Lin Rui, Wan Jiawei, Xiong Yu, Wu Konglin, Cheong Weng-Chon, Zhou Gang, Wang Dingsheng, Peng Qing, Chen Chen, Li Yadong
Department of Chemistry , Tsinghua University , Beijing 100084 , China.
Institute of Process Engineering , Chinese Academy of Sciences , Beijing 100084 , China.
J Am Chem Soc. 2018 Jul 25;140(29):9078-9082. doi: 10.1021/jacs.8b05293. Epub 2018 Jul 11.
Photocatalysts with different morphologies and specific exposed facets usually exhibit distinguished activities. Previous researches have focused on revealing the essence of the facet effect in photocatalysis; however, quantitative analyses on the differences of carrier dynamic between different facets are scarce. Herein, we successfully synthesized WO nanosheets and nanowires with dominant exposed facets of {001} and {110}, respectively. The lower hole effective mass on {110} (0.94 m) than on {001} (1.28 m) calculated by density functional theory leads to the higher hole mobility on {110} (4.92 cm V s) than on {001} (3.14 cm V s). Combined with the Einstein equation and the lifetime of the hole, the calculated hole diffusion length on {110} (74.8 nm) is larger than on {001} (53.4 nm). Overall, the lower hole effective mass, higher hole mobility, and greater hole diffusion length on {110} collectively result in a photocatalytic activity on benzyl alcohol oxidation 2.46 times as high as that on {001}.
具有不同形态和特定暴露晶面的光催化剂通常表现出不同的活性。以往的研究主要集中在揭示光催化中晶面效应的本质;然而,对不同晶面间载流子动力学差异的定量分析却很少。在此,我们成功合成了分别以{001}和{110}为主暴露晶面的WO纳米片和纳米线。通过密度泛函理论计算得出,{110}面上的空穴有效质量(0.94 m)低于{001}面上的空穴有效质量(1.28 m),这导致{110}面上的空穴迁移率(4.92 cm² V⁻¹ s⁻¹)高于{001}面上的空穴迁移率(3.14 cm² V⁻¹ s⁻¹)。结合爱因斯坦方程和空穴寿命,计算得出{110}面上的空穴扩散长度(74.8 nm)大于{001}面上的空穴扩散长度(53.4 nm)。总体而言,{110}面上较低的空穴有效质量、较高的空穴迁移率和较大的空穴扩散长度共同导致其对苯甲醇氧化的光催化活性是{001}面的2.46倍。