Dynamic reconstruction of metal sulphides during electrocatalytic oxygen evolution reaction (OER) has hampered the acquisition of legible evidence for comprehensively understanding the phase-transition mechanism and electrocatalytic activity origin. Herein, modelling on a series of cobalt-nickel bimetallic sulphides, we for the first time establish an explicit and comprehensive picture of their dynamic phase evaluation pathway at the pre-catalytic stage before OER process. By utilizing the in-situ electrochemical transmission electron microscopy and electron energy loss spectroscopy, the lattice sulphur atoms of (NiCo)S_1.33particles are revealed to be partially substituted by oxygen from electrolyte to form a lattice oxygen-sulphur coexisting shell surface before the generation of reconstituted active species. Such S-O exchange process is benefitted from the subtle modulation of metal-sulphur coordination form caused by the specific Ni and Co occupation. This unique oxygen-substitution behaviour produces an (NiCo)O_xS_1.33-xsurface to reduce the energy barrier of surface reconstruction for converting sulphides into active oxy/hydroxide derivative, therefore significantly increasing the proportion of lattice oxygen-mediated mechanism compared to the pure sulphide surface. We anticipate this direct observation can provide an explicit picture of catalysts’ structural and compositional evolution during the electrocatalytic process.

Nanostructured metal-nitrides have attracted tremendous interest as a new generation of catalysts for electroreduction of CO₂, but these structures have limited activity and stability in the reduction condition. Herein, we report a method of fabricating FeN/Fe₃N nanoparticles with FeN/Fe₃N interface exposed on the NP surface for efficient electrochemical CO₂ reduction reaction (CO₂RR). The FeN/Fe₃N interface is populated with Fe−N₄ and Fe−N₂ coordination sites respectively that show the desired catalysis synergy to enhance the reduction of CO₂ to CO. The CO Faraday efficiency reaches 98% at −0.4 V vs. reversible hydrogen electrode, and the FE stays stable from −0.4 to −0.9 V during the 100 h electrolysis time period. This FeN/Fe₃N synergy arises from electron transfer from Fe₃N to FeN and the preferred CO₂ adsorption and reduction to *COOH on FeN. Our study demonstrates a reliable interface control strategy to improve catalytic efficiency of the Fe–N structure for CO₂RR.

Effective and robust catalyst is the core of water splitting to produce hydrogen. Here, we report an anionic etching method to tailor the sulfur vacancy (V_S) of NiS₂ to further enhance the electrocatalytic performance for hydrogen evolution reaction (HER). With the V_S concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS₂-V_S 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential (68 mV) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy (ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S- H* peak of the NiS₂-V_S 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the NiS₂-V_S 5.9% has the optimal |ΔG_H*| of 0.17 eV. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.