achieved. This work illustrates band bending of MOFs for the first time, supporting their semiconductor‐like nature, which would greatly promote MOF photocatalysis.

Abstract Low‐dimensional (LD) perovskites can effectively passivate and stabilize 3D perovskites for high‐performance perovskite solar cells (PSCs). Regards CsPbI 3 ‐based PSCs, the influence of high‐temperature annealing on the LD perovskite passivation effect has to be taken into account due to fact the black‐phase CsPbI 3 crystallization requires high‐temperature treatment, however, which has been rarely concerned so far. Here, the thermal stability of LD perovskites based on three hydrophobic organic ammonium salts and their passivation effect toward CsPbI 3 and the whole device performance, have been investigated. It is found that, phenyltrimethylammonium iodide (PTAI) and its corresponding LD perovskites exhibit excellent thermal stability. Further investigation reveals that PTAI‐based LD perovskites are mainly distributed at grain boundaries, which not only enhances the phase stability of CsPbI 3 but also effectively suppresses non‐radiative recombination. As a consequence, the champion PSC device based on CsPbI 3 exhibits a record efficiency of 21.0 % with high stability.

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have emerged as attractive platforms for solar‐to‐chemical energy conversion. In this study, we have implemented a gradient heating strategy to synthesize a sp 2 ‐carbon‐linked triazine‐based COF, COF‐JLU100, exhibiting high crystallinity, large surface area, good durability and carrier mobility for solar‐driven photocatalytic hydrogen evolution. The Pt‐doped COF‐JLU100 demonstrated a high hydrogen evolution rate of over 100 000 μmol g −1 h −1 for water splitting under visible‐light illumination (λ>420 nm). Experimental and theoretical studies corroborate that the cyano‐vinylene segments in COF‐JLU100 extend the π‐delocalization and enable fast charge transfer and separation rates as well as good dispersion in water. Moreover, COF‐JLU100 can be prepared by low‐cost and easily available monomers and has excellent stability, which is desirable for practical solar‐driven hydrogen production.

Abstract Single‐atom alloys hold great promise for electrocatalytic nitrogen reduction reaction (NRR), while the comprehensive experimental/theoretical investigations of SAAs for the NRR are still missing. Herein, PdFe1 single‐atom alloy metallene, in which the Fe single atoms are confined on a Pd metallene support, is first developed as an effective and robust NRR electrocatalyst, delivering exceptional NRR performance with an NH3 yield of 111.9 μg h−1 mg−1, a Faradaic efficiency of 37.8 % at −0.2 V (RHE), as well as a long‐term stability for 100 h electrolysis. In‐depth mechanistic investigations by theoretical computations and operando X‐ray absorption/Raman spectroscopy indentify Pd‐coordinated Fe single atoms as active centers to enable efficient N2 activation via N2‐to‐Fe σ‐donation, reduced protonation energy barriers, suppressed hydrogen evolution and excellent thermodynamic stability, thus accounting for the high activity, selectivity and stability of PdFe1 for the NRR.

Covalent organic frameworks (COFs) are an emerging category of organic polymers with highly porous crystalline structures. In the last decade, reports on the use of COFs as heterogeneous photocatalysts for organic transformations have shown significant progress. Still, comprehensive reviews on the mechanisms of the photocatalytic organic transformations using COFs are lacking. This Review provides a comprehensive and systematic overview of COF-based photocatalysts for organic transformations. Firstly, we discuss the photophysical properties and the characterization methods of COF-based photocatalysts. Then, the general photocatalytic mechanism, the advantages, and the strategies to improve the photocatalytic efficiency of COF-based photocatalysts are summarized. After that, advanced examples of COF-based photocatalysts for organic transformations are analyzed with regard to the underlying mechanisms. The Review ends with a critical perspective on the challenges and prospects.

Despite rapid progress in the field of metal-organic frameworks (MOFs), the potential of using machine learning (ML) methods to predict MOF synthesis parameters is still untapped. Here, we show how ML can be used for rationalization and acceleration of the MOF discovery process by directly predicting the synthesis conditions of a MOF based on its crystal structure. Our approach is based on: i) establishing the first MOF synthesis database via automatic extraction of synthesis parameters from the literature, ii) training and optimizing ML models by employing the MOF database, and iii) predicting the synthesis conditions for new MOF structures. The ML models, even at an initial stage, exhibit a good prediction performance, outperforming human expert predictions, obtained through a synthesis survey. The automated synthesis prediction is available via a web-tool on https://mof-synthesis.aimat.science.

Abstract Cuproptosis is a new form of programmed cell death and exhibits enormous potential in cancer treatment. However, reducing the undesirable Cu ion release in normal tissue and maximizing the copper‐induced therapeutic effect in cancer sites are two main challenges. In this study, we constructed a photothermally triggered nanoplatform (Au@MSN‐Cu/PEG/DSF) to realize on‐demand delivery for synergistic therapy. The released disulfiram (DSF) chelated with Cu2+ in situ to generate highly cytotoxic bis(diethyldithiocarbamate)copper (CuET), causing cell apoptosis, and the formed Cu+ species promoted toxic mitochondrial protein aggregation, leading to cell cuproptosis. Synergistic with photothermal therapy, Au@MSN‐Cu/PEG/DSF could effectively kill tumor cells and inhibit tumor growth (inhibition rate up to 80.1 %). These results provide a promising perspective for potential cancer treatment based on cuproptosis, and may also inspire the design of advanced nano‐therapeutic platforms.

Abstract Fabricating single‐atom electrodes via atomic dispersion of active metal atoms into monolithic metal supports is of great significance to advancing the lab‐to‐fab translation of the electrochemical technologies. Here, we report an inherent oxide anchoring strategy to fasten ligand‐free isolated Ru atoms on the amorphous layer of monolithic Ti support by regulating the electronic metal‐support interactions. The prepared Ru single atom electrode exhibited exceptional electrochemical chlorine evolution activity, three orders of magnitude higher mass activity than that of commercial dimensionally stable anode, and also selectively reduced nitrate to ammonia with an unprecedented ammonia yield rate of 22.2 mol g−1 h−1 at −0.3 V. Furthermore, the Ru single atom monolithic electrode can be scaled up from 2×2 cm to 25×15 cm at least, thus demonstrating great potential for industrial electrocatalytic applications.

Abstract Covalent organic frameworks (COFs) are gaining increasing attention as renewable cathode materials for Li‐ion batteries. However, COF electrodes reported so far still exhibit unsatisfying capacity due to their limited active site density and insufficient utilization. Herein, a new two‐dimensional polyimide‐linked COF, HATN‐AQ‐COF with multiple redox‐active sites for storing Li+ions, was designed and fabricated from a new module of 2,3,8,9,14,15‐hexacarboxyl hexaazatrinaphthalene trianhydrides with a 2,6‐diaminoanthraquinone linker. HATN‐AQ‐COF possessing excellent stability, good conductivity, and a large pore size of 3.8 nm enables the stable and fast ion transport. This, in combination with the abundant redox active sites, results in a high reversible capacity of 319 mAh g−1at 0.5 C (1 C=358 mA g−1) for the HATN‐AQ‐COF electrode with a high active site utilization of 89 % and good cycle performance, representing one of the best performances among the reported COF electrodes.

As a consequence of rapid industrialization throughout the world, various environmental pollutants have begun to accumulate in water, air, and soil. This endangers the ecological environment of the earth, and environmental remediation has become an immediate priority. Among various environmental remediation techniques, piezocatalytic techniques, which uniquely take advantage of the piezoelectric effect, have attracted much attention. Piezoelectric effects allow pollutant degradation directly, while also enhancing photocatalysis by reducing the recombination of photogenerated carriers. In this Review, we provide a comprehensive summary of recent developments in piezocatalytic techniques for environmental remediation. The origin of the piezoelectric effect as well as classification of piezoelectric materials and their application in environmental remediation are systematically summarized. We also analyze the potential underlying mechanisms. Finally, urgent problems and the future development of piezocatalytic techniques are discussed.

Abstract A large variety of nickel‐based catalysts has been investigated for the oxygen evolution reaction (OER) in alkaline media. However, their reported activity, as well as Tafel slope values, vary greatly. To understand this variation, we studied electrodeposited Ni80Fe20OOH catalysts with different loadings at varying rotation rates, hydroxide concentrations, with or without sonication. We show that, at low current density (<5 mA cm−2), the Tafel slope value is ≈30 mV dec−1for Ni80Fe20OOH. At higher polarization, the Tafel slope continuously increases and is dependent on rotation rate, loading, hydroxide concentration and sonication. These Tafel slope values are convoluted by non‐kinetic effects, such as bubbles, potential‐dependent changes in ohmic resistance and (internal) OH−gradients. As best practise, we suggest that Tafel slopes should be plotted vs. current or potential. In such a plot, it can be appreciated if there is a kinetic Tafel slope or if the observed Tafel slope is influenced by non‐kinetic effects.

Abstract Constructing monodispersed metal sites in heterocatalysis is an efficient strategy to boost their catalytic performance. Herein, a new strategy using monodispersed metal sites to tailor Pt‐based nanocatalysts is addressed by engineering unconventional p–d orbital hybridization. Thus, monodispersed Ga on Pt3Mn nanocrystals (Ga‐O‐Pt3Mn) with high‐indexed facets was constructed for the first time to drive ethanol electrooxidation reaction (EOR). Strikingly, the Ga‐O‐Pt3Mn nanocatalyst shows an enhanced EOR performance with achieving 8.41 times of specific activity than that of Pt/C. The electrochemical in situ Fourier transform infrared spectroscopy results and theoretical calculations disclose that the Ga‐O‐Pt3Mn nanocatalyst featuring an unconventional p–d orbital hybridization not only promote the C−C bond‐breaking and rapid oxidation of ‐OH of ethanol, but also inhibit the generation of poisonous CO intermediate species. This work discloses a promising strategy to construct a novel nanocatalysts tailored by monodispersed metal site as efficient fuel cell catalysts.

Abstract The design of efficient copper(Cu)‐based catalysts is critical for CO 2 electroreduction into multiple carbon products. However, most Cu‐based catalysts are favorable for ethylene production while selective production of ethanol with high Faradaic efficiency and current density still remains a great challenge. Herein, we design a carbon‐coated CuO x (CuO x @C) catalyst through one‐pot pyrolysis of Cu‐based metal‐organic framework (MOF), which exhibits high selectivity for CO 2 electroreduction to ethanol with Faradaic efficiency of 46 %. Impressively, the partial current density of ethanol reaches 166 mA cm −2 , which is higher than that of most reported catalysts. Operando Raman spectra indicate that the carbon coating can efficiently stabilize Cu + species under CO 2 electroreduction conditions, which promotes the C−C coupling step. Density functional theory (DFT) calculations reveal that the carbon layer can tune the key intermediate *HOCCH goes the hydrogenation pathway toward ethanol production.

Abstract All‐inorganic CsPbI 3 perovskite presents preeminent chemical stability and a desirable band gap as the front absorber for perovskite/silicon tandem solar cells. Unfortunately, CsPbI 3 perovskite solar cells (PSCs) still show low efficiency due to high density of defects in solution‐prepared CsPbI 3 films. Herein, three kinds of hydrazide derivatives (benzoyl hydrazine (BH), formohydrazide (FH) and benzamide (BA)) are designed to reduce the defect density and stabilize the phase of CsPbI 3 . Calculation and characterization results corroborate that the carboxyl and hydrazine groups in BH form strong chemical bonds with Pb 2+ ions, resulting in synergetic double coordination. In addition, the hydrazine group in the BH also forms a hydrogen bond with iodine to assist the coordination. Consequently, a high efficiency of 20.47 % is achieved, which is the highest PCE among all pure CsPbI 3 ‐based PSCs reported to date. In addition, an unencapsulated device showed excellent stability in ambient air.

The use of nanoparticles and nanostructured electrodes are abundant in electrocatalysis. These nanometric systems contain elements of nanoconfinement in different degrees, depending on the geometry, which can have a much greater effect on the activity and selectivity than often considered. In this Review, we firstly identify the systems containing different degrees of nanoconfinement and how they can affect the activity and selectivity of electrocatalytic reactions. Then we follow with a fundamental understanding of how electrochemistry and electrocatalysis are affected by nanoconfinement, which is beginning to be uncovered, thanks to the development of new, atomically precise manufacturing and fabrication techniques as well as advances in theoretical modeling. The aim of this Review is to help us look beyond using nanostructuring as just a way to increase surface area, but also as a way to break the scaling relations imposed on electrocatalysis by thermodynamics.

Abstract Electrolyte design has become ever more important to enhance the performance of lithium‐ion batteries (LIBs). However, the flammability issue and high reactivity of the conventional electrolytes remain a major problem, especially when the LIBs are operated at high voltage and extreme temperatures. Herein, we design a novel non‐flammable fluorinated ester electrolyte that enables high cycling stability in wide‐temperature variations (e.g., −50 °C–60 °C) and superior power capability (fast charge rates up to 5.0 C) for the graphite||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) battery at high voltage (i.e., >4.3 V vs. Li/Li + ). Moreover, this work sheds new light on the dynamic evolution and interaction among the Li + , solvent, and anion at the molecular level. By elucidating the fundamental relationship between the Li + solvation structure and electrochemical performance, we can facilitate the development of high‐safety and high‐energy‐density batteries operating in harsh conditions.

Abstract Zn metal as one of promising anode materials for aqueous batteries suffers from notorious dendrite growth, serious Zn corrosion and hydrogen evolution. Here, a bifunctional electrolyte additive, N‐methyl pyrrolidone (NMP), is developed to improve the electrochemical performance of Zn anode. NMP not only alters the solvation structure of Zn 2+ , but also in situ produces a dense N‐rich solid‐electrolyte‐interphase layer on Zn foils. This layer protects Zn foils from corrosive electrolytes and benefits the uniform plating/stripping of Zn. Hence, the asymmetrical cells with NMP in the electrolyte retain a high coulombic efficiency of 99.8 % over 1000 cycles. The symmetric cells survive ≈200 h for 10 mAh cm −2 at a high Zn utilization of 85.6 %. The full cells of Zn||MnO 2 show an impressive cumulative capacity even with lean electrolyte (E/C ratio=10 μL mAh −1 ), limited Zn supply (N/P ratio=2.3) and high areal capacity (5.0 mAh cm −2 ).

Abstract Synergistic optimization of the elementary steps of water dissociation and hydrogen desorption for the hydrogen evolution reaction (HER) in alkaline media is a challenge. Herein, the Ru cluster anchored on a trace P‐doped defective TiO 2 substrate (Ru/P‐TiO 2 ) was synthesized as an electrocatalyst for the HER; it exhibited a commercial Pt/C‐like geometric activity and an excellent mass activity of 9984.3 mA mg Ru −1 at −0.05 V vs. RHE, which is 34.3 and 18.7 times higher than that of Pt/C and Ru/TiO 2 , respectively. Experimental and theoretical studies indicated that using a rutile‐TiO 2 ‐crystal‐phase substrate enhanced the HER activity more than the anatase phase. Rich surface oxygen vacancies on rutile‐TiO 2 facilitated the adsorption and dissociation of water, while the partial substitution of Ti 4+ with P 5+ enhanced H 2 generation by facilitating hydrogen spillover from the Ru site to the surface P site, synergistically enhancing the HER activity.

Abstract We present a facile route towards a dual single‐atom nanozyme composed of Zn and Mo, which utilizes the non‐covalent nano‐assembly of polyoxometalates, supramolecular coordination complexes as the metal‐atom precursor, and a macroscopic amphiphilic aerogel as the supporting substrate. The dual single‐atoms of Zn and Mo have a high content (1.5 and 7.3 wt%, respectively) and exhibit a synergistic effect and a peroxidase‐like activity. The Zn/Mo site was identified as the main active center by X‐ray absorption fine structure spectroscopy and density functional theory calculation. The detection of versatile analytes, including intracellular H 2 O 2 , glucose in serum, cholesterol, and ascorbic acid in commercial beverages was achieved. The nanozyme has an outstanding stability and maintained its performance after one year's storage. This study develops a new peroxidase‐like nanozyme and provides a robust synthetic strategy for single‐atom catalysts by utilizing an aerogel as a facile substrate that is capable of stabilizing various metal atoms.

Abstract Pyroptosis provides a new direction and broad prospects for cancer immunotherapy. However, the development of a nanoplatform as a pyroptosis inducer is limited, and the discovery of a new type of nano‐pyroptosis inducer for cancer immunotherapy is still imminent. Herein, biodegradable Ca 2+ nanomodulators (CaNMs) are prepared as pyroptosis inducers for cancer immunotherapy via mitochondrial Ca 2+ overload. The obtained CaNMs can decompose under low pH to release Ca 2+ and curcumin, leading to a sudden surge in mitochondrial Ca 2+ ions, eventually resulting in pyroptosis. We not only confirm the occurrence of mitochondrial Ca 2+ overload‐triggered pyroptosis for the first time but also reveal the robust immune responses via CaNMs, along with remarkably suppressing tumor proliferation and lung metastasis. This work will provide new strategies and inspiration for pyroptosis‐mediated cancer treatments, greatly contributing to the further development of Ca 2+ nanomodulators.

Abstract Herein, we report a general strategy for achieving ultra‐pure green emissions by suppressing the shoulder peaks in the emission spectra of conventional polycyclic aromatic hydrocarbons (PAHs). Through precise synthetic fusion of multi‐resonance (MR) fragments with conventional PAH, extended π‐conjugation lengths, increased molecular rigidity, and reduced vibrational frequency could be simultaneously realized. The proof‐of‐concept emitters exhibited ultra‐pure green emissions with dominant peaks at ca. 521 nm, photoluminescence quantum yields that are greater than 99 %, a small full‐width‐at‐half‐maximum of 23 nm, and CIE coordinates of (0.16, 0.77). The bottom‐emitting organic light‐emitting diode (OLED) exhibited a record‐high CIEy value of 0.74 and a high maximum external quantum efficiency of 30.5 %. The top‐emitting OLED not only achieved a BT.2020 green color (CIE: 0.17, 0.78) for the first time but also showed superior performance among all green OLED devices, with a current efficiency of 220 cd A − .

Abstract Copper oxide‐based materials effectively electrocatalyze carbon dioxide reduction (CO 2 RR). To comprehend their role and achieve high CO 2 RR activity, Cu + in copper oxides must be stabilized. As an electrocatalyst, Cu 2 O nanoparticles were decorated with hexagonal boron nitride (h‐BN) nanosheets to stabilize Cu + . The C 2 H 4 /CO ratio increased 1.62‐fold in the CO 2 RR with Cu 2 O−BN compared to that with Cu 2 O. Experimental and theoretical studies confirmed strong electronic interactions between the two components in Cu 2 O−BN, which strengthens the Cu−O bonds. Electrophilic h‐BN receives partial electron density from Cu 2 O, protecting the Cu−O bonds from electron attack during the CO 2 RR and stabilizing the Cu + species during long‐term electrolysis. The well‐retained Cu + species enhanced the C 2 product selectivity and improved the stability of Cu 2 O−BN. This work offers new insight into the metal‐valence‐state‐dependent selectivity of catalysts, enabling the design of advanced catalysts.