CAJ | 학술논문

采用密度泛函理论广义梯度近似平面波赝势法结合周期平板模型，研究 F-离子在γ-Al2O3(110)非极性表面的吸附行为，分析了 F-离子在其表面不同吸附位以及不同覆盖度下吸附构型和电子特性。结果表明：表面配位不饱和的 Al 为 F-离子活性吸附位，F-离子在γ-Al2O3(110)表面化学吸附后形成 F-Al 键促使 F-离子活化；F-离子在 AlI I(1)桥位吸附时最稳定。随着覆盖度增加，吸附能增大，F-离子与表层原子的距离(dF--surf)缩短；同时表面吸附F-离子引起表层及次表层原子层间距发生不同程度偏移，最大幅度为10.07%。差分电荷密度与电子态密度分析指出，F-离子在γ-Al2O3(110)表面吸附主要是由F-离子2s和2p轨道与γ-Al2O3基底Al的3p轨道相互作用所致。
채용밀도범함이론엄의제도근사평면파안세법결합주기평판모형，연구 F-리자재γ-Al2O3(110)비겁성표면적흡부행위，분석료 F-리자재기표면불동흡부위이급불동복개도하흡부구형화전자특성。결과표명：표면배위불포화적 Al 위 F-리자활성흡부위，F-리자재γ-Al2O3(110)표면화학흡부후형성 F-Al 건촉사 F-리자활화；F-리자재 AlI I(1)교위흡부시최은정。수착복개도증가，흡부능증대，F-리자여표층원자적거리(dF--surf)축단；동시표면흡부F-리자인기표층급차표층원자층간거발생불동정도편이，최대폭도위10.07%。차분전하밀도여전자태밀도분석지출，F-리자재γ-Al2O3(110)표면흡부주요시유F-리자2s화2p궤도여γ-Al2O3기저Al적3p궤도상호작용소치。
The adsorption of F- anion onγ-Al2O3(110) non-polar surface has been studied with periodic slab model by PW91 approach of GGA using density functional theory (DFT). The adsorption configurations and electronic property for F- anion onγ-Al2O3(110) surface at various adsorption sites and different coverages were analyzed. The calculated results indicate that the F- anions tend to adsorb on the unsaturated coordination Al atoms at the furface. Strong chemisorption occurs, and F-Al structures form when F- anions adsorb on the furface. Under these conditions, the F- anions are activated and may have possibility to participate in next step chemical reaction. The bridge site of AlII(1) where F- anion adsorbed onγ-Al2O3(110) surface is energetically stable. Moreover, the adsorption energy decreases with the increasing of coverage, while the vertical separation between adsored F- and the surface layer atoms shortens. Meanwhile, the F- anions adsorption leads to the different degrees of skewing of the space between the surface and subsurface atom layer, the biggest one reach up to 10.07 %. Charge density difference and density of states indicated that the adsorption behavior is dominated by the interaction between the 2s, 2p orbit of F- anion and the 3p orbit of the base metal Al on the surface.