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.

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 Ni-N coordination structure has been shown to be conducive to the electrochemical CO2 reduction reaction (CO2RR) to CO, and this process has been extensively validated. However, the impact of Ni-N coordination structures within Ni-based clusters on CO2RR has received relatively limited research attention to date. In this study, catalysts containing Ni single atoms and Nin clusters (Ni-N/Nin) were synthesised, and subsequently, Nin clusters were transformed into NinNx clusters (Ni-N/NinNx) through secondary nitridation. The experimental results, as illustrated by X-ray photoelectron spectra and X-ray absorption fine structure spectra, demonstrate that the Ni-N bond in Ni-N/NinNx increased and Ni-N-Ni bonds within atomic clusters were generated, thereby confirming the transformation from Nin clusters to NinNx clusters. Density functional theory calculations show that the NinNx clusters have a lower energy barrier for the *CO2- + H+ → *COOH step compared to Nin clusters, and promote the entire reaction. Furthermore, in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations collectively indicate that abundant Ni-N coordination structures in clusters effectively reduce the energy barrier of CO2 + e- → *CO2- and facilitate the activation of CO2 to *CO2- across a broader potential window. Ni-N/NinNx demonstrates high Faraday efficiency of CO (FECOmax = 98.6 % at -0.4 V vs. RHE), a wider potential window (-0.3 to -0.8 V vs. RHE, FECO > 90 %) and high CO partial current density (jCO > 100 mA cm-2). In comparison with Ni-N/Nin, the maximum CO partial current density of Ni-N/NinNx is enhanced by approximately 4.6 times. These findings offer valuable insights into the structure-activity relationship of Ni-based cluster catalysts and facilitate the development of more advanced atomically cluster catalysts.

Cr leaching is anticipated to extensively advance the activity of Cr-containing catalysts towards the oxygen evolution reaction（OER）,but the underlying catalytic enhancement mechanism requires further investigation.Herein,NiFeCr layered double hydroxide（NiFeCr-LDH） is proposed as a proof-of-concept catalyst to elucidate the evolution of Cr species and its enhancement mechanism in OER.The incorporation of Cr（Ⅲ） ions into the lattice of NiFe-LDH is achieved through a meticulously controlled electrodeposition process,which not only promotes Cr leaching but also deepens surface reconstruction.More importantly,experimental and theoretical results demonstrate that protogenetic CrO 4 2- anions,derived from the oxidation of leached Cr ions,adsorb onto the surface NiFeCr-LDH under the anodic potential to create a CrO 4 2- -rich electrical double layer(CrO 4 2- -rich EDL) and function as co-catalyst to trigger OER.CrO 4 2- -rich EDL integrated with vacancies balances the Gibbs free energies of the reconstructed NiFeCr-LDH for oxygen-containing intermediates,resulting in an exceptionally low overpotential of 286 mV at 500 mA cm -2 ,which outperforms most state-of-the-art metallic catalysts.Additionally,the anion exchange membrane water electrolysis system assembled with NiFeCr-LDH and Pt/C demonstrates1000-h stability at a current density of 1.0 A cm -2 under a voltage of 1.74 V（at 70℃）,highlighting its promising potential for practical,large-scale and sustainable applications.

Exquisite design of RuO2 -based catalysts to simultaneously improve activity and stability under harsh conditions and reduce the Ru dosage is crucial for advancing energy conversion involving oxygen evolution reaction (OER). Herein, a distinctive cobalt-doped RuOx framework is constructed on Co3 O4 nanocones (Co3 O4 @CoRuOx ) as a promising strategy to realize above urgent desires. Extensive experimental characterization and theoretical analysis demonstrate that cobalt doped in RuOx lattice brings the oxygen vacancies and lattice contraction, which jointly redistribute the electron configuration of RuOx . The optimized d-band center balances the adsorption energies of oxygenated intermediates, lowing the thermodynamical barrier of the rate-determining step; and meanwhile, the over-oxidation and dissolution of Ru species are restrained because of the p-band down-shifting of the lattice oxygen. Co3 O4 @CoRuOx with 3.7 wt.% Ru delivers the extremely low OER overpotentials at 10 mA cm-2 in alkaline (167 mV), neutral (229 mV), and acidic electrolytes (161 mV), and super operating stability over dozens of hours. The unprecedented activity ranks first in all pH-universal OER catalysts reported so far. These findings provide a route to produce robust low-loading Ru catalysts and an engineering approach for regulating the central active metal through synergy of co-existing defects to improve the catalytic performance and stability.

The renewable-energy-driven integration of hydrogen production and biomass conversion into value-added products is desirable for the current global energy transition, but still a challenge. Herein, carbon-coated CoO–Co heterojunction arrays were built on copper foam (CoO–Co@C/CF) by the carbothermal reduction to catalyze the hydrogen evolution reaction (HER) coupled with a 5-hydroxymethylfurfural electrooxidation reaction (HMFEOR). The electronic modulation induced by the CoO–Co heterojunction endows CoO–Co@C/CF with a powerful catalytic ability. CoO–Co@C/CF is energetic for HER, yielding an overpotential of 69 mV at 10 mA·cm−1 and Tafel slope of 58 mV·dec−1. Meanwhile, CoO–Co@C/CF delivers an excellent electrochemical activity for the selective conversion from HMF into 2,5-furandicarboxylic acid (FDCA), achieving a conversion of 100%, FDCA yield of 99.4% and faradaic efficiency of 99.4% at the lower oxidation potential, along with an excellent cycling stability. The integrated CoO–Co@C/CF||CoO–Co@C/CF configuration actualizes the H2O–HMF-coupled electrolysis at a satisfactory cell voltage of 1.448 V at 10 mA·cm−2. This work highlights the feasibility of engineering double active sites for the coupled electrolytic system.

The renewable electricity-driven hydrogen evolution reaction (HER) coupled with biomass oxidation is a powerful avenue to maximize the energy efficiency and economic feedback, but challenging. Herein, porous Ni-VN heterojunction nanosheets on nickel foam (Ni-VN/NF) are constructed as a robust electrocatalyst to simultaneously catalyze HER and 5-hydroxymethylfurfural electrooxidation reaction (HMF EOR). Benefiting from the surface reconstruction of Ni-VN heterojunction during the oxidation process, the derived NiOOH-VN/NF energetically catalyzes HMF into 2,5-furandicarboxylic acid (FDCA), yielding the high HMF conversion (>99%), FDCA yield (99%), and Faradaic efficiency (>98%) at the lower oxidation potential along with the superior cycling stability. Ni-VN/NF is also surperactive for HER, exhibiting an onset potential of ≈0 mV and Tafel slope of 45 mV dec-1 . The integrated Ni-VN/NF||Ni-VN/NF configuration delivers a compelling cell voltage of 1.426 V at 10 mA cm-2 for the H2 O-HMF paired electrolysis, about 100 mV lower than that for water splitting. Theoretically, for Ni-VN/NF, the superiority in HMF EOR and HER is mainly dominated by the local electronic distribution at the heterogenous interface, which accelerates the charge transfer and optimize the adsorption of reactants/intermediates by modulating the d-band center, therefore being an advisable thermodynamic and kinetic process.

Pairing the hydrogen evolution reaction (HER) with the thermodynamics-friendly electrooxidation reaction (EOR) is a powerful way to maximize the energy/economic effectiveness, but still a challenge. Herein, the symbiotic Ni/MoN heterojunction arrays were constructed on foam (Ni/MoN/NF) by the nitridation-induced in situ reduction/conversion strategy. The fascinating interfacial electronic structure and surface reconstruction of Ni/MoN/NF heterojunction are responsible for the enhanced HMF-H2O paired electrolysis. Ni/MoN/NF only requires a low overpotential of 53 mV to reach the HER current density of 10 mA cm(-2), as well as the good durability; and NiOOH derived on the anode are electronically activated by MoN to achieving high-efficiency conversion from HMF to FDCA (similar to 100 % conversion, 97.5 % yield and 97.4 % Faradaic efficiency). For the HMF-H2O paired electrolysis, the assembled Ni/MoN/NF||Ni/MoN/NF electrolyzer only requires a low potential of 1.391 V to yield the current density of 10 mA cm(-2), ranking at the forefront in the reported coupling catalysts. Theoretical calculations manifest that the upshift of d-band center of the NiOOH/MoN heterojunction contributes to HMF chemisorption and activation, thereby enhancing its catalytic activity towards HMFEOR. Our study sheds light on the significance of designing the paired electrolysis with low voltage input for renewable energy applications.

The "Fe effect" can maximize the activity of nickel-iron layered double hydroxides (NiFe-LDH) toward oxygen evolution reaction (OER) when the iron content, the lattice distortion, the conductivity, and other related factors are well balanced. It is difficult for the homogeneous NiFe-LDH to take good care of the above requirements at the same time. Herein, we proposed an elaborate atmosphere corrosion strategy to construct porous NiFe-LDH with rich edge/surface-Fe defects on Ni foam (NF). Such edge/surface-Fe defects, mainly caused by the local unequal-stoichiometric ratio of Fe/Ni in the nanometer or subnanometer region, are determined by the unbalanced permeating of the acid vapor and the confined reaction of local Fe and Ni species ionized by the acid vapor. Benefiting from the abundant and fantastic edge/surface-Fe defects, the optimal NiFe-LDH prepared by atmosphere corrosion is more energetic for OER than that synthesized in conventional liquid phase, only a potential of 1.481 and 1.552 VRHE to respectively achieve the current density of 100 and 1000 mA cm-2 as well as a satisfactory stability and reproducibility. An overall water-splitting system assembled by inhomogeneous NiFe-LDH and commercial Pt-C can reach a current density of 100 mA cm-2 at a solar cell of 1.72 V. Additionally, the atmosphere corrosion is very suitable for the large-scale, green, and economic synthesis of metal-based catalysts with high enrichment of defects, highlighting its potential for device and industrial applications.

The hierarchical porous nitrogen-doped two-dimensional carbon (HNGC) was prepared by simple calcination of magnesium sulfate (MgSO4) and self-synthesized nitrogen-doped two-dimensional graphene-like carbon at a mild temperature in oxygen. The influence MgSO4 on the morphology, structure and chemical composition of the prepared HNGC samples were studied using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, surface area analysis, X-ray photoelectron microscopy and elemental analyzer. HNGC-2 exhibited a uniform three-dimensional coral-like porous inter-connected structure, large specific surface area, high pore volume, and no loss of nitrogen content. HNGC-2 demonstrated an excellent rate capability of 62.8% at 20 A g(-1), outstanding stability of 96.1% following 5000 cycles and the assembled symmetric supercapcitor achieved 12.5 Wh kg(-1) at a 350 Wkg(-1) and 7.5 Wh kg(-1) at 3500 Wkg(-1). The novel method was also found to be effective for facilitating the electrochemical performance of commercial biomass active carbon. In addition, HNGC-2 was used for the photo-catalytic degradation of methylene blue and over 99% of methylene blue was successfully degraded under 25-min visible irradiation in the presence of potassium per -sulfate. The enhanced electrochemical performance and the excellent photo-catalytic performance of HNGC-2 indicated that porous carbon can be successfully activated using an appropriate oxidation strategy.

At present, formic acid with the high energy value is the promising product generated by the large-scale renewable electricity-driven CO2 conversion, yet challenges remain in the high-throughput and low-energy production accompanied by the considerable selectivity. Herein, in view of the contribution of electronic modulation to electrocatalytic CO2 reduction reaction (CO2RR) activity of catalysts, the thin BiCu-bimetallic film was designed and built on Cu foam (BiCu/CF) by coupling a facile hydrothermal reaction and an immediate electrochemical transformation. The theoretical evidences demonstrate that Bip-orbital delocalization triggered by the close-contact metal Cu optimizes reaction pathway of CO2RR, and also favours the orbital hybridization between Bi atom and *OCHO intermediate to form more anti-bonding orbitals, resulting in stabilizing *OCHO intermediate and lowering the thermodynamic barrier of CO2RR. Meanwhile, the electron transferred from catalyst-sites to reaction species also accelerates during CO2RR. Integrating the improved intrinsic activity of Bi catalytic-sites and the superiority of Cu foam in exposing more active sites and the mechanical strength, the BiCu/CF electrode with optimal thickness can acquire satisfactory indicators for industrial application, yielding a record formate current density of 856 mA cm(-2), higher than 85% Faradic efficiency, along with a remarkable stability, which outperforms state-of-the-art Bi-based catalysts. This study offers potential avenues of engineering orbital delocalization to rationally construct advanced CO2RR electrodes for the carbon-neutral cycle and utilization.

The electro-Fenton oxidation is one of the powerful approaches for achieving the complete mineralization of organic pollutants in water. The key dilemma for efficient industrial application of electro-Fenton oxidation is the complicated post-processing of iron sludge, and the cost and risk associated with H2O2 transportation and storage. Herein, Cu-coupled Fe/Fe3C covered with carbon layer on carbon felt (Cu-Fe/Fe3C@C), engineered by a hydrothermal reaction followed by the consequent thermal-treatment in N2 atmosphere, as a self-supported integrated cathode were used for an onsite oxygen reduction reaction and a Fenton oxidation reaction. Experimental evidences demonstrate that, at the operating potential of -1.1 V, Fe3C can selectively catalyze O2 into H2O2 by 2e reduction pathways with assistance of metal Cu. Meanwhile, metal Fe and Cu incorporated into Cu-Fe/Fe3C@C simultaneously motivate the onsite Fenton oxidation arose by H2O2. Such a win-win catalyst presented high activity in the electro-Fenton process. In acidic environment, the efficient mineralization rate of methylene blue, nitrobenzene, phenol, and bisphenol A can reach more than 70% in 60 min, as well as the excellent stability and durability due to the protection of graphited carbon layer. Compared with tradition electrochemical degrade system, the prepared Cu-Fe/Fe3C@C electrode as cathode for practical refractory brewing leachate treatment reveal more efficient decolorization and mineralization, saving 14.3% of electricity.

The successful isolation of metal phthalocyanines into graphene-supported microporous polyanilines results in rich exposure to active sites, rapid electron transfer and efficient gas transport channels, which synergically enhance NH3 sensing.

Water splitting, as a powerful technology for converting renewable energy into hydrogen energy, suffers from the kinetically sluggish oxygen evolution reaction (OER). Herein, encouraged by the structural characteristic of layered double hydroxide (LDH), CoCr LDH was proposed, for the first time, to verify the photoelectric synergy towards catalyzing OER. Under AM 1.5 irradiation, the optimal CoCr LDH presents a 1.35 similar to 1.5-fold enhanced OER intrinsic activity and a faster charge transfer, thus achieving a decreased overpotential of 28 mV at 100 mA cm(-2) in 1.0 M KOH. Meanwhile, the H-2 amount produced at the cathode also increases 1.8 times. The synergistic enhancement in the highly active Co3+ sites and the charge transfer, both triggered by the photo-generated carriers on CoCr LDH, is mainly responsible for such a remarkably improved activity. This proof-of-concept study provides a reasonable and scalable platform towards engineering the self-consistent catalysts for the photoelectric synergy system.

Although the activity of electrocatalysts towards oxygen evolution reaction (OER) has achieved considerable improvement by modulating the intrinsic electron structure, the role of supports to OER performance, often being reduced to enhancing the conductivity, is not fully explored. In this paper, a proof-of-concept study based on a series of hybrids of nickel iron (hydr)oxide nanoparticles (NiFeO NPs) and carbon supports with different oxidation level compared the motivation of supports for OER activity. The key to implementation lay in anchoring and growing of NiFeO NPs on the various carbon supports by electrostatic assembly and subsequent in-situ reduction. A series of experiments indicated that the strong coupling of metal ions and graphene oxide (GO) contributed to the formation of ultrasmall NiFeO NPs (approximate to 2 nm) and the firm interaction between NiFeO NPs and GO, which in turn resulted in exposing more metal atoms, modulating local electron structure of active sites, and accelerating the charge-transfer ability. The OER activity of optimal NiFeO NPs anchored on rGO (NiFeO NPs/rGO) was significantly elevated, achieving an overpotential as small as 201 mV at 10 mA cm(-2) and a low Tafel slope of 68 mV dec(-1), as well as remarkable stability. Such exciting capacity for catalyzing OER prevailed over the vast majority of previously reported transition-metal electrocatalysts, even superior to numerous noble metal-containing catalysts. The electrolyzer employing NiFeO NPs/rGO and commercial Pt/C for anode and cathode could be powered by a solar cell for efficient alkaline seawater splitting. This work opens up a universal and scalable way for further advancing the intrinsic activity of energy-related materials.

Electrochemical detection of catechol (CC) based on the integrated nanocomposite electrodes with high sensitivity and excellent selectivity is highly desirable for environment monitoring and assessment. In this work, the methylated tetra-β-(N,N-diethylaminoethoxy)phthalocyanine cobalt(II)/electrochemically reduced graphene oxide ((MtPcCo/ErGO)n) multilayer films were successfully constructed via a directly coupled layer-by-layer assembly strategy based on the electrostatic attraction as well as π-π stacking interaction, and consequent in situ electroreduction. The formation of the robust multilayer films only relies on the alternately self-driven combination of the [MtPcCo]4+ and GO but without addition of any polymer or surfactant adhesives. The directly coupled multilayer films can play such roles of coordination as promoting sensitive response signal, regulable layer architecture, oriented transmission of electrons, and electrical conductivity. As a result, the tailored (MtPcCo/ErGO)10 film can work as an efficient electrocatalyst for CC oxidation and sensitive detection. The oxidation current density (j) of CC is widely linear to its concentration from 5 to 150 μm and 150 to 350 μm, respectively, with a low detection limit of 0.53 μm (S/N = 3). Furthermore, the good selectivity, reproducibility and long-term storage stability make the multilayer film suitable for the practical CC determination.

Sn-based electrocatalysts have been gaining increasing attention due to their potential contribution in the conversion of CO2 into HCOOH driven by sustainable energy sources; however, their actual capability to catalyze CO2 reduction reaction (CO2RR) still cannot meet the requirements of commercial-scale applications. Therefore developing Sn-based catalyst is of vital importance. Herein, the sheet-like heterophase SnO2/Sn3O4 with a high density of phase interfaces has been first engineered by a facile hydrothermal process, with Sn3O4 as the dominant phase. The evidences from experiments and theoretical simulation indicate that the charge redistribution and built-in electric field at heterophase interfaces boost CO2 adsorption and HCOO* formation, accelerate the charge transfer between the catalysts and reactants, and ultimately greatly elevate the intrinsic activity of the heterophase SnO2/Sn3O4 towards CO2RR. Meanwhile, the in-situ generated porous structure and metal Sn during CO2 RR improve the mass transmission within the interlayer volume and the conductivity of SnO2/Sn3O4. The heterophase SnO2/Sn3O4 displays high activity and selectivity for CO2RR, achieving an improvement in CO2 reduction current density, 88.3% Faradaic efficiency of HCOOH conversion at −0.9 VRHE, along with a long-term tolerance in CO2RR. This study demonstrates that heterophase interface engineering is an efficient strategy to regulate advanced catalysts for different applications.

Although Sn-based catalysts have recently achieved considerable improvement in selective electro-catalyzing CO2 into HCOOH, the role of various valence Sn species is not fully understood due to the complexity and uncertainty of their evolution during the reaction process. Here, inspired by the theoretical simulations that the concomitant multivalent Sn (Sn0, Sn11 and SnIV) can significantly motivate the intrinsic activity of Sn-based catalyst, the Sn/SnO/SnO2 nanosheets were proposed to experimentally verify the synergistic effect of multivalent Sn species on the CO2-into-HCOOH conversion. During CO2 reduction reaction, the Sn/SnO/SnO2 nanosheets, which are prepared by the sequential hydrothermal reaction, calcined crystallization and low-temperature H2 treatment, exhibit a high FEHCOOH of 89.6% at −0.9 VRHE as well as a large cathodic current density. Systematic experimental and theoretical results corroborate that multivalent Sn species synergistically energize the CO2 activation, the HCOO* adsorption, and the electron transfer, which make Sn/SnO/SnO2 favour the conversion from CO2 into HCOOH in both thermodynamics and kinetics. This proof-of-concept study establishes a relationship between the enhanced performance and the multivalent Sn species, and also provides a practicable and scalable avenue for rational engineering high-powered electrocatalysts.