Single-atom catalysts (SACs) have triggered great interest in the field of catalysis due to their high atom utilization and unique structures. Tailoring the electronic metal-support interaction (EMSI) of SACs is crucial to enhancing the catalytic performance. Herein, a novel Ce1/ZnO SAC has been precisely constructed by a facile one-pot hydrothermal strategy, and the modulation of EMSI with different d-orbital electrons (Ce, Fe, and Zr) is for the first time proposed for electrochemical CO2 reduction (CO2RR). The Ce1/ZnO catalyst exhibits an excellent performance with a Faradaic efficiency of 84% for CO production and a record-high turnover frequency of 10658h-1 at -1.1V vs. RHE, exceeding Zr1/ZnO and Fe1/ZnO counterparts. Detailed characterizations and theoretical calculations reveal that the EMSI effect induces charge redistribution via the asymmetric metal-O-Zn moieties, while the unique Ce3+/Ce4+ redox feature can exert a more pronounced electronic communication with the substrate. The strong electronic interaction between single-atom Ce and ZnO alters the d-band center structure of Ce sites, facilitating the adsorption of CO2 and lowering the energy barrier of *COOH formation, thus accelerating CO production. This work elucidates the pivotal role of the electronic metal-support communication effect in engineering SACs toward boosted catalysis.

Lithium-rich manganese oxides (LRMOs) show great promise as high capacity, cost effective cathodes for next-generation Li-ion batteries, Nevertheless, they still confront issues such as voltage decline, capacity loss, and structural instability. Recent breakthroughs in situ/operando characterization methods have emerged as highly effective means for uncovering the dynamic changes in structure and electrochemical activity of these materials. This review delves into advanced methodologies enabling the real time observation of phase alterations, oxygen redox interactions, and the migration of transition metals (TMs) throughout the battery's charge/discharge cycles. By combining various characterization tools, researchers can reveal crucial connections between defect formation, redox mechanisms, and the stability of the battery's structure, enabling the development of novel approaches to suppress performance degradation. The study illustrates that mechanistic insights into phase transitions and failure modes, gained through advanced characterization, are instrumental in improving LRMOs. Prioritizing multiscale in situ methodologies coupled with machine learning for data interpretation will be crucial for rapidly developing viable LRMOs. These advancements in real time analysis hold promise for addressing current limitations and fast tracking the market introduction of high-energy-density materials for future energy storage.

The remarkable catalytic activity of heme enzymes originates from distinctive allosteric effects mediated by macrocyclic deformations. However, the role of dome‐type deformation remains poorly understood. To elucidate this mechanism, we synthesized a series of 5,15‐monostrapped iron(III) porphyrins exhibiting dome‐like deformation with precisely tunable ring distortions, serving as structural mimics of the dome conformation. These compounds were employed to catalyze the oxidative degradation of methylene blue (MB). The results demonstrate a strong correlation between catalytic efficiency and metallic axial asymmetry. Mechanistic studies reveal that this correlation stems from axial charge dismutation in the dz2 orbital induced by the asymmetry, which facilitates peroxo bond cleavage to form two reactive oxygen species (ROS), thereby enhancing degradation energy. This study provides the first definitive mechanistic elucidation of heme dome deformation, offering crucial experimental insights into the heme cycle.

ABSTRACT Hydrogen energy, celebrated for its high energy density and zero carbon emissions, is widely regarded as an indispensable pillar of 21 st ‐century green energy systems. Against this backdrop, transition metal phosphides (TMPs) have attracted considerable attention due to their distinctive physicochemical properties when applied in electrochemical water splitting (EWS). Nevertheless, their intrinsic activity remains limited by the suboptimal adsorption energetics of reaction intermediates, high kinetic barriers for water dissociation, and often lengthy or energy‐intensive synthesis protocols. This review begins with a concise overview of microwave‐assisted synthesis, a rapid, energy‐efficient, and highly controllable strategy for material fabrication. Then, we provide a comprehensive introduction to the rational design of TMP‐based electrocatalysts through diverse modification strategies, with particular information on their dynamic electrochemical reconstruction behavior under operational conditions. Special focus is placed on advanced engineering approaches that enable scalable, efficient hydrogen production by integrating advanced techniques powered by renewable sources. The final section highlights recent application advances, ongoing challenges, and emerging opportunities for TMP electrocatalysts within the evolving landscape of next‐generation energy structure. Collectively, this review provides a comprehensive summary of precisely engineered TMP electrocatalysts with reconstruction behavior that functions as high‐performance bifunctional electrocatalysts for EWS‐based renewable energy generation.

Precise regulation of carrier kinetics in heterogeneous photocatalytic materials to improve water purification is crucial for alleviating the global water crisis. Herein, we report the successful synthesis of a novel KBC/CeO2/Cd0.5Zn0.5S (KCCZS) S-scheme heterojunction with KOH-activated biochar (KBC) as an electron transport medium. A synergistic mechanism involving "surface active sites-internal electric field (IEF)-optimized carrier kinetics" is established, achieving rapid imidacloprid (IMI) removal. Comprehensive characterizations and DFT calculations validate the "internal and external cultivation" strategy, for which photogenerated carriers are efficiently separated spatially by IEF at the heterojunction interface. Concurrently, KBC functions as an "electron pump" to continuously supply electrons, further enhancing carrier generation and separation efficiency. Under visible light irradiation, 10%KCCZS exhibits exceptional IMI removal performance (99.4%, 30 min) with a rate constant of 0.1521 min-1, representing 23.0 times higher than CeO2 (0.0066 min-1) and surpassing most previous reports. Furthermore, the catalyst maintains excellent purification performance across a broad pH range (3-11), complex water matrices (interfering ions/organics), and various organic pollutants. Mechanistic investigations confirm effective utilization of photogenerated carriers and the dominant role of center dot O2 -. LC-MS analysis coupled with comprehensive toxicity assessment (computational toxicity and biological culture assays) elucidates the IMI degradation pathways and environmental safety. This "internal and external cultivation" strategy fundamentally improves carrier kinetics, not only providing innovative perspectives for future heterojunction design but also paving the way for green and sustainable water purification technologies.

For supported metal catalysts, phase engineering emerges as an effective route to elevate electrocatalytic efficacy. However, conventional phase regulation strategies based on thermal reduction often suffer from prolonged synthesis processes and tend to induce metal aggregation, which ultimately limit the exposure of active sites. Herein, an ultrafast microwave quasi-solid approach (90 s) is adopted to synthesize Ru nanoclusters embedded into black anatase TiO2 lattice (Ru/TiO2-A) with abundant oxygen vacancy, and surface decorated Ru nano-particles onto black rutile TiO2. Engineered lattice-embedded configurations and co-generated oxygen vacancies collectively dictate catalytic performance and structural durability. As an electrocatalyst for hydrogen-related reactions (HER/HOR), Ru/TiO2-A featuring Ru nanoclusters exhibits superior performance to Ru nanoclusters on black rutile TiO2 (Ru/ TiO2-R) in alkaline electrolyte, demonstrating a lower overpotential (44 mV vs. 90 mV @ 10 mA cm-2) and higher mass activity (20.99 A mg-Ru1 vs. 6.71 A mg-Ru1 @ 100 mV). Support phase engineering enhances water dissociation kinetics and modulates adsorption-desorption equilibria of reactive intermediates. This work is expected to advance the catalytic systems and provide novel approach to rational prepare efficient electrocatalysts toward hydrogen electrode reactions.

Aqueous ammonium-ion batteries (AAIBs) have emerged as a promising post-lithium energy-storage technology, combining intrinsic safety with sustainable viability. However, unlike other aqueous-ion batteries, the engineering of AAIB electrolytes confronts a fundamental dilemma: their unique hydrogen-bond (HB)-rich environment, which enabling ultrafast NH4 + transport, concurrently exacerbates water decomposition and undermines electrolyte stability. In this review, we present the first comprehensive analysis of the dual role of HB networks in AAIB electrolytes and delineate their consequences for battery performance. We then systematically examine and evaluate the prevailing strategies devised to circumvent this dilemma, specifically anion engineering, salt-concentration tuning, pH regulation, organic co-solvent design, functional-additive introduction, and semi-solid electrolyte construction, while concurrently discussing their respective trade-offs and future outlook. Finally, we outline future directions involving coupled-reaction batteries, interfacial modeling, machine-learning-assisted electrolyte discovery, and sustainable ammonium sourcing. These insights provide a framework for balancing ion-transport kinetics and electrolyte stability in next-generation AAIBs.

Electrochemical reactive carbon dioxide capture (eRCC) couples CO2 absorption and conversion, yet the identity of the true electroactive carbon species remains contested. Across carbonate- and amine-based systems, accumulating evidence demonstrates that dissolved CO2, regenerated from capture equilibria, dominates CO formation under practical operating conditions. Transport-controlled measurements reveal that CO generation rate scales with dissolved CO2 activity and is bounded by its mass-transfer limit. Direct carbamate reduction emerges only within a narrow, deeply reducing regime and does not generally replace molecular CO2 as the operative substrate. In contrast, specific diamine-derived zwitterionic carbamates can attain kinetic relevance when structural and interfacial factors align. Clarifying this potential-dependent crossover resolves longstanding ambiguity and establishes interfacial CO2 availability, rather than bulk speciation alone, as the decisive parameter for rational eRCC design.

A mass-loss-based identification method for solid-state batteries is proposed under standardized vacuum-heating conditions. The method quantifies the overall level of volatile components by comparing cell mass before and after heating, thereby providing a practical indicator of whether liquid-phase constituents are present across different material systems. The magnitude of the mass-loss ratio serves as the basis for distinguishing solid-state batteries from liquid-containing counterparts. Application to hundreds of commercial and prototype cells reveals clearly differentiated mass-loss distributions among liquid, hybrid solid–liquid, and solid-state categories, providing dataset-level evidence for defining and tightening identification boundaries. From a standardization perspective, the method was first incorporated into the draft of a Chinese national standard (GB/T) and has been continuously refined during the development process. The optimized testing procedure and associated identification requirements will be formally issued through the forthcoming GB/T standard.

In situ-polymerized 1,3-dioxolane (DOL) electrolytes offer a promising route to quasi-solid-state lithium metal batteries (QSSLMBs), yet their limited oxidative tolerance and unstable electrode interfaces restrict high-voltage operation. Here, a simulation-guided dual-track regulation strategy uses MoCl5 as a multifunctional initiator to couple DOL ring-opening polymerization with Li-salt dissociation and inorganic interphase construction. MoCl5 promotes formation of a high-molecular-weight poly(1,3-dioxolane) (PDOL) matrix and LiF/LiCl/LixMoy-enriched solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI), improving bulk stability, Li+ transport, and interfacial robustness. The resulting MoCl5-regulated PDOL electrolyte achieves a Li+ transference number of 0.71 and an electrochemical stability window of 4.7 V. Li||Li symmetric cells cycle for over 1000 hours at 5 mA cm-2, while high-voltage Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) cells retain over 95% capacity after 50 cycles at 2 C. This work establishes a design principle for multifunctional initiators and unlocks the high-voltage potential of ether-based electrolytes, advancing the practical application of QSSLMBs.

Coupling N2 electroreduction with kinetically and/or thermodynamically favored oxidation reactions in one system can realize the co-production of NH3 and value-added oxygen-containing fine chemicals at lower energy consumption. Here, a new N2 electrolysis system based on nitrogen-doped carbon-supported Bi2O3 and NiO catalysts (Bi2O3/NC and NiO/NC) is demonstrated, in which the methanol oxidation reaction in the anode to make formic acid is coupled with N2 electroreduction for NH3. The optimal NH3 yield of 2.79 μ g_ NH_3 h^-1 cm^-2 is achieved at the voltage of 2.35 V with a high Faradaic efficiency of 5.04

Biomass-derived fluorine and nitrogen co-doped carbon dots (F, N-CDs) were synthesized via a one-step hydrothermal method using Rhododendron simsii flowers as the precursor. The prepared F, N-CDs exhibited favorable optical properties, good water solubility, and a pronounced enhancement effect on the chemiluminescence (CL) of the Luminol-K2S2O8-NaOH system. The optical characteristics were systematically investigated by UV-Vis absorption spectroscopy, fluorescence spectroscopy, and fluorescence lifetime analysis. The possible CL enhancement mechanism was further investigated through reactive oxygen species scavenging experiments and singlet oxygen probe experiments. On this basis, an enhanced flow-injection chemiluminescence (FI-CL) method was developed for the determination of levetiracetam (LEV). Under the optimized conditions, the relative CL intensity exhibited a satisfactory linear relationship with LEV concentration over the range of 0.10-10.00 mM, with a limit of detection (LOD) of 2.02 × 10-3 mM and a limit of quantification (LOQ) of 6.71 × 10-3 mM. The proposed method was successfully applied to the commercial LEV pharmaceutical formulations, giving recoveries of 94.8-103.1% and relative standard deviations (RSDs) below 4.68%. These results demonstrate the potential of biomass-derived carbon dots for spectroscopic and characterization and chemiluminescence-based analytical applications.

Polarisation in covalent organic framework (COF) catalysts has emerged as an effective strategy to reduce strong excitonic binding and to improve charge transport through built-in electric fields. Unlike conventional inorganic ferroelectrics or polar materials, COFs enable programmable polarisation through molecular and lattice design, allowing internal fields to be tuned in strength and direction. In this review, we provide a comprehensive analysis of polarisation in COFs, from its physical origins to its functional roles in catalysis. We first examine the multiscale origins of polarisation in COFs, encompassing bond-level electronic asymmetry, conjugation-mediated propagation, and framework-level structural organisation that governs dipole alignment and cancellation. We then summarise how polarisation is characterised experimentally and theoretically across different electronic and catalytic states, including ground-state electrostatic potential landscapes, photoexcited-state charge dynamics, and polarisation effects at solid-liquid catalytic interfaces. Finally, through representative photocatalytic and electrocatalytic case studies, we illustrate how deliberate polarisation engineering reshapes charge separation, transport, and reaction pathways across diverse catalytic reactions, and conclude by discussing the key opportunities and challenges for translating polarisation into a predictive design principle for COFs. By connecting the origins, characterisations, regulating strategies, and catalytic mechanisms, this review provides a more integrated perspective on polarisation phenomena in next-generation COF catalysts.

A sustainable future relies on the development of advanced catalyst materials through exploring their quantum-level mechanisms and integrating multiple catalytic effects to achieve optimal performance. Piezocatalysis and piezo-assisted catalysis have recently emerged as promising catalytic strategies based on the piezo effect, which enables the conversion of mechanical energy and thermal fluctuation into chemical energy. In these systems, piezoelectric materials effectively transform mechanical deformation into an intrinsic polarization field, which facilitates charge carrier separation and migration, suppresses recombination, and thereby enhances catalytic activity. These unique advantages have demonstrated great potential for constructing high-performance and cost-effective catalytic platforms for sustainable energy conversion and environmental remediation. In this review, we comprehensively summarize recent progress in piezocatalysis and piezo-assisted catalysis, with a particular focus on our research contributions alongside related advances in the field. We systematically discuss charge transfer behaviors and catalytic mechanisms in piezocatalysis, piezo-photocatalysis, as well as ferroelectric- and pyroelectric-assisted multifunctional catalysis, with representative applications in hydrogen generation, CO2-to-fuel conversion, and the production of H2O2 and reactive oxygen species (ROS). Furthermore, we highlight the development of novel piezocatalysts and hybrid catalyst systems for integrated catalysis. Finally, we propose future perspectives on the integration of piezocatalysis with other polarization-based catalytic strategies to expand their applicability and accelerate their practical deployment.

Solid polymer electrolytes face a fundamental trade-off between ionic conductivity and interfacial stability, particularly when incorporating the plasticizer succinonitrile (SN): specifically, SN boosts Li+ conductivity by tailoring the Li+ coordination environment and facilitating Li+ transport; However, the uncontrolled diffusion and electrochemical degradation of SN undermine the stability of Li metal anode interface. We address this challenge by constructing coordination-engineered ion highways within a hierarchical iron-based metal-organic framework (MOF) architecture, through rationally designing Fe3+-cyano (CN-) coordination bonds as molecular anchors to permanently immobilize SN within the MOF nanopores while simultaneously regulating the competitive coordination of Li+ among MOF-immobilized SN, poly(ethylene oxide) (PEO), and TFSI-anions. This dual-regulation strategy simultaneously constructs continuous 3D Li+ transport pathways and suppresses parasitic reactions, delivering a high room-temperature ionic conductivity (1.16 mS cm-1), a high Li+ transference number (0.80), and a extended electrochemical window of 5.2 V. The dual-regulation strategy enables dendrite-free Li plating/stripping for 1600 h in Li/Li symmetric cells, while a LiFePO4 (LFP) full cell retains 85.6% of its initial capacity after 1200 cycles at 2 C. Multiscale characterizations and modeling reveal how the Fe3+-CN "molecular lock" impedes SN degradation, while optimized Li+ flux homogenization facilitates the formation of an inorganic-rich interphase that suppresses dendrite growth. This work provides a versatile strategy for decoupling ion conduction from interfacial degradation in solid-state batteries.

Due to poor carrier migration and sluggish water oxidation kinetics, bismuth vanadate (BiVO4) photoanodes show limited photoelectrochemical (PEC) performance and stability. Coupling a hole-selective layer (HSL) can mitigate these issues. Here, we construct an organic-inorganic hybrid HSL by combining a self-assembled monolayer (Me-4PACz) with NiOx on BiVO4. Through systematic control experiments that decouple the contributions of the individual layers, we quantitatively reveal a genuine synergy between NiOx and Me-4PACz. NiOx rapidly extracts holes and provides catalytic sites. The Me-4PACz adopts a vertical, non-dense orientation, generating a molecular dipole that forms a continuous SAM-NiOx-BiVO4 energy cascade and lowers the hole transfer barrier. More importantly, we uncover a "local anchoring and remote activation" mechanism: a single Me-4PACz binds via P-O-Ni to a surface Ni site (passivating a harmful defect), while its electron-withdrawing effect propagates through the Ni-O-Ni lattice to convert adjacent Ni2+ into active, defect‑free Ni3+ sites. The phosphonate group further stabilizes these Ni3+ centers. The resulting SAM-NiOx-BiVO4 photoanode achieves a photocurrent density of 6.90 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE) and retains stable performance for over 60 h. This work expands SAM applicability in PEC water oxidation and offers a rational design principle for organic-inorganic hybrid photoanodes.

Engineering bifunctional electrocatalysts featuring promoted adsorption for multiple intermediates and reactants via interface modulation strategies is critical for urea-assisted water splitting toward sustainable energy conversion. However, exploring efficient bifunctional electrocatalysts capable of driving both the hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) at high current densities remains challenging. Herein, a self-supported bifunctional electrode is constructed on nickel foam, where the cooperative CoNi LDH is decorated with low-content Pt nanospheres (Pt-CoNi LDH/NF) for urea-assisted H2 production. The strong metal-support interaction (SMSI) and multi-metal synergy collectively regulate the adsorption/desorption behavior of key reaction species, thereby lowering the energy barrier for the rate-determining step and improving overall catalytic efficiency. The optimized catalyst exhibits substantially reduced potentials of 1.32V (UOR) and -30 mV (HER) to reach 10mAcm-2. A urea-assisted electrolytic cell merely requires 1.36V to afford 10mAcm-2. Notably, in a practical anion-exchange membrane (AEM) electrolyzer configuration, the Pt-CoNi LDH/NF electrode maintains stable at 2Acm-2, while preserving high UOR/HER bifunctional activity. This study develops an integrated approach that couples urea-containing wastewater remediation with energy-efficient hydrogen production.

Porous materials, particularly covalent organic frameworks (COFs), exhibit well-defined porosity, tunable structural features, and high chemical and thermal stability. These intrinsic properties render COFs highly promising candidates for the rational design of efficient functional materials, thereby attracting significant interest across diverse scientific and engineering disciplines. Nevertheless, pristine COF frameworks often suffer from an insufficient density of active sites and functional moieties, thereby constraining their practical performance. Accordingly, the incorporation of metal components into COF architectures has emerged as a promising strategy to enhance their functionalities. In this review, we introduce a novel classification scheme grounded in the interaction strength between metal species and COFs, which enables a systematic organization of existing metal-modified COF materials. This framework facilitates an in-depth analysis of this intriguing class of materials by elucidating the intrinsic relationships and distinctions among different metal-modified COF materials from the perspective of metal-COF interaction strength, thereby advancing the fundamental understanding of their structure-property correlations. Furthermore, we comprehensively summarize recent progress in metal-modified COF materials with respect to applications including adsorption and separation, photocatalysis, electrocatalysis, energy storage, sensing, and biomedicine. Emphasis is placed on structural design principles, synthetic methodologies, characterization techniques, and how different metal-modified COF materials influence reaction pathways and underlying mechanisms. Ultimately, the current challenges and future research directions pertaining to metal-modified COF materials are critically discussed.

Efficient catalytic materials are vital for addressing the polysulfide shuttle and sluggish redox kinetics in lithium-sulfur batteries. Herein, we report a facile sugar-blowing method to prepare porous carbon-supported FeCoNiCuPt high-entropy alloy (HEA) nanospheres with abundant lattice defects in a single crystalline phase. The multiple constituent metals endow the HEA catalyst with moderate polysulfide adsorption and enhanced catalytic activity, which favors suppressing polysulfide migration, accelerating sulfur redox reactions, and reducing activation energies of Li2S oxidation. Consequently, the battery with HEA-modified separator delivers a high initial capacity of 1429 mAh g-1 at 0.1C and maintains exceptional cycling stability at 0.5C. Remarkably, under a sulfur loading of 4.32 mg cm-2, a superior capacity above 700 mAh g-1 is achieved after 60 cycles. Density functional theory calculations confirm the strong binding of polysulfides on the HEA surface and the reduced conversion barriers. This work establishes HEAs as a robust catalytic shield to effectively address polysulfide adsorption-conversion.

The electrochemical synthesis of urea from nitrate (NO3 -) and carbon dioxide (CO2) presents a sustainable alternative to conventional methods, mitigating pollution and reducing energy consumption. Herein, a rationally designed Ni-Fe bimetallic pyromellitic acid polymer catalyst (Ni-PMDA@Fe) is developed for efficient urea electrosynthesis. This metal-organic polymer provides structural robustness, abundant active sites, and a tunable coordination environment, optimizing C-N coupling kinetics. Ni-PMDA@Fe achieves a urea yield of 449.56 mg h-1 gcat -1 and a Faradaic efficiency (FE) of 41.06% at -0.5 VRHE, significantly surpassing monometallic controls (Ni-BDC, Ni-PMDA). Fe incorporation modulates the electronic structure of Ni, enhances charge transfer, and stabilizes key reaction intermediates, enabling synergistic NO3 -/CO2 coupling. Comprehensive characterization confirms homogeneous Fe doping and a dual-metal-site configuration. Unlike single-atom or monometallic systems, the Ni-Fe dual-site architecture optimally tunes the adsorption kinetics of critical intermediates. The catalyst maintains a FE exceeding 30% over a 30 h stability test, demonstrating robust operational stability. Furthermore, techno-economic analysis (TEA) indicates competitive production costs when powered by renewable energy, highlighting scalability potential. This word demonstrates a practical pathway for sustainable urea synthesis by converting pollutants (NO3 -/CO2) into value-added product, thereby contributing to decarbonizing fertilizer production and mitigating nitrogen pollution.