Electrocatalytic nitrate reduction (eNO(3)RR) offers a sustainable, carbon-neutral route to ammonia (NH3) synthesis. However, its practical deployment is severely hampered by the kinetic mismatch between nitrate deoxygenation and intermediate hydrogenation, exacerbated by competing hydrogen evolution (HER). Here, we report a heterometallic interfacial engineering strategy to synchronize these tandem kinetics using a dynamically reconstructed Ni/Cu oxide nanoarray (h-Ni-Cu1-2O/CF). Comprehensive in situ spectroscopy and theoretical simulations reveal that the precatalyst undergoes structural reconstruction to in situ exsolve metallic Ni nanodomains anchored by highly stable Ni-O-Cu coordination motifs under working conditions. This unique bifunctional interface fundamentally stabilizes active Cu delta+ sites for accelerated initial deoxygenation, while the electronically modulated Ni sites act as an optimal "hydrogen pump". This configuration efficiently channels active hydrogen (*H) to the nitrogenous intermediates, eradicating the NO2- hydrogenation bottleneck and silencing the HER. Consequently, the catalyst achieves a near-unity Faradaic efficiency of 98.6% and sustains unprecedented performance at an aggressive industrial-level current density of 3000 mA cm(-2) (NH3 production rate: 12.1 mmol h(-1) cm(-2)). Furthermore, integrated into a continuous-flow system, macroscopic quantities (>5 g) of high-purity solid (NH4)(2)SO4 were successfully recovered. This work establishes a versatile interfacial design principle for coordinating proton-coupled multi-electron tandem electrocatalysis.

Molecular engineering provides effective strategies for optimizing electrocatalytic interfaces; however, a physically grounded conceptual framework that provides an intuitive picture of molecular engineering is still lacking. This perspective proposes a distance-aware framework that decouples molecular modification effects into three distinct spatial zones relative to the active site, each characterized by different dominant interactions. Inner-layer engineering targets the angstrom-scale region immediately adjacent to the surface, where modifiers directly participate in charge redistribution and intermediate stabilization to tailor surface energetics. Intermediate-layer modulation governs the local microenvironment, mediating reactivity through local concentration fields, hydrogen-bond networks, and electrostatic double-layer effects. Outer-layer engineering operates at the bulk interface, controlling macroscopic wettability, interfacial shielding, and long-term structural stability. By establishing this spatially resolved and decoupled perspective, we propose a distance-based framework to systematically organize and interpret the fragmented modification phenomena, thereby providing a physically grounded structured framework for organizing molecular engineering strategies.

The inadequate coordination at the solid-liquid interface imposes a fundamental limitation on nitrate electroreduction under neutral conditions, highlighting the urgent need for deliberate interfacial reorganization. Herein, a Lewis-acidic field is constructed within spinel Co3O4 by doping Zr via a lattice-confined pyrolysis strategy, enabling synergistic coupling of proton dynamics with nitrate activation. The high-valent Zr4+ centers enrich nitrate electrostatically and reorganize the interfacial hydrogen-bond network to accelerate water dissociation, while Zr-induced lattice strain further activates Co sites, jointly elevating the turnover frequency. As a result, the optimized Zr-Co3O4 catalyst achieves a near-unity ammonia Faradaic efficiency of 99.5% at -0.7 V vs. RHE and an impressive yield rate of 15.7 mg h-1 cm-2 at -0.9 V vs. RHE in a neutral electrolyte. This work establishes localized acidic-field engineering as a general strategy to overcome intrinsic kinetic limitations in neutral-pH electrosynthesis.

While copper complexes intrinsically provide Cu sites for electrocatalytic CO2 reduction (ECR), their efficacy toward multicarbon products (C2+) remains fundamentally limited by the operational instability of reactive Cu valence states and the inability to synchronously optimize *CO intermediate generation and C-C coupling within symmetric coordination environments. Herein, we judiciously design a single-crystal N, O co-coordinated copper complex (Cu(ICA)2) featuring asymmetric N2-Cu-O2 centers that precisely modulate the electronic structure and local adsorption environment. The Cu-N bonds stabilize partially reduced Cu delta+ sites while weakening Cu-O interactions, thus balancing structural integrity with catalytic reactivity. This asymmetric dual-site coordination concurrently hosts distinct *CO intermediates (atop-adsorbed *CO at Cu sites and bridge-adsorbed *CO at Cu-N sites), enabling cooperative C-C coupling into C2 products. The catalyst achieves a record 69.2 % Faradaic efficiency for C2 products at 400 mA cm-2 and 57.4 % for C2H4 at 500 mA cm-2 in 1.0 M KOH, rivaling the stateof-the-art Cu-based complexes. In situ characterization and DFT calculations mechanistically corroborate that bridge-adsorbed *CO at Cu-N sites drives energetically favorable hydrogenation and C-C coupling pathways. This work establishes a coordination-asymmetry design principle for constructing robust molecular catalysts capable of efficient CO2-to-C2+ conversion.

ABSTRACT Fragmented hydrogen‐bond networks relegate proton transport to sluggish diffusion, leading to mismatched proton supply that compromises catalytic efficiency and selectivity, thereby necessitating strategies to enhance water‐network ordering. Inspired by the proton channel mechanism in enzymatic catalysis, this work anchors silicotungstate (SiW 12 ) onto Co 3 O 4 to construct a SiW 12 /Co 3 O 4 catalyst. The domain electrostatic field of SiW 12 induces the ordered arrangement of interfacial water molecules, establishing an ordered water channel for proton migration. The results demonstrate that SiW 12 promotes interfacial water activation and alleviates proton‐transfer limitations, enabling rapid and directional proton delivery to nitrogen‐containing intermediates. Leveraging this unique proton channel, SiW 12 /Co 3 O 4 achieves near 100% selectivity over a wide potential window (−0.3 to −0.9 V vs. RHE) and a broad nitrate concentration range (0.01–1 M), achieving 99.3% NH 3 FE and 15.1 mg h −1 cm −2 yield at −0.8 V versus RHE. Furthermore, the assembled Zn–NO 3 − battery delivers the highest reported power density (26.1 mW cm −2 ) under neutral conditions. This work establishes interfacial solvation‐structure engineering as a general strategy for regulating proton delivery and developing highly selective electrocatalysts for sustainable ammonia electrosynthesis.

Achieving high-selectivity electrocatalytic CO2-to-CO conversion on copper-based catalysts is fundamentally hindered by the precarious stability of active Cu+ sites and the intrinsic tendency of Cu0/Cu+ interfaces to drive C-C coupling. Herein, we report a strategically engineered Sb-doped Cu/Cu2O heterostructure that transcends these limitations via a dual-functional electronic anchoring mechanism. The Sb dopants electronically stabilize metastable Cu+ species against over-reduction to suppress hydrogen evolution while, more critically, bridging the interfacial charge disparity. This electronic modulation homogenizes the charge state of adsorbed CO intermediates on Cu+ and Cu0 sites, thereby attenuating their electrostatic attraction and effectively deactivating the C-C dimerization pathway. Consequently, the catalyst delivers a Faradaic efficiency of nearly 100% for CO production and an industrial-scale current density of 297.9 mA cm- 2 at -0.85 VRHE. Most significantly, this exceptional selectivity is sustained across an expansive operational window of 1.0 V (-0.65 to -1.65 VRHE), breaking the traditional potential-dependent selectivity. This work establishes a generalizable paradigm for manipulating interfacial electronic landscapes to realize durable, high-throughput carbon-neutral catalysis.

The development of a visual sensing system for ultrasensitive detection of high-risk chlorophenols (CPs) at ng level is of considerable importance, with a critical focus on the construction of effective adsorption sites for CPs. In this study, we have successfully synthesized atomically dispersed Ag-anchored g-C3N4 nanosheets (Ag/CN) via the coordination of rich N supermolecule precursor with Ag, which were employed to establish an eosin Y (EY) photosensitization sensing system for ultrasensitive detection of CPs. This system showed a wide visual detection range for CPs, especially for 2-chlorophenol, encompassing concentrations from 1 ng center dot L- 1 to 1 mg center dot L- 1, with an exceptionally low detection limit of (LOD) 0.5 ng center dot L- 1. Additionally, it demonstrated excellent detection performance for 2,4,6-trichlorophenol with an LOD of 4.2 ng center dot L- 1 and 2,4-dichlorophenol with an LOD of 38 ng center dot L- 1. Moreover, the system displayed remarkable selectivity, as evidenced by comparative analyses with other 15 interferents. Time-resolved and in-situ technologies have revealed that the superior sensing performance is due to the constructed atomically dispersed Ag sites, which significantly facilitate the preferential selective adsorption of CPs through the interactions between the Ag and Cl, thereby effectively and quantifiably inhibiting the photosensitization decolorization of EY. This method also demonstrated high suitability for application in the analysis of actual water samples, exhibiting significant sensitivity and selectivity. This research presents a visual light-driven sensing system, which enables ultra-trace detection of Cl-containing pollutants, highlighting its considerable potential for application in water monitoring.

The highly sensitive photoelectric detection of hydrogen (H2) at room temperature (RT) is highly desired, but it is crucial to boost •O2- generation by improving charge transfer and favorable O2 adsorption. Herein, we construct a novel all-organic polydopamine/poly(heptazine imide) (PDA/PHI) nanosheet heterojunction through in situ polymerization for photoelectric H2 detection. The optimized one exhibits high sensitivity (an ultralow detection limit of 500 ppm and a high gas response of 42.8% for 5000 ppm H2), along with good linearity from 500 to 5000 ppm, under 405 nm irradiation at RT based on the dynamic detection process. Moreover, good repeatability in 40 cycles, long-term stability (over 210 days), and high selectivity are confirmed. The outstanding performance is attributed to the efficient Z-scheme charge transfer and the promoted O2 adsorption for facilitating the •O2- species generation. Interestingly, the in situ μs-transient absorption spectra quantitatively reveal that the electron transfer efficiency (ETE) to the adsorbed O2 of the PDA/PHI heterojunction is changed from 68.0% to 31.1% after introducing H2, while the change rate of ETE is more pronounced than that of PHI. This study demonstrates great potential of all-organic heterojunctions for RT photoelectric detection and provides deep insight into the •O2- species and gas sensing property.

The image shows that the Al/Co double-doped polyhedron SrTiO 3 with nanoclusters and satellite single atoms of Co offers a highly efficient photoreduction of Ni 2+ to Ni 0 . Most of the Ni elements are enriched in the (112) facet.

Ulcerative colitis (UC) is a chronic relapsing inflammatory bowel disease characterized by persistent oxidative stress, dysregulated immunity, epithelial barrier disruption, and microbial imbalance, all of which synergistically exacerbate mucosal injury. Addressing these multifactorial challenges remains a critical obstacle in UC therapy.Here, we present a targeted ternary nano-therapeutic platform that integrates cobalt single-atom nanozymes (Co SA), ginsenoside Rb1 (Rb1), and Bifidobacterium bifidum (BB) for multidimensional intervention. Co SA exhibits enzyme-like catalytic activity to scavenge reactive oxygen species and mitigate oxidative stress. Rb1 suppresses pro-inflammatory signaling, promotes tight junction expression, and restores barrier integrity. Meanwhile, BB colonizes the inflamed colon, modulates gut microbiota, and enhances metabolic recovery. Through this synergistic design, the ternary system effectively attenuates oxidative injury, alleviates inflammation, repairs barrier dysfunction, and rebalances the gut microenvironment.In both acute and chronic UC models, this strategy achieved markedly superior therapeutic outcomes compared to individual components or clinical positive controls. Collectively, this work demonstrates a cost-effective, multifunctional, and translatable therapeutic approach, offering a new paradigm for the clinical management of UC.

The industrial viability of electrochemical biomass valorization is fundamentally throttled by the parasitic oxygen evolution reaction (OER), which severely confines the stable operational window. Here, we report a strategy for expanding the operational horizon of ampere-scale biomass electrorefining using a cuprous-integrated NiCo-spinel heterostructure (Ni1.5Co1.5O4-Cu2O) that effectively decouples these competing pathways. By engineering a cuprous-integrated heterostructure, we establish a functional dichotomy wherein synergistic Ni/Co sites activate 5-hydroxymethylfurfural, while the Cu2O moiety selectively suppresses OER by thermodynamically elevating the *OH deprotonation barrier. This design unlocks a record-broad anodic window and, when integrated into a flow cell, delivers an exceptional 2,5-furandicarboxylic acid yield (> 90%) at industrial-scale currents (> 4A) across an extended voltage range (up to 2200mV). In situ spectroscopy and density functional theory calculations validate this mechanism, confirming that optimized interfacial coupling drives the selective 5-hydroxymethyl-2-furancarboxylic acid pathway. This work provides a generalizable electronic-structure engineering strategy for high-performance, scalable organic electrosynthesis.

Achieving high selectivity in the electrocatalytic hydrogenation (ECH) of concentrated 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) remains a challenge due to competitive adsorption at high HMF concentrations, which limits active-site availability and suppresses *H generation. Regulating the balance between *H generation and HMF adsorption is therefore essential for maintaining selectivity under practical conditions. Here we show a surface amide-functionalized copper nitride catalyst (Ami-Cu3N) featuring dual-nitrogen active sites. The catalyst achieves >99% DHMF selectivity and >98% Faradaic efficiency, with a production rate of 63.4 mmol cm-2 h-1 at 500 mA cm-2 under concentrated HMF conditions. Mechanistic studies indicate that the combined roles of lattice nitrogen (promoting water dissociation) and amide nitrogen (modulating HMF adsorption) lower the energy barriers for both *H formation and HMF hydrogenation, facilitating high activity and selectivity. In addition, a coupled electrolysis system enables simultaneous production of value-added products at both electrodes. These findings provide design principles for electrocatalysts that enable selective biomass conversion at high reaction rates.

The efficiency of alkaline electrocatalytic water splitting is fundamentally restricted by the divergent functional requirements for the sluggish water dissociation (Volmer step) and the subsequent hydrogen desorption (Sabatier principle). Developing non-noble metal catalysts that can decouple and synchronize these distinct elementary steps within an integrated structure remains a formidable challenge. Herein, we report a ceria-molybdenum dual-engineering strategy on nickel phosphide (Mo-Ni2P-CeO2/NF) designed to overcome these mechanistic constraints through synergistic component interplay. The oxygen-vacancy-rich CeO2 domains serve as dedicated water-cleaving centers to drastically lower the dissociation barrier, while simultaneous Mo-doping of the Ni2P lattice optimizes the electronic structure of Ni sites to achieve near-ideal hydrogen binding energetics. This site-specific synergy effectively matches the proton supply with subsequent H* intermediate turnover, enabling unimpeded reaction pathways even at high current densities. Consequently, the optimized catalyst Mo-Ni2P-CeO2/NF delivers an industrial-relevant current density of 500 mA cm-2 at an ultralow overpotential of 221 mV. When integrated into an anion exchange membrane water electrolyzer, the system operates efficiently at 1.69 V (500 mA cm-2) with robust stability exceeding 500 h. This work establishes a rational protocol for synchronizing active site engineering with interface design, offering a robust pathway toward high-throughput hydrogen production.

The electrochemical CO2 reduction reaction (ECR) to multi-carbon (C2+) chemicals is intrinsically hindered by the rigid scaling relations and geometric homogeneity of pristine copper surfaces, which enforce a singular atop-type ⁎CO intermediate. Herein, we implement a ligand-directed motif inheritance strategy to synthesize nitrogen-doped CuO (N-CuO) nanoparticles, uniquely characterized by asymmetric Cu–N/Cu–O lattice motifs. Under severe cathodic polarization, these robust Cu–N bonds structurally modulate the metallic reconstruction, preserving local non-metal coordination to sustain a highly active, mixed-valence Cuδ+ species. Operando spectroscopic and theoretical analyses reveal that this local structural asymmetry disrupts adsorption homogeneity, explicitly driving the spatial co-adsorption of bridge- and atop-type ⁎CO intermediates. This dual-mode configuration bypasses conventional kinetic bottlenecks to drastically accelerate C–C dimerization. Consequently, the N-CuO catalyst delivers a record-level C2+ Faradaic efficiency of 82.2% at an industrially relevant current density of 0.9Acm-2, exhibiting exceptional structural and catalytic stability over 50hours of continuous flow-cell operation. This work establishes atomic-scale lattice asymmetry as a decisive design principle for stabilizing active Cuδ+ species and steering multi-carbon electrosynthesis at practical reaction rates.

The sluggish kinetics of water decomposition in alkaline/neutral media, combined with the challenge of balancing the adsorption/desorption behavior of hydrogen intermediates (H*), severely restrict the pH-universal hydrogen evolution reaction (HER) performance. Herein, we incorporate ruthenium (Ru) into the cobalt phosphide (CoP) and composite the CoP with MXene for efficient pH-universal HER. As revealed by multiply characterizations including in situ FTIR and DFT calculation, the incorporated Ru destructs the rigid network structure of interfacial water, which facilitate its migration and accelerates the Volmer step while lowering the water dissociation energy barrier. The incorporated Ru and composited MXene balance the H* adsorption/ desorption behavior via the optimizeddband center of Co sites, which promotes the Tafel step. Accordingly, Ru-CoP/MXene exhibits efficient and stable HER performance with the low overpotentials of 9.0, 17.3, and 80.6 mV at 10 mA cm-2 in alkaline, acidic, and neutral electrolytes, composite delivering the remarkably low over-potentials 202 mV at 5.0 A cm-2 in alkaline electrolyte. And the anion exchange membrane water electrolyzer (AEMWE) based on Ru-CoP/MXene||RuO2 realizes 1.0 and 2.0 A cm-2 at the voltages of 1.75 and 1.88 V and maintains 97 % of its initial voltage during 200-hour continuous operation.

Electrocatalytic nitrate reduction reaction (NitRR) utilizing water as a hydrogen source under ambient conditions represents a highly promising avenue for sustainable ammonia synthesis and environmental remediation. However, achieving high efficiency and selectivity in NitRR is fundamentally challenged by the complex lifecycle management of active hydrogen derived from water splitting. This review provides a timely and comprehensive analysis centered on the pivotal role and meticulous regulation of active hydrogen throughout the NitRR process. We first elucidate the distinct functions and characteristics of various hydrogen species, followed by a survey of advanced characterization techniques crucial for monitoring the dynamics of active hydrogen. Critically, three core strategies were systematically dissected to modulate the active hydrogen lifecycle: accelerating water activation and dissociation, enhancing the directional transport of hydrogen species, and precisely tuning active hydrogen coupling pathways while suppressing parasitic hydrogen evolution. By consolidating current understanding from both catalyst design and reaction mechanism perspectives, this review offers a hydrogen-centric roadmap and highlights emerging opportunities for rationally engineering advanced NitRR systems.

Although cobalt nitride (Co2N) presents considerable hydrogen evolution reaction (HER) activity, its inability to balance water dissociation and H* adsorption results in sluggish HER kinetics. To overcome this limitation, we propose a strategy to optimize the interfacial water structure by incorporating Ru into Co2N (Ru-Co2N), aiming for efficient and stable HER catalysis across the full pH range. As revealed by a series experimental characterizations and density functional theory (DFT) calculation, the incorporated Ru facilitates the interfacial water migration via disrupting its rigid hydrogen-bond network structure while simultaneously decrease the charge transfer resistance, which accelerates kinetics of water dissociation and the follow-up H2 evolution process. Furthermore, the electron rearrangement within Co2N originated from the Ru incorporation moves up the dorbital center of Co sites, which promotes thermodynamic favorability through the reduced energy barriers for both water dissociation and H* adsorption. Accordingly, Ru-Co2N exhibits low overpotentials of 20, 24, and 37 mV at 10 mA cm-2 in alkaline, neutral, and acidic electrolytes with no obvious activity attenuation in the longterm stability test. This work provides a new idea for the design of low-cost and high-efficiency bimetallic nitride catalysts.

Although it has been recognized that surface modification and microenvironment modulation of catalytic materials holds powerful promise in improving catalytic performance, especially for electricity-driven CO2 reduction reaction (CO2RR), it still remains a formidable challenge due to the lack of effective technical methods and limited understanding. Herein, a distinctive ethylene-glycol-functionalized lead carbonate nanoparticles were successfully anchored on reduced graphene oxide surfaces (EG-PbCO3/rGO) by the successive self-assembly/ reduction anchoring and in situ electrochemical transformation. The comprehensive understanding of the enhanced mechanism of EG-mediated CO2RR on PbCO3/rGO is achieved by integrating experimental and theoretical analysis. The presence of EG creates a thermodynamically favorable microenvironment for Pb sites, thereby facilitating the CO2-to-HCOOH conversion, which is achieves through enhanced enrichment of CO2, modulation of the electronic structure as well as the generation of *OCHO key intermediates. The optimal EGPbCO3/rGO yields a sustained FEC1 above 90 % in an electrolysis potential range from -0.75 V vs. RHE to -0.90 V vs.-RHE, superior to other Pb-based catalysts. This work deeply reveals the significant impact of microenvironment modulation on electrochemical system, thereby highlighting its positive contribution.

Although the potential of microenvironment modulation to enhance electricity-driven CO2 reduction has been recognized, substantial challenges remain, particularly in effectively integrating multiple favorable microenvironments. Herein, we synthesize CeO2 with abundant oxygen vacancies to effectively disperse and anchor small-sized Ag2O nanoparticles (Ag2O/Vo-CeO2). Vo-CeO2 acts as a multifunctional modulator, regulating both the reaction microenvironment and the electronic structure of Ag sites, thereby boosting CO2 reduction (CO2RR) efficiency. Its strong CO2 adsorption and H2O dissociation capabilities facilitate the supply of CO2 and active *H species to Ag sites. The electron-withdrawing effect of Vo-CeO2 induces polarization at interfacial Ag sites, generating Ag delta+ species that enhance CO2 affinity and activation. Moreover, the electronic coupling between Vo-CeO2 and Ag upshifts the d-band center of Ag, optimizing COOH binding and lowering the thermodynamic barrier of the potential-determining step. Ag2O/Vo-CeO2 delivers a consistently high Faraday efficiency (FE) of over 99% for CO production even at industrially current density (up to 365 mA cm(-2) herein), and the operational potential window spans an astonishing 1700 mV (FE >95%). The unprecedented activity, which overcomes the trade-off between the selectivity and current density for CO2RR, outperforms state-of-the-art Ag-based catalysts reported to date. These findings offer a promising pathway to develop robust CO2RR catalysts and present an engineering strategy for constructing the optimal microenvironment of active sites via the synergistic effects of multifunctional modulation. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Integrating renewable electricity-powered hydrogen evolution (HER) with oxidative biomass valorization presents a promising strategy to enhance energy utilization and cost-effectiveness. However, achieving an industrial-scale production rate at a low potential remains a critical challenge. Herein, a dense dual-phase NiSe-CoNiSe2 heterostructure is engineered through sequential hydrothermal and selenization processes. During the electro-oxidation of 5-hydroxymethylfurfural (HMFEOR), the spatially separated yet complementary CoNiSe2 and NiSe active components at the interface effectively balance the adsorption kinetics of HMF/intermediates and *OH species, and facilitate sequential C & horbar;H/O & horbar;H bond cleavage, ultimately unlock a dynamically regulated pathway for reactant capture and processing. This synergistic effect achieves unprecedented HMFEOR performance of Ni/Co-based catalysts reported to date, including a record-low onset potential of 1.16 VRHE, a current density of approximate to 400 mA cm-2 at 1.33 VRHE, and an astonishing 2,5-furandicarboxylic acid (FDCA) production rate of 430 mu mol cm-2 h-1 (at 1.28 VRHE), which breaks the trade-off between energy consumption and production rate. When applied to coupled HMFEOR-HER flow electrolysis, the system delivers an industrially viable FDCA output of 4.92 mmol cm-2 h-1 (at 1.50 V). This heterointerface-driven strategy establishes a scalable platform for energy-minimized and high-flux biomass upgrading, advancing the simultaneous production of renewable chemicals and green hydrogen toward industrial feasibility.