The 100 most-cited articles in Angewandte Chemie, 2022

Abstract 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.

Abstract 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 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…

Abstract 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 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.

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 (ΔGH) on hollow sites. Herein, by studying the ΔGH 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 ΔGH 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 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, PdFe 1 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 NH 3 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 N 2 activation via N 2 ‐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 PdFe 1 for the NRR.

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 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 (Ru1‐NiO) as a catalyst in the neutral medium. For electrooxidation of 5‐hydroxymethylfurfural (HMF), Ru1‐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, Ru1‐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.

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 (Ti3C2TX/Cu‐BTC, Ti3C2TX/Fe,Co‐PBA, Ti3C2TX/ZIF‐8, and Ti3C2TX/ZIF‐67) that combine the advantages of MOFs and MXenes to enhance stability and improve conductivity. Subsequently, 3D hollow Ti3C2TX/ZIF‐67/CoV2O6 composites with excellent electron‐ and ion‐transport properties derived from Ti3C2TX/ZIF‐67 were synthesized. The specific capacitance of the Ti3C2TX/ZIF‐67/CoV2O6 electrode was 285.5 F g−1, which is much higher than that of the ZIF‐67 and Ti3C2TX/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 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 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.

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 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 Two‐dimensional metal–organic frameworks (2D MOFs) can be used as the cathodes for high‐performance zinc‐ion battery due to their large one‐dimensional channels. However, the conventionally poor electrical conductivity and low structural stability hinder their advances. Herein, we report an alternately stacked MOF/MX heterostructure, exhibiting the 2D sandwich‐like structure with abundant active sites, improved electrical conductivity and exceptional structural stability. Ex situ characterizations and theoretical calculations reveal a reversible intercalation mechanism of zinc ions and high electrical conductivity in the 2D heterostructure. Electrochemical tests confirm excellent Zn 2+ migration kinetics and ideal pseudocapacitive behaviors. As a consequence, Cu‐HHTP/MX shows a superior rate performance (260.1 mAh g −1 at 0.1 A g −1 and 173.1 mAh g −1 at 4 A g −1 ) and long‐term cycling stability of 92.5 % capacity retention over 1000 cycles at 4 A g −1 .

Abstract 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 Manganese oxides are promising cathode materials for aqueous zinc‐ion batteries (ZIBs) due to their high energy density and low cost. However, in their discharging processes, the Jahn–Teller effect and Mn 3+ disproportionation often lead to irreversible structural transformation and Mn 2+ dissolution, deteriorating the cycling stability of ZIBs. Herein, ZnMn 2 O 4 quantum dots (ZMO QDs) were introduced into a porous carbon framework by in‐situ electrochemically inducing Mn‐MIL‐100‐derived Mn 3 O 4 quantum dots and the carbon composite. In such ZMO QDs and carbon composite, the quantum dot structure endows ZnMn 2 O 4 with a shorter ion diffusion route and more active sites for Zn 2+ . The conductive carbon framework is beneficial to the fast transport of electrons. Furthermore, at the interface between the ZMO QDs and the carbon matrix, the Mn−O−C bonds are formed. They can effectively suppress the Jahn–Teller effect and manganese dissolution of discharge products. Therefore, Zn/ZMO QD@C batteries display remarkably enhanced electrochemical performance.

Abstract 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.

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 Pickering emulsions are particle‐stabilized surfactant‐free dispersions composed of two immiscible liquid phases, and emerge as attractive catalysis platform to surpass traditional technique barrier in some cases. In this review, we have comprehensively summarized the development and the catalysis applications of Pickering emulsions since the pioneering work in 2010. The explicit mechanism for Pickering emulsions will be initially discussed and clarified. Then, summarization is given to the design strategy of amphiphilic emulsion catalysts in two categories of intrinsic and extrinsic amphiphilicity. The progress of the unconventional catalytic reactions in Pickering emulsion is further described, especially for the polarity/solubility difference‐driven phase segregation, “smart” emulsion reaction system, continuous flow catalysis, and Pickering interfacial biocatalysis. Challenges and future trends for the development of Pickering emulsion catalysis are finally outlined.

Abstract The electrochemical nitrate reduction reaction (NO3RR) is an appealing technology for regulating the nitrogen cycle. Metallic iron is one of the well‐known electrocatalysts for NO3RR, but it suffers from poor durability due to leaching and oxidation of iron during the electrocatalytic process. In this work, a graphene‐nanochainmail‐protected iron nanoparticle (Fe@Gnc) electrocatalyst is reported. It displays superior nitrate removal efficiency and high nitrogen selectivity. Notably, the catalyst delivers exceptional stability and durability, with the nitrate removal rate and nitrogen selectivity remained ≈96 % of that of the first time after up to 40 cycles (24 h for one cycle). As expected, the conductive graphene nanochainmail provides robust protection for the internal iron active sites, allowing Fe@Gnc to maintain its long‐lasting electrochemical nitrate catalytic activity. This research proposes a workable solution for the scientific challenge of poor lasting ability of iron‐based electrocatalysts in large‐scale industrialization.

Abstract The regulation of electron distribution of single‐atomic metal sites by atomic clusters is an effective strategy to boost their intrinsic activity of oxygen reduction reaction (ORR). Herein we report the construction of single‐atomic Mn sites decorated with atomic clusters by an innovative combination of post‐adsorption and secondary pyrolysis. The X‐ray absorption spectroscopy confirms the formation of Mn sites via Mn‐N4coordination bonding to FeMn atomic clusters (FeMnac/Mn‐N4C), which has been demonstrated theoretically to be conducive to the adsorption of molecular O2and the break of O−O bond during the ORR process. Benefiting from the structural features above, the FeMnac/Mn‐N4C catalyst exhibits excellent ORR activity with half‐wave potential of 0.79 V in 0.5 M H2SO4and 0.90 V in 0.1 M KOH as well as preeminent Zn‐air battery performance. Such synthetic strategy may open up a route to construct highly active catalysts with tunable atomic structures for diverse applications.

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.

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 Photocatalytic CO2 reduction reaction (CO2RR) is an attractive process to convert CO2 into valuable chemicals. But this reaction is often restricted by the poor mass transfer of CO2 in the liquid phase. Here, we have developed a triphase photocatalytic CO2RR system by supporting Ag‐decorated TiO2 nanoparticles at a gas–water boundary with hydrophobic–hydrophilic abrupt interfacial wettability. Such a triphase system allows the rapid delivery of gas‐phase CO2 to the surface of photocatalysts while maintaining an efficient water supply and uncovered active sites. Ag‐TiO2 supported at the gas–water boundary showed a CO2 reduction rate of 305.7 μmol g−1 h−1, without hole scavengers, approximately 8 times higher than the nanoparticles dispersed in the liquid phase. Even using diluted CO2 (10 %) as the reactant, the CO2RR activity was superior to most reported Ag‐TiO2 based photocatalysts using pure CO2. The findings provide a general strategy to promote the interfacial CO2 mass transfer to improve photoactivity and selectivity.

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 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 The global utilization of H2O2 is currently around 4 million tons per year and is expected to continue to increase in the future. H2O2 is mainly produced by the anthraquinone process, which involves multiple steps in terms of alkylanthraquinone hydrogenation/oxidation in organic solvents and liquid–liquid extraction of H2O2. The energy‐intensive and environmentally unfriendly anthraquinone process does not meet the requirements of sustainable and low‐carbon development. The electrocatalytic two‐electron (2 e−) oxygen reduction reaction (ORR) driven by renewable energy (e.g. solar and wind power) offers a more economical, low‐carbon, and greener route to produce H2O2. However, continuous and decentralized H2O2 electrosynthesis still poses many challenges. This Minireview first summarizes the development of devices for H2O2 electrosynthesis, and then introduces each component, the assembly process, and some optimization strategies.

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 It remains a great challenge to develop polymer‐based materials with efficient and color‐tunable organic afterglow. Two indolocarbazole derivatives IaCzA and IbCzA have been synthesized and doped into poly(vinyl alcohol) (PVA) matrices. It is found that the resulting films can produce unique dual‐mode afterglow, which is composed of persistent thermally activated delayed fluorescence and ultralong organic phosphorescence. Besides, the IbCzA‐doped PVA film exhibits intense blue afterglow with Φ afterglow and τ afterglow up to 19.8 % and 1.81 s, respectively, representing state‐of‐the‐art dual‐mode organic afterglow performance. Moreover, our reported film has high flexibility, excellent transparency, and large‐area producibility; and the afterglow color of the film can be linearly tuned by temperature. Inspired by these distinctive properties, the PVA doped with IbCzA was employed as temperature‐sensitive security ink for anti‐counterfeiting and information encryption.

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||LiNi0.8Co0.1Mn0.1O2 (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 We propose the pseudobrookite Fe 2 TiO 5 nanofiber with abundant oxygen vacancies as a new electrocatalyst to ambiently reduce nitrate to ammonia. Such catalyst achieves a large NH 3 yield of 0.73 mmol h −1 mg −1 cat. and a high Faradaic Efficiency (FE) of 87.6 % in phosphate buffer saline solution with 0.1 M NaNO 3 , which is lifted to 1.36 mmol h −1 mg −1 cat. and 96.06 % at −0.9 V vs. RHE for nitrite conversion to ammonia in 0.1 M NaNO 2 . It also shows excellent electrochemical durability and structural stability. Theoretical calculation reveals the enhanced conductivity of this catalyst and an extremely low free energy of −0.28 eV for nitrate adsorption at the presence of vacant oxygen.

Abstract As hot topics in the chemical conversion of CO 2 , the photo‐/electrocatalytic reduction of CO 2 and use of CO 2 as a supporter for energy storage have shown great potential for the utilization of CO 2 . However, many obstacles still exist on the road to realizing highly efficient chemical CO 2 conversion, such as inefficient uptake/activation of CO 2 and 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 CO 2 owing 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 CO 2 conversion and energy storage. This Minireview discusses recent breakthroughs in the basic knowledge, mechanisms, and pathways of chemical CO 2 conversion strategies that use COF‐based functional catalysts. In addition, the challenges and prospects of COF‐based functional catalysts for the efficient utilization of CO 2 are also introduced.

Abstract Water scarcity caused by climate change and population growth poses a grave threat to human society. Of the different water purification technologies put forward, one presents a promising strategy that is spatially or temporally non‐restricted—atmospheric water harvesting (AWH). Here we review recent progress in the design and study of AWH sorbents, ranging from the innovative chemistries to the integration of sophisticated architectures and functional components, and clarify the structure–property–performance relationship that governs the water capture and release processes. Features and limitations of each type of sorbents are summarized to elucidate the optimal working environments and modes. Progress in applications extending from water generation to thermal management and agriculture are discussed. Future developments regarding material modifications, performance measurements, and system optimizations are provided to overcome lingering barriers to sorbent design and implementation.

Abstract Photoreduction of CO2 to C2+ 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 CO2 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 Exploring functional substrates and precisely regulating the electronic structures of atomic metal active species with moderate spin state are of great importance yet remain challenging. Hereon, we provide an axial Fe‐O‐Ti ligand regulated spin‐state transition strategy to improve the oxygen reduction reaction (ORR) activity of Fe centers. Theoretical calculations indicate that Fe‐O‐Ti ligands in FeN3O‐O‐Ti can induce a low‐to‐medium spin‐state transition and optimize O2 adsorption by FeN3O. As a proof‐of‐concept, the oriented catalyst was prepared from atomic‐Fe‐doped polymer‐like quantum dots and ultrathin o‐terminated MXene. The optimal catalyst exhibits an intrinsic activity that is almost 5 times higher than the control sample (without axial Fe‐O‐Ti ligands). It also delivers a superior performance in Zn‐air batteries and H2/O2 anion exchange membrane fuel cells in a wide‐temperature range.

Abstract 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.

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 Glass is a group of materials with appealing qualities, including simplicity in fabrication, durability, and high transparency, and they play a crucial role in the optics field. In this paper, a new organic–inorganic metal halide luminescent glass exhibiting >78 % transmittance at 506–800 nm range together with a high photoluminescence quantum yield (PLQY) of 28.5 % is reported through a low‐temperature melt‐quenching approach of pre‐synthesized (HTPP) 2 MnBr 4 (HTPP=hexyltriphenylphosphonium) single crystal. Temperature‐dependent X‐ray diffraction, polarizing microscopy, and molecular dynamics simulations were combined to investigate the glass‐crystal interconversion process, revealing the disordered nature of the glassy state. Benefiting from the transparent nature, (HTPP) 2 MnBr 4 glass yields an outstanding spatial resolution of 10 lp mm −1 for X‐ray imaging. The superb optical properties and facility of large‐scale fabrication distinguish the organic–inorganic metal halide glass as a highly promising class of materials for optical devices.

Abstract Redox‐active organic materials, as a new generation of sustainable resources, are receiving increasing attention in zinc‐ion batteries (ZIBs) due to their resource abundance and tunable structure. However, organic molecules with high potential are rare, and the voltage of most reported organic cathode‐based ZIBs is less than 1.2 V. Herein, we explored the redox process of p‐type organics and figured out the relationship between energy change and voltage output during the process. Then, we proposed a dual‐step strategy to effectively tune the energy change and eventually improve the output voltage of the organic electrode. Combining the regulation of the electron cloud of organic molecules and the manipulation of the solvation structure, the output voltage of an organosulfur compound based ZIB was greatly increased from 0.8 V to 1.7 V. Our results put forward a specific pathway to improve the working voltage and lay the foundation for the practical application of organic electrodes.

Abstract The minimization of thermal quenching, which leads to luminescence loss at high temperatures, is one of the most important issues for near‐infrared phosphors. In the present work, we investigated the properties of near‐infrared Ca(Sc,Mg)(Al, Si)O 6 : Cr 3+ phosphors with a pyroxene‐type structure under blue light excitation. The CaScAlSiO 6 : Cr 3+ end member of Ca(Sc,Mg)(Al,Si)O 6 : Cr 3+ phosphor led to broadband emission at a full‐width half maximum of 215 nm, whereas the CaMgSi 2 O 6 : Cr 3+ end member exhibited high thermal stability at 150 °C, with an intensity of 88.4 % of that at room temperature. The structural analysis and density functional theory calculations revealed the absence of soft conformations and local space confinement contributed to the high structural rigidity and weakened the thermal quenching effect.

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 Zn2+/H+, particularly the storage of Zn2+, due to the more favorable O⋅⋅⋅Zn⋅⋅⋅N coordination in HATNQ.

Abstract Water pollution is a growing threat to humanity due to the pervasiveness of contaminants in water bodies. Significant efforts have been made to separate these hazardous components to purify polluted water through various methods. However, conventional remediation methods suffer from limitations such as low uptake capacity or selectivity, and current water quality standards cannot be met. Recently, advanced porous materials (APMs) have shown promise in improved segregation of contaminants compared to traditional porous materials in uptake capacity and selectivity. These materials feature merits of high surface area and versatile functionality, rendering them ideal platforms for the design of novel adsorbents. This Review summarizes the development and employment of APMs in a variety of water treatments accompanied by assessments of task‐specific adsorption performance. Finally, we discuss our perspectives on future opportunities for APMs in water purification.

Abstract Poor oxygen diffusion at multiphase interfaces in an air cathode suppresses the energy densities of zinc–air batteries (ZABs). Developing effective strategies to tackle the issue is of great significance for overcoming the performance bottleneck. Herein, inspired by the bionics of diving flies, a polytetrafluoroethylene layer was coated on the surfaces of Co3O4 nanosheets (NSs) grown on carbon cloth (CC) to create a hydrophobic surface to enable the formation of more three‐phase reaction interfaces and promoted oxygen diffusion, rendering the hydrophobic‐Co3O4 NSs/CC electrode a higher limiting current density (214 mA cm−2 at 0.3 V) than that (10 mA cm−2) of untreated‐Co3O4 NSs/CC electrode. Consequently, the assembled ZAB employing hydrophobic‐Co3O4 NSs/CC cathode acquired a higher power density (171 mW cm−2) than that (102 mW cm−2) utilizing untreated‐Co3O4 NSs/CC cathode, proving the enhanced interfacial reaction kinetics on air cathode benefiting from the hydrophobization engineering.

Abstract Synthesizing H2O2 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 H2O2 production. Herein we prepare a bipyridine‐based covalent organic framework photocatalyst (denoted as COF‐TfpBpy) for H2O2 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 H2O2 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 H2O2 from water and air; and paves the way for wastewater treatment…

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 sp2‐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 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 CIE y coordinates below 0.08. Structure–property investigations demonstrate a strategic improvement of the oscillator strength ( f osc ) 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 Li–O 2 batteries have aroused considerable interest in recent years, however they are hindered by high kinetic barriers and large overvoltages at cathodes. Herein, a step‐scheme (S‐scheme) junction with hematite on carbon nitride (Fe 2 O 3 /C 3 N 4 ) is designed as a bifunctional catalyst to facilitate oxygen redox for a visible‐light‐involved Li–O 2 battery. The internal electric field and interfacial Fe−N bonding in the heterojunction boost the separation and directional migration of photo‐carriers to establish spatially isolated redox centers, at which the photoelectrons on C 3 N 4 and holes on Fe 2 O 3 remarkably accelerate the discharge and charge kinetics. These enable the Li–O 2 battery with Fe 2 O 3 /C 3 N 4 to present an elevated discharge voltage of 3.13 V under illumination, higher than the equilibrium potential 2.96 V in the dark, and a charge voltage of 3.19 V, as well as superior rate capability and cycling stability. This work will shed light on rational cathode design for metal–O 2 batteries.

Abstract 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 Alloy‐type anodes are one of the most promising classes of next‐generation anode materials due to their ultrahigh theoretical capacity (2–10 times that of graphite). However, current alloy‐type anodes have several limitations: huge volume expansion, high tendency to fracture and disintegrate, an unstable solid–electrolyte interphase (SEI) layer, and low Coulombic efficiency. Efforts to overcome these challenges are ongoing. This Review details recent progress in the research of batteries based on alloy‐type anodes and discusses the direction of their future development. We conclude that improvements in structural design, the introduction of a protective interface, and the selection of suitable electrolytes are the most effective ways to improve the performance of alloy‐type anodes. Furthermore, future studies should direct more attention toward analyzing their synergistic promoting effect.

Abstract A proton exchange membrane water electrolyzer (PEMWE) in acidic medium is a hopeful scenario for hydrogen production using renewable energy, but the grand challenge lies in substituting noble‐metal catalysts. Herein, a robust electrocatalyst of V−CoP2 porous nanowires arranged on a carbon cloth is successfully fabricated by incorporating vanadium into the CoP2 lattice. Structural characterizations and theoretical analysis indicate that lattice expansion of CoP2 caused by V incorporation results in the upshift of the d‐band center, which is conducive to hydrogen adsorption for boosting the hydrogen evolution reaction (HER). Besides, V promotes surface reconstruction to generate a thicker Co3O4 layer with an oxygen vacancy that enhances acid‐corrosion resistance and optimizes the adsorption of water and oxygen‐containing species, thus improving activity and stability toward the oxygen evolution reaction (OER). Accordingly, it presents a superior acidic overall water splitting activity (1.47 V@10 mA cm−2) to Pt−C/CC||RuO2/CC (1.59 V@10 mA cm−2), and remarkable stability. This…

Abstract Designing water‐deficient solvation sheath of Zn2+ by ligand substitution is a widely used strategy to protect Zn metal anode, yet the intrinsic tradeoff between Zn nucleation/dissolution kinetics and the side hydrogen evolution reaction (HER) remains a huge challenge. Herein, we find boric acid (BA) with moderate ligand field interaction can partially replace H2O molecules in the solvation sheath of Zn2+, forming a stable water‐deficient solvation sheath. It enables fast Zn nucleation/dissolution kinetics and substantially suppressed HER. Crucially, by systematically comparing the ligand field strength and solvation energies between BA and the ever‐reported electrolyte additives, we also find that the solvation energy has a strong correlation with Zn nucleation/dissolution kinetics and HER inhibition ability, displaying a classic volcano behavior. The modulation map could provide valuable insights for solvation sheath design of zinc batteries and beyond.

Abstract Regulating intermediates through elaborate catalyst design to control the reaction direction is crucial for promoting the selectivity of electrocatalytic CO2‐to‐CH4. M−C (M=metal) bonds are particularly important for tuning the multi‐electron reaction; however, its construction in nanomaterials is challenging. Here, via rational design of in situ anchoring of Cu SAs (single atoms) on the unique platform graphdiyne, we firstly realize the construction of a chemical bond Cu−C (GDY). In situ Raman spectroelectrochemistry and DFT calculations confirm that due to the fabrication of the Cu−C bond, during CO2 reduction, the formation of *OCHO intermediates is dominant rather than *COOH on Cu atoms, facilitating the formation of CH4. Therefore, we find that constructing the Cu−C bond in Cu SAs/GDY can supply an efficient charge transfer channel, but most importantly control the reaction intermediates and guide a more facile reaction pathway to CH4, thereby significantly boosting its catalytic performance. This work provides new insights on enhancing the selectivity for CO2RR at the…

Abstract Chlorine evolution reaction has been applied in the production since a century ago. After times of evolution, it has been widely realized by the electrocatalytic process on anode nowadays. However, the anode applied in production contains a large amount of precious metal, increasing the cost. It is thus an opportunity to apply sub‐nano catalysts in this field. By regulating the tip effect (TE) of the catalyst, it was discovered that the oxidized sub‐nano iridium clusters supported by titanium carbide exhibit much higher efficiency than the single‐atom one, which demonstrates the significance of modifying the electronic interaction. Moreover, it exhibits a ≈20 % decrease of the electricity, ≈98 % selectivity towards chlorine evolution reaction, and high durability of over 350 h. Therefore, this cluster catalyst performs great potential in applying in the practical production and the comprehension of the tip effect on different types of catalysts is also pushed to a higher level.

Abstract 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 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 −1 at 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.

Abstract All‐inorganic lead‐free perovskite‐derivative metal halides have shown great promise in optoelectronics, however, it remains challenging to realize efficient near‐infrared (NIR) luminescence in these materials. Herein, we report a novel strategy based on Te4+/Ln3+ (Ln=Er, Nd, and Yb) co‐doping to achieve efficient NIR luminescence in vacancy‐ordered double perovskite Cs2ZrCl6 phosphors, which are excitable by a low‐cost near‐ultraviolet light‐emitting diode (LED) chip. Through sensitization by the spin‐orbital allowed 1S0→3P1 transition of Te4+, intense and multi‐wavelength NIR luminescence originating from the 4f→4f transitions of Er3+, Nd3+, and Yb3+ was acquired, with a quantum yield of 6.1 % for the Er3+ emission. These findings provide a general approach to achieve efficient NIR emission in lead‐free metal halides through ns2‐metal and lanthanide ion co‐doping, thereby opening up a new avenue for exploring NIR‐emitting perovskite derivatives towards versatile applications such as NIR‐LEDs and bioimaging.

Abstract We report a cationic porphyrin 5,10,15,20‐tetrakis‐(4‐N‐methylpyridyl)‐porphyrin (TMPyP) that can respond to specific bacteria, followed by adaptable photodynamic/photothermal therapy processes. TMPyP could be reduced to phlorin by facultative anaerobes with a strong reducing ability such as E. coli and S. typhimurium in hypoxic environments, possessing strong NIR absorption and remarkable photothermal conversion capacity, thus demonstrating excellent antimicrobial activity (>99 %) by photothermal therapy. While in an aerobic environment with aerobic bacteria, TMPyP functioned as a typical photosensitizer that killed bacteria effectively (>99.9 %) by photodynamic therapy. By forming a host–guest complex with cucurbit[7]uril, the biocompatibility of TMPyP significantly improved. This kind of bacteria‐responsive porphyrin shows specificity and adaptivity in antimicrobial treatment and holds potential in non‐invasive treatments of bacterial infections.

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…

Abstract Advanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO4)2 was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at −35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm−2, and the Zn/PANI battery can provide ultra‐high stable specific capacity of 79.6 mAh g−1 for more than 70 000 cycles at 15 A g−1. This can be mainly ascribed to the −SO3−H+ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton‐supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.

Abstract Aqueous zinc‐ion batteries (AZBs) show promises for large‐scale energy storage. However, the zinc utilization rate (ZUR) is generally low due to side reactions in the aqueous electrolyte caused by the active water molecules. Here, we design a novel solvation structure in the electrolyte by introduction of sulfolane (SL). Theoretical calculations, molecular dynamics simulations and experimental tests show that SL remodels the primary solvation shell of Zn 2+ , which significantly reduces the side reactions of Zn anode and achieves high ZUR under large capacities. Specifically, the symmetric and asymmetric cells could achieve a maximum of ∼96 % ZUR at an areal capacity of 24 mAh cm −2 . In a ZUR of ∼67 %, the developed Zn−V 2 O 5 full cell can be stably cycled for 500 cycles with an energy density of 180 Wh kg −1 and Zn‐AC capacitor is stable for 5000 cycles. This electrolyte structural engineering strategy provides new insight into achieving high ZUR of Zn anodes for high performance AZBs.

Abstract 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.

Abstract Solar‐driven CO2 methanation with water is an important route to simultaneously address carbon neutrality and produce fuels. It is challenging to achieve high selectivity in CO2 methanation due to competing reactions. Nonetheless, aspects of the catalyst design can be controlled with meaningful effects on the catalytic outcomes. We report highly selective CO2 methanation with water vapor using a photocatalyst that integrates polymeric carbon nitride (CN) with single Pt atoms. As revealed by experimental characterization and theoretical simulations, the widely explored Pt−CN catalyst is adapted for selective CO2 methanation with our rationally designed synthetic method. The synthesis creates defects in CN along with formation of hydroxyl groups proximal to the coordinated Pt atoms. The photocatalyst exhibits high activity and carbon selectivity (99 %) for CH4 production in photocatalytic CO2 reduction with pure water. This work provides atomic scale insight into the design of photocatalysts for selective CO2 methanation.

Abstract Polyethylene terephthalate (PET) and CO2, two chemical wastes that urgently need to be transformed in the environment, are converted simultaneously in a one‐pot catalytic process through the synergistic coupling of three reactions: CO2 hydrogenation, PET methanolysis and dimethyl terephthalate (DMT) hydrogenation. More interestingly, the chemical equilibria of both reactions were shifted forward due to a revealed dual‐promotion effect, leading to significantly enhanced PET depolymerization. The overall methanol yield from CO2 hydrogenation exceeded the original thermodynamic equilibrium limit since the methanol was in situ consumed in the PET methanolysis. The degradation of PET by a stoichiometric ratio of methanol was significantly enhanced because the primary product, DMT was hydrogenated to dimethyl cyclohexanedicarboxylate (DMCD) or p‐xylene (PX). This synergistic catalytic process provides an effective way to simultaneously recycle two wastes, polyesters and CO2, for producing high‐value chemicals.

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 Highly efficient circularly polarized luminescence (CPL) emitters with narrowband emission remain a formidable challenge for circularly polarized OLEDs (CP‐OLEDs). Here, a promising strategy for developing chiral emitters concurrently featuring multi‐resonance thermally activated delayed fluorescence (MR‐TADF) and circularly polarized electroluminescence (CPEL) is demonstrated by the integration of molecular rigidity, central chirality and MR effect. A pair of chiral green emitters denoted as (R)‐BN‐MeIAcand (S)‐BN‐MeIAcis designed. Benefited by the rigid and quasi‐planar MR‐framework, the enantiomers not only display mirror‐image CPL spectra, but also exhibit TADF properties with a high photoluminescence quantum yield of 96 %, a narrow FWHM of 30 nm, and a high horizontal dipole orientation of 90 % in the doped film. Consequently, the enantiomer‐based CP‐OLEDs achieved excellent external quantum efficiencies of 37.2 % with very low efficiency roll‐off, representing the highest device efficiency of all the reported CP‐OLEDs.

Abstract With fascinating photophysical properties and a strong potential to utilize solar energy, metal halide perovskites (MHPs) have become a prominent feature within photocatalysis research. However, the effectiveness of single MHP photocatalysts is relatively poor. The introduction of a second component to form a heterojunction represents a well‐established route to accelerate carrier migration and boost reaction rates, thus increasing the photoactivity. Recently, there have been several scientific advances related to the design of MHP‐based heterojunction photocatalysts, including Schottky, type II, and Z‐scheme heterojunctions. In this Review, we systematically discuss and critically appraise recent developments in MHP‐based heterojunction photocatalysis. In addition, the techniques for identifying the type of active heterojunctions are evaluated and we conclude by briefly outlining the ongoing challenges and future directions for promising photocatalysts based on MHP heterojunctions.

Abstract The photocatalytic conversion of solar energy offers a potential route to renewable energy, and its efficiency relies on effective charge separation in nanostructured photocatalysts. Understanding the charge‐separation mechanism is key to improving the photocatalytic performance and this has now been enabled by advances in the spatially resolved surface photovoltage (SRSPV) method. In this Review we highlight progress made by SRSPV in mapping charge distributions at the nanoscale and determining the driving forces of charge separation in heterogeneous photocatalyst particles. We discuss how charge separation arising from a built‐in electric field, diffusion, and trapping can be exploited and optimized through photocatalyst design. We also highlight the importance of asymmetric engineering of photocatalysts for effective charge separation. Finally, we provide an outlook on further opportunities that arise from leveraging these insights to guide the rational design of photocatalysts and advance the imaging technique to expand the knowledge of charge separation.

Abstract Zinc metal battery (ZMB) is promising as the next generation of energy storage system, but challenges relating to dendrites and corrosion of the zinc anode are restricting its practical application. Here, to stabilize Zn anode, we report a controlled electrolytic method for a monolithic solid‐electrolyte interphase (SEI) via a high dipole moment solvent dimethyl methylphosphonate (DMMP). The DMMP‐based electrolytes can generate a homogeneous and robust phosphate SEI (Zn3(PO4)2 and ZnP2O6). Benefiting from the protecting impact of this in situ monolithic SEI, the zinc electrode exhibits long‐term cycling of 4700 h and a high Coulombic efficiency 99.89 % in Zn|Zn and Zn|Cu cell, respectively. The full V2O5|Zn battery with DMMP‐H2O hybrid electrolyte exhibits a high capacity retention of 82.2 % following 4000 cycles under 5 A g−1. The first success in constructing the monolithic phosphate SEI will open a new avenue in electrolyte design for highly reversible and stable Zn metal anodes.

Abstract 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 Single‐atom catalysts (SACs) are being pursued as economical electrocatalysts. However, their low active‐site loading, poor interactions, and unclear catalytic mechanism call for significant advances. Herein, atomically dispersed Ni/Co dual sites anchored on nitrogen‐doped carbon (a‐NiCo/NC) hollow prisms are rationally designed and synthesized. Benefiting from the atomically dispersed dual‐metal sites and their synergistic interactions, the obtained a‐NiCo/NC sample exhibits superior electrocatalytic activity and kinetics towards the oxygen evolution reaction. Moreover, density functional theory calculations indicate that the strong synergistic interactions from heteronuclear paired Ni/Co dual sites lead to the optimization of the electronic structure and the reduced reaction energy barrier. This work provides a promising strategy for the synthesis of high‐efficiency atomically dispersed dual‐site SACs in the field of electrochemical energy storage and conversion.

Abstract The construction of highly active, durable, and cost‐effective catalysts is urgently needed for green hydrogen production. Herein, catalysts consisting of high‐density Pt (24 atoms nm−2) and Ir (32 atoms nm−2) single atoms anchored on Co(OH)2 were constructed by a facile one‐step approach. Remarkably, Pt1/Co(OH)2 and Ir1/Co(OH)2 only required 4 and 178 mV at 10 mA cm−2 for hydrogen evolution reaction and oxygen evolution reaction, respectively. Moreover, the assembled Pt1/Co(OH)2//Ir1/Co(OH)2 system showed mass activity of 4.9 A mgnoble metal−1 at 2.0 V in an alkaline water electrolyzer, which is 316.1 times higher than that of Pt/C//IrO2. Mechanistic studies revealed that reconstructed Ir−O6 single atoms and remodeled Pt triple‐atom sites enhanced the occupancy of Ir−O bonding orbitals and improved the occupation of Pt−H antibonding orbital, respectively, contributing to the formation of the O−O bond and the desorption of hydrogen. This one‐step approach was also generalized to fabricate other 20 single‐atom catalysts.

Abstract 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 Rather than just focusing on the catalyst itself in the electrocatalytic CO2 reduction reaction (eCO2RR), as previously reviewed elsewhere, we herein extend the discussion to the special topic of the microenvironment around the electrocatalytic center and present a comprehensive overview of recent research progress. We categorize the microenvironment based on the components relevant to electrocatalytic active sites, i.e., the catalyst surface, substrate, co‐reactants, electrolyte, membrane, and reactor. Supported by most of the reported articles, the relevant factors affecting the catalytic performance of eCO2RR are then discussed in detail, and existing challenges and potential solutions are mentioned. Perspectives for the future research on eCO2RR, including the integration of different microenvironment factors, the extension to industrial application by coupling with carbon capture and conversion, and separation of products, are also discussed.

Abstract 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 Developing robust electrocatalysts and advanced devices is important for electrochemical carbon dioxide (CO2) reduction toward the generation of valuable chemicals. We present herein a carbon‐confined indium oxide electrocatalyst for stable and efficient CO2 reduction. The reductive corrosion of oxidative indium to the metallic state during electrolysis could be prevented by carbon protection, and the applied carbon layer also optimizes the reaction intermediate adsorption, which enables both high selectivity and activity for CO2 reduction. In a liquid‐phase flow cell, the formate selectivity exceeds 90 % in a wide potential window from −0.8 V to −1.3 V vs. RHE. The continuous production of ca. 0.12 M pure formic acid solution is further demonstrated at a current density of 30 mA cm−2 in a solid‐state electrolyte mediated reactor. This work provides significant concepts in the parallel development of electrocatalysts and devices for carbon‐neutral technologies.

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 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 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 Dynamic bonds introduce unique properties such as self‐healing, recyclability, shape memory, and malleability to polymers. Significant efforts have been made to synthesize a variety of dynamic linkers, creating a diverse library of materials. In addition to the development of new dynamic chemistries, fine‐tuning of dynamic bonds has emerged as a technique to modulate dynamic properties. This Review highlights approaches for controlling the timescales of dynamic bonds in polymers. Particularly, eight dynamic bonds are considered, including urea/urethanes, boronic esters, Thiol–Michael exchange, Diels–Alder adducts, transesterification, imine bonds, coordination bonds, and hydrogen bonding. This Review emphasizes how structural modifications and external factors have been used as tools to tune the dynamic character of materials. Finally, this Review proposes strategies for tailoring the timescales of dynamic bonds in polymer materials through both kinetic effects and modulating bond thermodynamics.

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 BiFeO3@TpPa‐1‐COF photocatalyst revealed hydrogen (H2) and oxygen (O2) 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 Electroreduction of CO2to acetate provides a promising strategy to reduce CO2emissions and store renewable energy, but acetate is usually a by‐product. Here, we show a stable and conductive two‐dimensional phthalocyanine‐based covalent‐organic framework (COF) as an electrocatalyst for reduction of CO2to acetate with a single‐product Faradaic efficiency (FE) of 90.3(2)% at −0.8 V (vs. RHE) and a current density of 12.5 mA cm−2in 0.1 M KHCO3solution. No obvious degradation was observed over 80 hours of continuous operation. Combined with the comparison of the properties of other catalysts with isolated metal active sites, theoretical calculations and in situ infrared spectroscopy revealed that the isolated copper‐phthalocyanine active site with high electron density is conducive to the key step of C−C coupling of *CH3with CO2to produce acetate, and can avoid the coupling of *CO with *CO or *CHO to produce ethylene and ethanol.

Abstract Charge transfer between metal sites and supports is crucial for catalysis. Redox‐inert supports are usually unfavorable due to their less electronic interaction with metal sites, which, we demonstrate, is not always correct. Herein, three metal–organic frameworks (MOFs) are chosen to mimic inert or active supports for Pt nanoparticles (NPs) and the photocatalysis is studied. Results demonstrate the formation of a Schottky junction between Pt and the MOFs, leading to the electron‐donation effect of the MOFs. Under light irradiation, both the MOF electron‐donation effect and Pt interband excitation dominate the Pt electron density. Compared with the “active” UiO‐66 and MIL‐125 supports, Pt NPs on the “inert” ZIF‐8 exhibit higher electron density due to the higher Schottky barrier, resulting in superior photocatalytic activity. This work optimizes metal catalysts with non‐reducible supports, and promotes the understanding of the relationship between the metal–support interaction and photocatalysis.

Abstract The discovery and identification of novel active sites are paramount for deepening the understanding of the catalytic mechanism and driving the development of remarkable electrocatalysts. Here, we reveal that the genuine active sites for the hydrogen evolution reaction (HER) in LaRuSi are Si sites, not the usually assumed Ru sites. Ru in LaRuSi has a peculiar negative valence state, which leads to strong hydrogen binding to Ru sites. Surprisingly, the Si sites have a Gibbs free energy of hydrogen adsorption that is near zero (0.063 eV). The moderate adsorption of hydrogen on Si sites during the HER process is also validated by in situ Raman analysis. Based on it, LaRuSi exhibits an overpotential of 72 mV at 10 mA cm−2 in alkaline media, which is close to the benchmark of Pt/C. This work sheds light on the recognition of real active sites and the exploration of innovative silicide HER electrocatalysts.

Abstract Due to the large abundance, low redox potential, and multivalent properties of calcium (Ca), Ca‐ion batteries (CIBs) show promising prospects for energy storage applications. However, current research on CIBs faces the challenges of unsatisfactory cycling stability and capacity, mainly restricted by the lack of suitable electrolytes and electrode materials. Herein, we firstly developed a 3.5 m concentrated electrolyte with a calcium bis(fluorosulfonyl)imide (Ca(FSI)2) salt dissolved in carbonate solvents. This electrolyte significantly improved the intercalation capacity for anions in the graphite cathode and contributed to the reversible insertion of Ca2+ in the organic anode. By combining this concentrated electrolyte with the low‐cost and environmentally friendly graphite cathode and organic anode, the assembled Ca‐based dual‐ion battery (Ca‐DIB) exhibits 75.4 mAh g−1 specific discharge capacity at 100 mA g−1 and 84.7 % capacity retention over 350 cycles, among the best results known for CIBs.

Abstract Constructing stable surface modification layer is an effective strategy to suppress dendrite growth and side reactions of Zinc (Zn) metal anode in aqueous Zn‐ion battery. Herein, a multicomponent Cu−Zn alloy interlayer with superior Zn affinity, high toughness and effective inhibition effect on lattice distortion is constructed on Zn foil (Cu−Zn@Zn) to fabricate ultra‐stable Zn metal anode. Owning to the advantages of high binding energy of Cu−Zn alloy layer with Zn atoms and less contact area between metallic Zn and electrolyte, the as‐prepared Cu−Zn@Zn electrode not only restricts the aggregation of Zn atoms, but also suppresses the pernicious hydrogen evolution and corrosion, leading to homogeneous Zn deposition and outstanding electrochemical performances. Accordingly, the symmetric battery with Cu−Zn@Zn electrode exhibits an ultra‐long cycle life of 5496 h at 1 mA cm −2 for 1 mAh cm −2 , and the Cu−Zn@Zn//V 2 O 5 pouch cell demonstrates excellent cycling stability with a capacity retention of 88 % after 600 cycles.

Abstract Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single‐atom Pt1/hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2–C4 polyols to corresponding primary hydroxy acids. It is found that the Pt−(O−P) linkages with strong electron‐withdrawing function of PO43− (Pt1−OPO43− pair active site) not only realize the activation of the C−H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C−C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−‐coordination effect provides electrostatic stabilization for single‐atom Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours with superior leaching resistance.

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.

Abstract Minimizing surface defect is vital to further improve power conversion efficiency (PCE) and stability of inorganic perovskite solar cells (PSCs). Herein, we designed a passivator trifluoroacetamidine (TFA) to suppress CsPbI3−xBrxfilm defects. The amidine group of TFA can strongly chelate onto the perovskite surface to suppress the iodide vacancy, strengthened by additional hydrogen bonds. Moreover, three fluorine atoms allow strong intermolecular connection via intermolecular hydrogen bonds, thus constructing a robust shield against moisture. The TFA‐treated PSCs exhibit remarkably suppressed recombination, yielding the record PCEs of 21.35 % and 17.21 % for 0.09 cm2and 1.0 cm2device areas, both of which are the highest for all‐inorganic PSCs so far. The device also achieves a PCE of 39.78 % under indoor illumination, the highest for all‐inorganic indoor photovoltaic devices. Furthermore, TFA greatly improves device ambient stability by preserving 93 % of the initial PCE after 960 h.

Abstract Despite the high stability of bulk water, water microdroplets possess strikingly different properties, such as the presence of hydroxyl radicals (OH⋅) at the air–water interface. Previous studies exhibited the recombination of OH⋅ into H 2 O 2 molecules and the capture of OH⋅ by oxidizing other molecules. By spraying pure water microdroplets into a mass spectrometer, we detected OH⋅ in the form of (H 4 O 2 ) + that is essentially OH⋅−H 3 O + , a hydroxyl radical combined with a hydronium cation through hydrogen bonding. We also successfully captured it with two OH⋅ scavengers, caffeine and melatonin, and key oxidation radical intermediates that bear important mechanistic information were seen. It is suggested that some previous reactions involving (H 4 O 2 ) + should be attributed to reactions with OH⋅−H 3 O + rather than with the water dimer cation (H 2 O−OH 2 ) + .

Abstract Employing pure water, the ultimate green source of hydrogen donor to initiate chemical reactions that involve a hydrogen atom transfer (HAT) step is fascinating but challenging due to its large H−O bond dissociation energy (BDE H‐O =5.1 eV). Many approaches have been explored to stimulate water for hydrogenative reactions, but the efficiency and productivity still require significant enhancement. Here, we show that the surface hydroxylated graphitic carbon nitride (gCN−OH) only requires 2.25 eV to activate H−O bonds in water, enabling abstraction of hydrogen atoms via dehydrogenation of pure water into hydrogen peroxide under visible light irradiation. The gCN−OH presents a stable catalytic performance for hydrogenative N−N coupling, pinacol‐type coupling and dehalogenative C−C coupling, all with high yield and efficiency, even under solar radiation, featuring extensive impacts in using renewable energy for a cleaner process in dye, electronic, and pharmaceutical industries.

Abstract Regulating the distribution of reactive oxygen species generated from H2O2 activation is the prerequisite to ensuring the efficient and safe use of H2O2 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 Cu5 nanoclusters onto a FeS2 surface achieves selective H2O2 activation with high efficiency. Unlike its unitary Cu or Fe counterpart, the dual Cu−Fe sites residing at the perimeter zone of the Cu5/FeS2 interface facilitate H2O2 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 H2O2 activation on the surface molecular level towards efficient environmental control and beyond.

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 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 Synthesizing large‐area free‐standing covalent organic framework (COF) films is of vital importance for their applications but is still a big challenge. Herein, we reported the synthesis of large metalloporphyrin‐based COF films and their applications for oxygen electrocatalysis. The reaction of meso‐benzohydrazide‐substituted metal porphyrins with tris‐aldehyde linkers afforded free‐standing COF films at the liquid‐air interface. These films can be scaled up to 3000 cm2 area and display great mechanical stability and structural integrity. Importantly, the Co‐porphyrin‐based films are efficient for electrocatalytic O2 reduction and evolution reactions. A flexible, all‐solid‐state Zn‐air battery was assembled using the films and showed high performance with a charge–discharge voltage gap of 0.88 V at 1 mA cm−2 and high stability under bent conditions (0° to 180°). This work thus presents a strategy to synthesize functionalized COF films with high quality for uses in flexible electronics.

Abstract Interfacial photo‐vapor conversion has been suggested as a cost‐effective and sustainable technology for seawater desalination. However, the conversion performance was still limited by some drawbacks, like salt accumulation and poor mechanical stability. Herein, a scalable MoS2‐based porous hydrogel (SMoS2‐PH) with good mechanical stability and salt resistance was successfully constructed through a crosslinking foaming polymerization method. With the high porosity (92.63 %), the SMoS2‐PH performed an impressive evaporation rate of 3.297 kg m−2 h−1 and photothermal conversion efficiency of 93.4 % under 1‐sun illumination. Most importantly, the SMoS2‐PH could maintain high and stable photothermal properties for 15 days on the surface of seawater. We believe that the excellent salt resistance, the high photothermal conversion efficiency, the ease of scale preparation method and the available commercial MoS2 make the SMoS2‐PH a promising device for full‐scale seawater desalination.

Abstract A convenient and rapid detection method for methanol in ethanol remains a major challenge due to their indistinguishable physical properties. Herein, a novel fluorescence probe based on perovskite was successfully designed to overcome this bottleneck. We report a new zero‐dimensional (0D) hybrid perovskite of [MP]2InxSb1−xCl7 ⋅ 6 H2O (MP=2‐methylpiperazine) displaying an unusual green light emission with near‐unity photoluminescence quantum yield. Remarkably, this 0D perovskite exhibits reversible methanol‐response luminescence switching between green and yellow color but fail in any other organic vapors. Even for blended alcohol solutions, the luminescent probe exhibits excellent sensing performance with multiple superiorities of rapid response time (30 s) and ultra‐low detection limit (40 ppm), etc. Therefore, this 0D perovskite can be utilized as a perfect fluorescence probe to detect traces of methanol from ethanol with ultrahigh sensitivity, selectivity and repeatability. To the best of our knowledge, this work represents the first perovskite as fluorescence probe for…

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…

Abstract The construction of safe and environmentally‐benign solid‐state electrolytes (SSEs) with intrinsic hydroxide ion‐conduction for flexible zinc–air batteries is highly desirable yet extremely challenging. Herein, hierarchically nanostructured CCNF‐PDIL SSEs with reinforced concrete architecture are constructed by nanoconfined polymerization of dual‐cation ionic liquid (PDIL, concrete) within a robust three‐dimensional porous cationic cellulose nanofiber matrix (CCNF, reinforcing steel), where plenty of penetrating ion‐conductive channels are formed and undergo dynamic self‐rearrangement under different hydrated levels. The CCNF‐PDIL SSEs synchronously exhibit good flexibility, mechanical robustness, superhigh ion conductivity of 286.5 mS cm−1, and decent water uptake. The resultant flexible solid‐state zinc–air batteries deliver a high‐power density of 135 mW cm−2, a specific capacity of 775 mAh g−1 and an ultralong cycling stability with continuous operation of 240 hours for 720 cycles, far outperforming those of the state‐of‐the‐art solid‐state batteries. The marriage of…