Exploring durable electrocatalysts with high activity for oxygen evolution reaction (OER) in acidic media is of paramount importance for H₂ production via polymer electrolyte membrane electrolyzers, yet it remains urgently challenging. Herein, we report a synergistic strategy of Rh doping and surface oxygen vacancies to precisely regulate unconventional OER reaction path via the Ru–O–Rh active sites of Rh-RuO₂, simultaneously boosting intrinsic activity and stability. The stabilized low-valent catalyst exhibits a remarkable performance, with an overpotential of 161 mV at 10 mA cm⁻² and activity retention of 99.2% exceeding 700 h at 50 mA cm⁻². Quasi in situ/operando characterizations demonstrate the recurrence of reversible oxygen species under working potentials for enhanced activity and durability. It is theoretically revealed that Rh-RuO₂ passes through a more optimal reaction path of lattice oxygen mediated mechanism-oxygen vacancy site mechanism induced by the synergistic interaction of defects and Ru–O–Rh active sites with the rate-determining step of *O formation, breaking the barrier limitation (*OOH) of the traditional adsorption evolution mechanism.

CO₂ electroreduction reaction offers an attractive approach to global carbon neutrality. Industrial CO₂ electrolysis towards formate requires stepped-up current densities, which is limited by the difficulty of precisely reconciling the competing intermediates (COOH* and HCOO*). Herein, nano-crumples induced Sn-Bi bimetallic interface-rich materials are in situ designed by tailored electrodeposition under CO₂ electrolysis conditions, significantly expediting formate production. Compared with Sn-Bi bulk alloy and pure Sn, this Sn-Bi interface pattern delivers optimum upshift of Sn p-band center, accordingly the moderate valence electron depletion, which leads to weakened Sn-C hybridization of competing COOH* and suitable Sn-O hybridization of HCOO*. Superior partial current density up to 140 mA/cm² for formate is achieved. High Faradaic efficiency (>90%) is maintained at a wide potential window with a durability of 160 h. In this work, we elevate the interface design of highly active and stable materials for efficient CO₂ electroreduction.

The lack of available protons severely lowers the activity of alkaline hydrogen evolution reaction process than that in acids, which can be efficiently accelerated by tuning the coverage and chemical environment of protons on catalyst surface. However, the cycling of active sites by proton transfer is largely dependent on the utilization of noble metal catalysts because of the appealing electronic interaction between noble metal atoms and protons. Herein, an all-non-noble W/WO₂ metallic heterostructure serving as an efficient solid-acid catalyst exhibits remarkable hydrogen evolution reaction performance with an ultra-low overpotential of −35 mV at −10 mA/cm² and a small Tafel slope (−34 mV/dec), as well as long-term durability of hydrogen production (>50 h) at current densities of −10 and −50 mA/cm² in alkaline electrolyte. Multiple in situ and ex situ spectroscopy characterizations combining with first-principle density functional theory calculations discover that a dynamic proton-concentrated surface can be constructed on W/WO₂ solid-acid catalyst under ultra-low overpotentials, which enables W/WO₂ catalyzing alkaline hydrogen production to follow a kinetically fast Volmer-Tafel pathway with two neighboring protons recombining into a hydrogen molecule. Our strategy of solid-acid catalyst and utilization of multiple spectroscopy characterizations may provide an interesting route for designing advanced all-non-noble catalytic system towards boosting hydrogen evolution reaction performance in alkaline electrolyte.

The reaction pathways on supported catalysts can be tuned by optimizing the catalyst structures, which helps the development of efficient catalysts. Such design is particularly desired for CO₂ hydrogenation, which is characterized by complex pathways and multiple products. Here, we report an investigation of supported cobalt, which is known for its hydrocarbon production and ability to turn into a selective catalyst for methanol synthesis in CO₂ hydrogenation which exhibits good activity and stability. The crucial technique is to use the silica, acting as a support and ligand, to modify the cobalt species via Co‒O‒SiO_n linkages, which favor the reactivity of spectroscopically identified *CH₃O intermediates, that more readily undergo hydrogenation to methanol than the C‒O dissociation associated with hydrocarbon formation. Cobalt catalysts in this class offer appealing opportunities for optimizing selectivity in CO₂ hydrogenation and producing high-grade methanol. By identifying this function of silica, we provide support for rationally controlling these reaction pathways.