The instability of ruthenium-based catalysts during the acidic oxygen evolution reaction (OER) remains an obstacle to their practical implementation. In this work, we explore the dynamic self-optimization process (e.g., depletion, migration, and self-healing) of oxygen species in a Mn and Ta codoped RuO2 catalyst (i.e., MTRO), which acts as a model catalyst for stabilizing the active site during the acidic OER. By integrating tetramethylammonium cation (TMA+) chemical probes specific to deprotonated surface oxygen species with differential electrochemical mass spectrometry analysis, we tracked oxygen behavior, revealing that the reaction mechanism shifts from an initial lattice oxygen mechanism (LOM) to a subsequent adsorbate evolution mechanism (AEM). Analysis of the oxygen diffusion coefficient (e.g., DO) during the LOM pathway indicates that oxygen transportation drives reconstruction of the catalysts, while only moderate transportation could result in a structurally stable catalyst with a constant Ru-O coordination number and an optimal balance between high activity and durability: After codoping Mn and Ta into the RuO2, the DO reaches 1.40 × 10-15 cm2 s-1, which is 1/9 that of undoped RuO2, ∼25 times that of Mn-doped RuO2 (MRO). The optimized MTRO catalyst exhibits a low overpotential of 215 mV at 10 mA cm-2 and operates stably for over 1200 h in 0.5 M H2SO4, as well as 600 h of continuous operation in a proton exchange membrane electrolyzer at 0.5 A cm-2. This work elucidates that the "real" working OER catalysts based on RuO2 can be of a defective low-coordination structure (in contrast to perfect crystals) with moderate oxygen diffusion efficiency, formed through in situ self-optimization that simultaneously modulates the catalytic reaction pathway.

The development of stable, efficient, and low-cost catalysts for the oxygen evolution reaction (OER) in acidic media, along with a deeper understanding of the underlying reaction mechanisms, remains a central focus in the field of acidic water electrolysis. Herein, catalysts were strategically designed to selectively substitute octahedral and tetrahedral Co sites in Co3O4 with Ru to figure out the role of metal site in different coordination environments for acidic OER activity and stability. By regulating the synthesis strategy and tailoring the crystal coordination environment, we achieved Oct-RuxCo3-xO4 and Tet-RuxCo3-xO4 samples with selective substitution of Ru at octahedral and tetrahedral sites in Co3O4. Experimental and theoretical analysis confirm that Ru substitution at octahedral Co3+ sites activates a dual-metal Ruoct-O-Cooct active center through the oxide path mechanism (OPM) with a reduced energy barrier, whereas tetrahedral substitution disrupts orbital overlap due to excessive atomic spacing. The electron transfer within the Ruoct-O-Cooct configuration effectively suppresses cobalt over-oxidation and dissolution. Consequently, the octahedrally substituted Oct-Ru0.13Co2.87O4 catalyst with only 4 at

The sluggish mass and electron transport kinetics, along with the adhesion of in situ formed gas bubbles on the catalyst-electrolyte contact surface, significantly impede the catalytic activity of electrocatalysts for alkaline water electrolysis. Herein, we report a facile synthetic strategy for the fabrication of Ru-Co oxide composites with cross-doped heteroatoms. This composite only requires overpotentials of 11.25±1.54 mV for HER and 193.94 ± 5.84 mV for OER to reach 10 mA cm-2, respectively, enabling an alkaline electrolyzer at an ultralow cell voltage of 1.47 V to achieve 10 mA cm-2 for overall water-splitting with long-term stability at mimetic industrial current density (960 h@1000 mA cm-2). Combined experiments and theoretical calculations reveal that the electron transfer exists between Ru and Co sites across the cross-doped heteroatom, constructing a built-in electric field (BEF) that accelerates charge transport. Meanwhile, the "superaerophobic" surfaces of lotus-leaf-mimicking nanostructures enable a remarkable capability to facilitate the detachment of as-formed gas bubbles and mitigate bubble-induced mass transport limitations. This cross-doping strategy can extend to the material design of other high-performance Ru-based bimetal oxides for large-scale hydrogen production.

Developing highly active and durable electrodes for high-current-density alkaline water electrolysis is crucial for advancing cost-effective green hydrogen production. Herein, we report an atomic-to-macroscale assembly of an integrated Ni/MoO2 electrode possessing abundant atomic heterointerfaces with triscale (nano-micro-macro) porosity for high-performance hydrogen evolution. The electrode delivers an overpotential of 145 mV at 1 A cm-2 in 1 M KOH, markedly lower than the 300 mV of commercial Pt/C catalysts, while maintaining stable operation for over 3500 h. Practical application within an alkaline electrolyzer achieves a cell voltage of 1.80 V with an energy consumption of 4.3 kWh Nm-3 H2 at 1 A cm-2 under industrial conditions (30 wt % KOH at ≥85 °C), and operational durability exceeds 1000 h. Characterization and theoretical analysis elucidate a triple-enhancement effect on water electrolysis: (i) interfacial electron transfer from Ni to MoO2 moderately weakens H* adsorption and promotes the H2 desorption on the Ni sites, thereby boosting the intrinsic activity; (ii) triscale hierarchical porosity with hydrophilic MoO2 coating synergistically accelerates bubble detachment and electrolyte permeation, thereby enhancing mass transfer; and (iii) the strong Ni-MoO2 electronic interaction and their robust integration with the electrode skeleton significantly strengthen structural stability.

Electrocatalytic NO2 & oline;-to-NH3 reduction holds great promise for upcycling nitrogenous wastes to green ammonia. However, high NH3 selectivity under applied potential windows remains a challenge due to the mismatch of potential-dependent *H supply and sluggish hydrogenation kinetics of *NO2 on homogeneous catalytic sites. Herein, we constructed Cu-Pd catalytic pairs by integrating atomically dispersed Pd atoms into Cu matrix, in which the reactive *H adsorbed on the more hydrogenophilic Pd sites serves as atomic hydrogen pumps to enable hydrogenation of *NO2 on adjacent Cu sites and prevent *H self-coupling, whereas pure Cu catalyst suffers severe hydrogen evolution under high overpotentials. The paired CuPd catalyst shows Faradaic efficiencies of NH3 (FENH3) over 91 % from -0.3 to -0.9 V vs. RHE with a yield of 689.01 mu mol h- 1 mgcat.-1 at -0.9 V in the neutral electrolyte, significantly outperforming most reported catalysts in applied potential windows. The Ni, Fe, and Ru atoms with high adsorption ability of *H could also improve the FENH3 of Cu, which not only proves the efficiency of the proposed atomic-hydrogen-pump strategy, but also provides a potential active-site design principle for multi-intermediate catalysis.

Coal chemical parks serve as the primary hubs for the coal chemical industry within the Yellow River Basin. Clarifying the coupling coordination degree of their water-energy-carbon nexus holds substantial practical significance for promoting high-quality regional development. This research establishes a theoretical framework for understanding the water-energy-carbon interplay. Focusing on 16 coal chemical parks across six provinces (autonomous regions) in the Yellow River Basin, we analyzed the evolutionary characteristics and driving factors of their coupling coordination degree. The analysis employed a coupling coordination degree model, a grey relational degree model, and Moran's I index, based on data from 2014 to 2023 encompassing park-level economic performance, resource and energy consumption, and pollutant emissions. The results indicate that: (1) During the study period, the parks’ water resource efficiency increased by 25.60%, whereas energy efficiency decreased by 18.47%, and carbon emission intensity increased by 17.66%. A spatial gradient of efficiency was observed: Lower reaches > Upper reaches > Middle reaches. (2) The coupling coordination degree of the parks exhibited significant fluctuations, transitioning through stages characterized as " Intermediate coordination→Mild disorder→Excellent coordination→Severe disorder→Intermediate coordination." (3) Water consumption exhibits the highest correlation with the park‑level coupling coordination degree, with a correlation weight of 27.02%. (4) The spatial agglomeration effect strengthened over time, shifting from a non-significant spatial correlation to a positive spatial correlation, indicating enhanced regional synergy. Based on these findings, targeted policy recommendations are proposed.

Because arsenite (As(III)) is both highly poisonous and easily transported, arsenic pollution of water systems is a major threat to human and environmental health. When it comes to reducing arsenic toxicity and facilitating its removal from polluted water, one successful technique is the biological oxidation of As(III) to arsenate (As(V)). This work used the pRSFDuet-1 expression system to heterologously produce the aioA and aioB genes, producing arsenite oxidase subunits in Escherichia coli BL21 (DE3) strains of Thiomonas delicata. Separately and after reconstitution, the catalytic characteristics of the purified recombinant proteins were investigated. While AioB exhibited no discernible As(III) oxidation activity on its own, AioA exhibited far more enzymatic activity than AioB, in line with its role as the catalytic component. The catalytic efficiency and maximal reaction velocity were both improved when AioA and AioB were reconstituted in a 1:1 molar ratio, suggesting that AioB increases enzymatic activity by facilitating efficient electron transfer. The isolated enzyme was most active at room temperature and at neutral pH, although it maintained activity over a wide temperature range. The rapid conversion of As(III) at ecologically relevant concentrations was validated in batch oxidation studies, demonstrating that recombinant AioA exhibits excellent catalytic activity. Enzyme-based arsenic oxidation systems might provide long-term solutions for water treatment in areas where arsenic is present, according to policymakers. Improving the management of drinking water and guiding future environmental remediation efforts could be achieved by developing scalable biocatalytic systems based on recombinant arsenite oxidase.

CO2 electroreduction typically requires large overpotentials to sustain high reaction rates, which at current densities approaching 1 A cm-2 inevitably intensify competition from the hydrogen evolution reaction (HER), making it difficult to simultaneously sustain high product selectivity (>95%). In this study, hollow Ni─NC (H-Ni-NC) was synthesized using nanoscale silica sphere templates and atomic Zn as a sacrificial pore-former within the carbon shell. The optimized H-Ni-NC achieves a current density of -1.0 A cm-2 with over 95% CO Faradaic efficiency in a flow cell. The high performance was attributed to the hollow sphere architecture enriched with gas-permeable through-pores. Notably, the Zn dosage selectively modulates the shell through-porosity, without altering hollow sphere macrostructure or the active-site structure, thereby enabling a systematic investigation of porosity effects. Finite-element simulations provide a qualitative framework suggesting a trade-off between reactant transport and active surface area with increasing porosity in hollow spherical catalysts. This work underscores that engineering of the nanoscale mass-transport environment surrounding active sites plays a critical role in designing high-efficiency electrocatalysts.

Aqueous Zn-vanadium (Zn-V) batteries with high theoretical capacity are limited by sluggish Zn2+ diffusion kinetics, limited electronic conductivity, and structural instability, which impede the battery lifespan and rate capability. Herein, we fabricate a core-shell organic/inorganic heterostructure of modified VO2 (denoted as P-VO2) uniformly wrapped by poly(p-phenylenediamine, p-PDA) featuring interfacial V─N bonds for enhanced structural integrity and suppressed V dissolution. Theoretical calculations and in/ex situ characterizations proved the regulated proton insertion chemistry via ─C═N/─NH- chemistry in poly(p-PDA) for facilitated V5+/V4+/V3+ reaction kinetics and reversibility. As a result, the Zn//P-VO2 battery showed a superb capacity of 383 mAh g-1 at 0.2 A g-1, superior rate performance (330 mAh g-1 at 5 A g-1), and extraordinary lifespan over 16 000 cycles. Moreover, a 143.6 Wh kg-1 pouch cell shows ultrastability at -15°C after 200 cycles, underscoring its considerable potential. This work provides a new perspective on the study of organic-modified vanadium oxides for advanced Zn batteries.

Defective NiFe2+Fe3+Zn-LDHs (D-NiFe2+Fe3+Zn-LDHs) enable efficient and durable alkaline seawater oxidation, with 197 mV at 10 mA cm-2 and sustaining 2 A cm-2 for 800 h in alkaline simulated seawater. Fe2+ doping and Zn-vacancy accelerate reconstruction, while in situ-generated zincate suppresses chloride corrosion.

The development of durable electrocatalysts for hydrogen production under fluctuating current conditions is essential for advancing large-scale electrolysis systems powered by renewable energy. Ni4Mo/MoO2 catalysts have shown great promise for the hydrogen evolution reaction (HER) due to their cost-effectiveness and high catalytic activity. However, the behavior of catalysts under dynamic operating conditions remains poorly understood. In this study, we investigate the evolution of Ni4Mo/MoO2 catalysts subjected to intermittent shutdown cycling, simulating the current fluctuations typically encountered in renewable energy-driven electrolysis. Our results reveal that although Ni4Mo/MoO2 performs stably during continuous operation, it undergoes significant degradation upon shutdown cycling. This degradation is primarily attributed to the irreversible oxidation and dissolution of active Mo species, leading to the loss of the MoNi4 alloy phase and the formation of Ni(OH)2 and MoOx on the surface. The resultant phase transformation, surface reconstruction, and blockage of active sites collectively cause a sharp decline in intrinsic catalytic activity. These findings provide valuable insights into the failure mechanisms of Ni4Mo/MoO2-based electrocatalysts under dynamic conditions.

Abstract Organic molecular oxidation reactions are ideally regarded to be energy-saving alternative to replace oxygen evolution reaction (OER) for lowering the oxidation overpotential during green hydrogen production. However, the vast scale of hydrogen production is far beyond the fine chemical processes, inevitably resulting in substantial oxygen release. Here, we propose another type of coupled oxidation reactions to stably accommodate with high-current density hydrogen production, accompanied by easy separation. As taking benzylamine oxidation reaction (BOR) as a probe without other side reactions, we propose a bubble-assisted strategy by activating OER and utilizing the generated oxygen bubbles to timely take the insoluble product benzonitrile away from electrode surface, and effectively overcome the electrode poisoning issue. The assembled prototype water electrolyzer achieves a typical current density of 200 mA/cm 2 and faradaic efficiency of 55% at 1.65 V for over 40 hours, diversify high-value chemical outputs. Such hybrid electrolysis within bubble-assisted strategy endows system flexibility for next-generation integrated electrochemical energy platforms.

ABSTRACT The rational design and synthesis of Ir‐free acidic oxygen evolution catalysts combining high activity with long‐term durability remains a formidable challenge. This work demonstrates an addressable and dopant‐free strategy through the construction of Ru/RuO 2 heterostructures in a solely Ru‐based system, wherein interfacial charge redistribution and lattice‐oxygen participation jointly promote catalytic enhancement. The catalyst delivers an overpotential of 182 mV at 10 mA·cm −2 and retains operational durability for over 270 h at 100 mA·cm −2 in 0.5 M H 2 SO 4 . Spectroscopic characterizations, including X‐ray absorption spectroscopy (XAS), Raman spectroscopy, and X‐ray photoelectron spectroscopy (XPS), coupled with theoretical calculations, elucidate that interfacial electron transfer from metallic‐Ru phase to RuO 2 phase, assisted by the formation of a built‐in electric field, results in increased work functions across the heterointerface and lowered interfacial Ru oxidation states, suppressing Ru‐site overoxidation into soluble RuO 4 and accounting for the exceptional durability. Lattice‐oxygen participation, which corresponds to excellent activity, was verified by operando investigations, including differential electrochemical mass spectrometry (DEMS), attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS), and tetramethylammonium (TMA + ) chemical probing. The overall findings establish heterointerface engineering as a powerful tool for the simultaneous enhancement of the coupled activity‐stability in Ru‐based acidic OER catalysts.

ABSTRACT Synergy between metallic nanoparticles and single‐atom sites offers considerable potential for developing advanced electrocatalysts. However, the synergistic mechanism in such complex architectures under operating conditions remains elusive. Herein, a two‐step approach involving selective etching and co‐confined adsorption was developed to precisely construct CoRu/Ru NPs catalyst, featuring Ru–Co diatomic sites coupled with Ru sub‐nanoparticles, which demonstrates excellent oxygen reduction reaction (ORR) performance with a half‐wave potential of 0.91 V and a peak power density of 369 mW cm −2 in zinc‐air batteries, along with outstanding cycling stability over 1350 h. Beyond modulating the electronic structure to weaken OH* adsorption on Ru–Co diatomic sites, the Ru sub‐nanoparticles also induce an alternative thermodynamic pathway for enhanced ORR kinetics, in which interfacial water dissociate on oxyphilic Ru sub‐nanoparticles and facilely supply protons to oxygen‐containing intermediates on neighboring Ru–Co diatomic sites. This work not only advances the construction of synergistic active sites but also opens a new paradigm for designing advanced electrocatalysts by harnessing the interfacial environment beyond electronic structure modulation.

RuO2 undergoes severe structural degradation during acidic oxygen evolution reaction (OER) under high anodic potentials, including Ru oxidation into high‐valence species and lattice oxygen depletion, limiting its practical application. Tungsten, featuring strong oxophilicity and multiple valence states, effectively modulates the electronic structure of Ru sites due to electronegativity difference between Wn+ and Ru4+, stabilizing both Ru centers and lattice oxygen. Accordingly, a W‐doped RuO2 catalyst (W0.05Ru0.95O2, WRO) is developed to achieve dynamic oxygen species evolution via regulated lattice oxygen diffusion kinetics. The optimized oxygen diffusion coefficient (2.11 × 10−15 cm2 s−1) ensures a balance between oxygen vacancy replenishment and lattice oxygen retention. X‐ray absorption spectroscopy and tetramethylammonium probing reveal that WRO undergoes LOM‐dominated dynamic reconstruction at the initial stage, transforming from low‐coordination defective sites to a stable six‐coordinated Ru‐O framework. Consequently, WRO exhibits high activity with overpotential of 200 mV at 10 mA cm−2 in a three‐electrode system and promising durability of >400 h at 100 mA cm−2 in a two‐electrode system. A PEM electrolyzer with WRO as the anode operates stably for over 130 h at 200 mA cm−2. This work demonstrates that tuning oxygen diffusion kinetics enables dynamic coordination regulation, offering new insights for designing robust acidic OER catalysts.

ABSTRACT Aqueous Zn─I 2 batteries offer an attractive route toward risk‐free, cost‐efficient, and sustainable energy storage. However, their practical implementation is hindered by the challenges of sluggish iodine conversion kinetics and severe polyiodide shuttling. Herein, we reported a bio‐derived p‐toluquinone (TQ) confined onto porous activated carbon (denoted as TQ@AC) as redox‐catalytic cathode that leverages its quinoid backbone and carbonyl redox centers to simultaneously stabilize TQ redox cycling and boost iodine conversion efficiency. According to a combination of in/ex situ analyses and theoretical calculations, carbonyl groups within TQ serve as proton storage sites, and undergo reversible proton‐coupled electron transfer (PCET) process during battery working. Moreover, protonated carbonyl sites effectively confine iodine species via proton‐driven C═O/C─OH reaction and catalyze highly‐reversible iodine conversion, achieving a four‐electron proton‐iodine dual‐redox mechanism. Therefore, electrolytic Zn─I 2 battery based on TQ@AC cathode delivers an impressive capacity of 410 mAh g −1 , superior rate capability and achieves 85% capacity retention over 63 000 cycles. Additionally, the outstanding working stability and excellent temperature tolerance of the pouch cell within −15°C–45°C underscore its practical applicability, highlighting the effectiveness of synergistic organic‐iodine modulation for advanced Zn‐halogen batteries.

To settle inherent irreversible phase transition and motivate re-dissolution of deposited “dead” MnO2 without acid and redox mediator addition, we introduced atomic-dispersed Co atoms with high-spin state into layered MnO2, denoted as Co–MnO2, via an in situ topological phase transformation strategy, thereby unlocking reversible multi-electron transfer chemistry for superb Zn–Mn batteries. Specifically, atomic-distributed Co atoms within Co–MnO2 effectively modulate [MnO6] octahedral symmetry and reduce Co–O bond covalency along with enhanced lattice oxygen activity. Based on this, high-spin Co (t2g4eg2) greatly mitigates the Jahn–Teller distortion as well as promotes electrolytic MnO2 deposited onto the cathode surface completely converted from adsorbed Mn2+ for inhibited “Mn dendrites”, achieving reversible MnO2/Mn3+ and electrolytic MnO2/Mn2+ reactions with highly thermodynamical favorability. Benefiting from the “two-step, three-electron” mechanism triggered by high-spin Co, Zn//Co–MnO2 battery delivers an outstanding capacity of 658 mAh g–1 and ultra-long lifespan over 15,000 cycles. This work reveals the critical role of transition-metal spin state modulation for energy-dense and durable Zn-MnO2 batteries with reversible multi-electron storage mechanisms.

Green hydrogen production and utilization represent a promising carbon-neutral energy strategy, basically being categorized into alkaline, anion-exchange membrane, and proton exchange membrane electrolysis according to the types of electrolytes. Apart from the optimization of intrinsic activity of catalysts, electrolyte engineering has become an emerging and effective approach. Aiming to get deeper insights into the electrode-electrolyte interface, this perspective highlights two primary mechanisms: restructuring of hydrogen-bond networks that govern reactant transport and modulation of intermediate adsorption through hydration layers or electrostatic interactions. Electrolyte effects are systematically discussed across key reactions involved in hydrogen energy production and utilization, including the two half-reactions of water electrolysis, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), as well as the two half-reactions in fuel cells (FCs), hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR). We conclude by outlining strategic opportunities to leverage ion-mediated effects through electrolyte engineering, offering guidance toward more efficient, selective, and durable electrocatalytic systems for future energy conversion.

ABSTRACT Chlorohydrins are essential intermediates in organic synthesis, playing a critical role in drug discovery, green catalysis, and bioactive molecule manufacturing. However, conventional chlorohydrin synthesis usually requires harsh conditions, which create safety risks and poor selectivity. Here we develop a direct and efficient electrocatalytic strategy for synthesizing chlorohydrins from commodity alkenes, which are globally produced at over 200 million metric tons annually. Utilizing a RuSnNbO x polymetallic oxide catalyst, cyclohexene is directly converted to 2‐chlorocyclohexanol in NaCl solution with a Faradaic efficiency of 96.1 ± 3% and selectivity of 98.2 ± 0.4% at 1.6 V versus reversible hydrogen electrode. This approach is generalizable to other alkenes, such as styrene and cyclopentene, yielding 2‐chloro‐1‐phenylethanol and 2‐chlorocyclopentanol with uncompromised Faradaic efficiency. Mechanistic investigations reveal that the adsorbed active chlorine species, electrogenerated via Cl − oxidation on the RuSnNbO x anode, serve as key intermediates for direct alkene chlorination. Notably, this electrosynthesis method is further upscaled to gram‐level in acidic seawater, delivering 3.01 g of 2‐chlorocyclohexanol and 0.87 g of 2‐chloro‐1‐phenylethanol. This work provides a sustainable and scalable alternative to conventional chlorohydrin production and offers insights into designing efficient electrolysis for related transformations.

Aqueous Zn batteries (AZBs) utilizing vanadium-iodine dual energy storage mechanisms hold great promise for large-scale energy storage applications. Yet, the development of such AZBs is plagued by severe vanadium dissolution and uncontrolled polyiodide shuttling during the multi-step electron transfer process. Herein, we reported a core-shell VO2 cathode wrapped in situ by a conjugated poly(phenylenediamine) (pPDA) layer, denoted VO2-pPDA, which enables highly reversible and efficient V5+/V4+/V3+ and I-/I0 redox reactions in ZnI2-containing electrolytes. According to in/ex situ characterizations and theoretical calculation results, abundant ─C═N─ moieties in poly(PDA) enabled a synergistic optimization for the stabilization of VO2 and interfacial iodine anchoring. Meanwhile, the π-conjugated framework of poly(PDA) collaborated with VO2 to catalyze the high-efficiency iodine conversion. Due to V-I co-regulation, Zn//VO2-pPDA battery exhibited a high working voltage of 1.09 V, ultrahigh capacity of 610 mAh g-1, and outstanding lifespan over 40 000 cycles. Moreover, a practical 1.0 Ah pouch cell further demonstrated the strong application potential of this system, highlighting the effectiveness of multifunctional interfacial organic engineering for high-performance Zn batteries.