噻吩在M(111)(M=Pd, Pt, Au)表面的吸附

引用本文: 施炜, 张连阳, 夏盛杰, 倪哲明. 噻吩在M(111)(M=Pd, Pt, Au)表面的吸附[J]. 物理化学学报, 2014, 30(12): 2249-2255. doi: 10.3866/PKU.WHXB201408283 shu

Citation: SHI Wei, ZHANG Lian-Yang, XIA Sheng-Jie, NI Zhe-Ming. Adsorption of Thiophene on M(111) (M=Pd, Pt, Au) Surfaces[J]. Acta Physico-Chimica Sinica, 2014, 30(12): 2249-2255. doi: 10.3866/PKU.WHXB201408283 shu

噻吩在M(111)(M=Pd, Pt, Au)表面的吸附

摘要:

采用密度泛函理论(DFT), 选取DMol³程序模块, 对噻吩在M(111) (M=Pd, Pt, Au)表面上的吸附行为进行了探讨. 通过对噻吩在不同底物金属上的吸附能、吸附构型、Mulliken 电荷布居、差分电荷密度以及态密度的分析发现, 噻吩在Pd(111)面上的吸附能最大, Pt(111)面次之, Au(111)面最小. 吸附后, 噻吩在Au(111)面上的构型几乎保持不变, 最终通过S端倾斜吸附于top 位; 噻吩在Pd(111)及Pt(111)面上发生了折叠与变形, 环中氢原子向上翘起, 最终通过环平面平行吸附于hollow 位. 此外, 噻吩环吸附后芳香性遭到了破坏, 环中碳原子发生sp³杂化, 同时电子逐渐由噻吩向M(111)面发生转移, M(111)面上的部分电子也反馈给了噻吩环中的空轨道, 这种协同作用最终导致了噻吩分子稳定吸附于M(111)面.

关键词:

Pd(111)面
/ Pt(111)面
/ Au(111)面
/ 噻吩
/ 吸附

English

Adsorption of Thiophene on M(111) (M=Pd, Pt, Au) Surfaces

1.
Laboratory of Advanced Catalytic Materials, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. China
Received Date: 01 July 2014
Available Online: 27 November 2014

Abstract:

The adsorption of thiophene on Pd(111), Pt(111), and Au(111) surfaces was investigated by periodic density functional theory (DFT) calculations at the GGA/PW91 level. The results showed that the adsorption energies of thiophene on the different surfaces following the order Pd(111)>Pt(111)>Au(111). The adsorption structure on the Au(111) surface showed almost no change, and the most stable adsorption structure was tilted adsorption on the top site through the S atom of thiophene. For the Pd(111) and Pt(111) surfaces, the most stable adsorption structure was parallel adsorption to the hollow site through the ring plane of thiophene. After adsorption, the H atom of thiophene moved upward and the structure of thiophene was distorted and folded. The aromaticity of thiophene was disrupted and the C atoms were characteristic of sp³ hybridization. Furthermore, the electrons of the M(111) surfaces and thiophene were redistributed after adsorption. The electron transfer from thiophene to the M(111) surfaces was in the order Pd(111)>Pt(111)>Au(111). The electrons of the M(111) surfaces were also back-denoted to the empty orbitals of the thiophene molecule. These processes eventually lead to the adsorption of thiophene on the M(111) surfaces.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

噻吩在M(111)(M=Pd, Pt, Au)表面的吸附

English

Adsorption of Thiophene on M(111) (M=Pd, Pt, Au) Surfaces

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中国化学会秘书处

噻吩在M(111)(M=Pd, Pt, Au)表面的吸附

English

Adsorption of Thiophene on M(111) (M=Pd, Pt, Au) Surfaces

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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