Keywords: 
• 第一性原理 /
• 三氧化钨 /
• 氢气 /
• 吸附能

Abstract: With the development of modern industrial technology, tungsten products prepared from normal tungsten pow-der cannot meet the demands of industry. The tungsten product produced from ultra-fine tungsten powder exhibits high strength, high toughness, and low metal plasticity-brittleness transition temperature, which greatly improves the performance of materials. Hence, it is necessary to carry out theoretical research on the micro adsorption dynamics during hydrogen reduction of tungsten trioxide to prepare ultra fine tungsten powder. In order to understand crystal characteristics of WO3 and WO3(001) surface characteristics, and to provide beneficial theoretical support for reaction law of hydrogen reduction on the WO3(001) surface, the mechanisms of H atom adsorption on cubic WO3 and WO3(001) surface are studied by the first-principles calculation based on the density functional theory (DFT) plane wave pseudo-potential method. The results show that theoretically calculated band gap of the cubic crystalline WO3 is 0.587 eV. There are two kinds of WO3(001) surfaces, WO-terminated (001) surface and O-terminated (001) surface. The W—O bond length and the bond angle of W—O—W structure change after the geometric optimization of the surface, and thus the surface relaxation is realized. The WO-terminated (001) surface shows n-type semiconductor characteristics while the O-terminated (001) surface shows p-type semiconductor characteristics. Four adsorption configurations of H atoms on the WO-terminated (001) surface and the O-terminated (001) surface, including H—O2c—H, H—O2c · · · H—O2c, H—O1c—H, and H—O1c · · · H—O1c, are calculated. Among them, the adsorption energy of the H—O1c—H configuration is the smallest (?3.684 eV) with the shortest bond length of H—O bond (0.0968 nm), and hydrogen atoms lose the most of electrons (0.55e), which indicates that the H—O1c—H adsorption configuration is the most stable one. The band gap of the H—O1c—H configuration increases from 0.624 eV to 1.004 eV after adsorption, while the bandwidth of valence band is almost unchanged. The results about the density of states (DOS) reveal that 1s state of the H atom interacts with 2p and 2s states of the O atom. Strong isolated electron peaks are formed to be at about?8 and?20 eV. The outermost O1c atoms of O-terminated (001) surface contain an unsaturated bond, facilitating the bonding between two H atoms and one O1c atom. Thus, two H atoms and one O1c atom form chemical bonds respectively, and an H2O molecule is generated, leaving an oxygen vacancy on the surface after adsorption reaction. By combining experimental observations with simulation results, the mechanism of hydrogen reducing tungsten trioxide can be elaborated profoundly from a micro view.