关键字：TOTAL-ENERGY CALCULATIONS; DYNAMICS; SURFACES; METALS; OXIDE

摘要：Understanding the role of cations within the catalysts in the interfacial water behavior at the electrolyte/catalyst interface is of pivotal importance for designing advanced catalysts toward hydrogen evolution reaction (HER), which remains obscure and requires deep probing. Herein, we demonstrate the first investigation of interfacial water behavior on the surface of a series of sodium tungsten bronzes (NaxWO3, 0 < x < 1) by using electrochemical, operando spectroscopic and theoretical characterizations, aiming to gain fundamental insight into the role of sodium ion in the interfacial water structure and subsequent HER at the NaxWO3/electrolyte interface. Our integrated studies indicate that the Na ions significantly enrich the electronic state of WO6 octahedrons in NaxWO3, which leads to the regulated electronic and atomic structures, endowing NaxWO3 with disordered interfacial water network containing more isolated H3O and subsequently moderate H* adsorption to speed the Volmer step at the NaxWO3 surface, thus boosting the HER. Consequently, the intrinsic HER activities achieved on those NaxWO3 are tens of times higher than those on WO3. Particularly, it is found that Na concentration x = 0.69 endows NaxWO3 with the highest intrinsic HER activity, and the resultant Na0.69WO3 with a unique porous octahedral structure exhibits a low overpotential of only 64 mV at current density of 10 mA cm(-2) in acidic electrolyte. This study provides the first insight into the cation-dependent interfacial water behavior induced by the cations within the catalyst and establishes the interfacial water-activity relationship of HER, thus allowing for the design of a more advanced catalyst with efficient interfacial structures towards HER. (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.

卷号：105

期号：-

是否译文：否