Susan Meñ Aspera, ez, Ryan Lacdao Arevalo, Hiroshi Nakanishi, Hideaki Kasai, Shinobu Sekine, Hiroyuki Kawai
We analyzed the electronic and structural properties of an α-Keggin type molybdenum-based polyoxometalate (POM) [[PMo12O40]3-] and its capacity for reduction reaction via H adsorption using ab initio calculations based on density functional theory (DFT). We also determined the change in the electronic properties brought about by vanadium substitutional doping, and its effect on the capacity of POM to adsorb H atom. We found that the optimal substitutional doping of four vanadium per one unit of POM is adequate to maintain its structural stability. Furthermore, increasing dopant concentration changes charge redistribution such that it induces charge transfer to an initially less active sites for H adsorption on pristine POM. This may increase the possibility of creating active sites from an initially inert H adsorption sites and allows for a higher density of H adsorption. This phenomenon could be relevant for chemical reactions that initially requires high number of pre-adsorbed H atoms. © 2020 IOP Publishing Ltd.
National Institute of Technology, Akashi College, 679-3 Nishioka, Uozumi, Akashi, Hyogo, 674-8501, Japan; Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Osaka, Suita, 565-0871, Japan; Institute of Industrial Science, University of Tokyo, Meguro, Tokyo, 153-8505, Japan; Toyota Motors Corporation, Mishuku, Susuno, 410-1193, Shizuoka, 1200, Japan; Department of Physics, University of San Carlos, Talamban Campus, Cebu City, Philippines
