CAJ | 학술논문

运用广义梯度近似密度泛函理论方法(GGA-PW91)结合周期平板模型,研究水分子在二氧化铪(111)和(110)表面不同吸附位置在不同覆盖度下的吸附行为.通过比较不同吸附位的吸附能和几何构型参数发现:(111)和(110)表面铪原子(top位)是活性吸附位.水分子与表面的吸附能值随覆盖度的变化影响较小.在(111)和(110)表面,水分子都倾向以氧端与表面铪原子相互作用.同时也计算了羟基、氧和氢在表面的吸附, Mul iken电荷布居,态密度及部分频率.结果表明,在两种表面羟基以氧端与表面铪相互作用,氧原子与表面铪和氧原子同时成键,而氢原子直接与表面氧原子相互作用形成羟基.通过过渡态搜索,水分子在(111)和(110)表面发生解离,反应能垒分别为9.7和17.3 kJ·mol-1,且放热为59.9和47.6 kJ·mol-1.
운용엄의제도근사밀도범함이론방법(GGA-PW91)결합주기평판모형,연구수분자재이양화협(111)화(110)표면불동흡부위치재불동복개도하적흡부행위.통과비교불동흡부위적흡부능화궤하구형삼수발현:(111)화(110)표면협원자(top위)시활성흡부위.수분자여표면적흡부능치수복개도적변화영향교소.재(111)화(110)표면,수분자도경향이양단여표면협원자상호작용.동시야계산료간기、양화경재표면적흡부, Mul iken전하포거,태밀도급부분빈솔.결과표명,재량충표면간기이양단여표면협상호작용,양원자여표면협화양원자동시성건,이경원자직접여표면양원자상호작용형성간기.통과과도태수색,수분자재(111)화(110)표면발생해리,반응능루분별위9.7화17.3 kJ·mol-1,차방열위59.9화47.6 kJ·mol-1.
First-principles calculations based on density functional theory (DFT) with the generalized gradient approximation (GGA-PW91) have been used to investigate the adsorption and dissociation of H2O molecules on HfO2(111) and (110) surfaces at different sites with different coverages. It was found that the surface hafnium atom was the active adsorption position of the (111) and (110) surfaces when compared different adsorption energies and various geometrical parameters. Adsorption energies of water on the HfO2 (111) and (110) surfaces varied slightly as the coverage increased. It was shown that the most favorable configuration of H2O on the HfO2(111) and (110) surfaces corresponded to the coordination of H2O via its oxygen to a surface hafnium atom. Adsorption geometries, Mul iken population charges, density of states, and frequency calculations for HfO2-OH, HfO2-O, and HfO2-H at both surfaces were also carried out. The results showed that the hydroxyl group interacted with the surface by its oxygen atom to surface hafnium atoms. Isolated oxygen atoms bound to surface hafnium and oxygen atoms, while hydrogen atoms interact only with surface oxygen atoms to form hydroxyl groups. For the dissociation reaction, according to transition searching, H2O→H (ads)+OH (ads). The energy barriers were endothermic by 9.7 and 17.3 kJ· mol-1 for the (111) surfaces and exothermic by-59.9 and-47.6 kJ·mol-1 for the (110) surfaces.