Shicheng Yan

Cr-triggered electronic modulation optimizes OER intermediate adsorption and accelerates electron transfer. The CrNiFe-LDH/NF electrode has 219 mV overpotential at 100 mA cm ⁻² and 500 h stability, showing potential for industrial water splitting.

A Co-doping and thermal modulation strategy is proposed for sulfidized NiFe(OH) ₂ . In situ -formed NiFeCoO _x H _y with ferrimagnetic–paramagnetic structure contributes to stabilize intermediates, delivering a 199 mV overpotential at 90 °C in 1 M KOH.

Electrochemical synthesis of hydrogen peroxide (H2O2) on carbon-based catalysts often faces a persistent activity-stability dilemma: while defects can enhance catalytic activity, they frequently overstabilize the *OOH intermediate, leading to O–O bond cleavage and consequent radical-induced degradation of the catalyst. To address this challenge, we engineered an asymmetric O–Si–N–C structure at the interface between amorphous SiOx and nitrogen-doped reduced graphene oxide (Si-N-rGO), thereby electronically regulating adjacent carbon sites to weaken excessive *OOH adsorption. Combined experimental studies and microkinetic modeling show that electronegative nitrogen acts as an electron buffer, redistributing the local charge density across the O–Si–N–C interface through spatial charge transfer. This electronic adjustment weakens excessive *OOH binding and brings its adsorption free energy into a moderate Sabatier region, facilitating efficient oxygen activation and smooth product desorption via a proton-coupled electron transfer pathway, effectively suppressing radical-mediated structural degradation. As a result, the Si-N-rGO catalyst operates stably for over 160 h at an industrial current density of 300 mA cm–2 in a flow cell, continuously producing 5.0 wt % H2O2 with a Faradaic efficiency of 80%. These findings offer a design strategy for developing durable catalysts toward industrial-scale electrosynthesis of H2O2.

Unraveling electron transfer (ET) mechanisms at photoelectrochemical (PEC) interfaces is crucial for advancing device efficiency. Contrary to the established paradigm of redox‐mediated ET, we report a nonredox mechanism operating at photoelectrode/cocatalyst/electrolyte interfaces. This mechanism utilizes unoccupied orbitals within the cocatalyst's active centers to enable direct, conductor‐like ET without valence change during catalysis. Specifically, using a Ni(OH) ₂ ‐modified Fe ₂ O ₃ photoanode, we demonstrate that applied photovoltage transforms Ni(OH) ₂ into NiOOH, generating Ni ³⁺ active sites ( t _2g ⁶ e _g ¹ ) with an unoccupied e _g orbital. Crucially, this transformation induces a substantial energy level downshift of these sites (from −4.95 to −7.40 eV vs. vacuum), definitively excluding redox mediation under constant photovoltage. Within these Ni ³⁺ sites, the unoccupied e _g orbital serves as the direct conduit for ET without valence variation. This non‐redox, unoccupied orbital‐mediated mechanism provides a rational explanation for electron transfer at PEC interfaces and serves as a fundamental descriptor to guide the rational design of efficient active centers in PEC devices.

Achieving stable and selective electrocatalytic nitrate reduction (NO₃RR) at high current densities demands a fundamental understanding of the hydrogenation mechanism. We demonstrate that alloying cobalt with ruthenium (RuCo) switches the dominant hydrogenation pathway from the Eley-Rideal (E-R) mechanism, involving solvated protons, to the Langmuir-Hinshelwood (L-H) mechanism, utilizing adsorbed protons. Microkinetic modeling, in situ spectroscopy and density functional theory (DFT) calculations reveal that the competitive E-R pathway on pure Co causes sluggish hydrogenation kinetics and low Faradaic efficiency. In contrast, the L-H pathway on RuCo sustains high hydrogen coverage (θ_H ≈ 0.45), enabling efficient hydrogen-atom transfer for high-rate and deep hydrogenation. Leveraging this mechanistic insight, we achieve a satisfactory ammonia yield rate of 135.53 ± 1.18 mg h^-1 cm^-2 with 100% Faradaic efficiency and robust 1000-h stability at 1 A cm⁻². This work provides critical understanding of electrochemical hydrogenation pathways for designing efficient catalysts operating under industrially relevant conditions.