Humphrey Nicholas, Tsung Alicia, Singh Shantanu, Irshad Ahamed, Zhao Boyang, Narayan Sri, Ravichandran Jayakanth, Mallikarjun Sharada Shaama
Mork Family Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles CA, USA.
Department of Chemistry, University of Southern California, Los Angeles CA, USA.
Chemphyschem. 2024 Jul 2;25(13):e202300953. doi: 10.1002/cphc.202300953. Epub 2024 May 29.
Chalcogenide perovskites are a class of materials with electronic and optoelectronic properties desirable for solar cells, infrared optics, and computing. The oxide counterparts of these chalcogenides have been studied extensively for their electrocatalytic and photoelectrochemical properties. As chalcogenide perovskites are more covalent, conductive, and stable, we hypothesize that they are more viable as electrocatalysts than oxide perovskites. The goal of this synthetic, experimental, and computational study is to examine the hydrogen evolution reaction (HER) activity of three Barium-based chalcogenides in perovskite and related structures: BaZrS, BaTiS, and BaVS. Potential energy surfaces for hydrogen adsorption on surfaces of these materials are calculated using density functional theory and the computational hydrogen electrode model is used to contrast overpotentials with experiment. Although both experiments and computations agree that BaVS is the most active of the three materials, high overpotentials of these materials make them less viable than platinum for HER. Our work establishes a framework for future studies in the chemical and electrochemical properties of chalcogenide perovskites.
硫族钙钛矿是一类具有电子和光电特性的材料，这些特性对于太阳能电池、红外光学和计算领域来说是理想的。这些硫族化合物的氧化物对应物因其电催化和光电化学性质而受到广泛研究。由于硫族钙钛矿具有更强的共价性、导电性和稳定性，我们推测它们作为电催化剂比氧化物钙钛矿更具可行性。这项合成、实验和计算研究的目的是考察三种钙钛矿及相关结构的钡基硫族化合物：BaZrS、BaTiS和BaVS的析氢反应（HER）活性。使用密度泛函理论计算这些材料表面氢吸附的势能面，并使用计算氢电极模型将过电位与实验进行对比。尽管实验和计算都表明BaVS是这三种材料中活性最高的，但这些材料的高过电位使得它们在析氢反应中比铂的可行性更低。我们的工作为未来硫族钙钛矿化学和电化学性质的研究建立了一个框架。
