Theoretical Study of Plasmon-Enhanced Surface Catalytic Coupling Reactions of Aromatic Amines and Nitro Compounds.
Taking advantage of the unique capacity of surface plasmon resonance, plasmon-enhanced heterogeneous catalysis has recently come into focus as a promising technique for high performance light-energy conversion. This work performs a theoretical study on the reaction mechanism for conversions of p-aminothiophenol (PATP) and p-nitrothiophenol (PNTP) to aromatic azo species, p,p'-dimercaptoazobenzene (DMAB). In the absence of O2 or H2, the plasmon-driven photocatalysis mechanism (hot electron-hole reactions) is the major reaction channel. In the presence of O2 or H2, the plasmon-assisted surface catalysis mechanism (activated oxygen/hydrogen reactions) is the major reaction channel. The present results show that the coupling reactions of PATP and PNTP strongly depend on the solution pH, the irradiation wavelength, the irradiation power, and the nature of metal substrates as well as the surrounding atmosphere. The present study has drawn a fundamental physical picture for understanding plasmon-enhanced heterogeneous catalysis.
†State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China.
Liu-Bin
LB
Zhao
†State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China.
Meng
M
Zhang
†State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China.
Yi-Fan
YF
Huang
‡Department of Chemical Engineering, University of South Carolina, Columbia, South Carolina 29208, United States.
Christopher T
CT
Williams
†State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China.
De-Yin
DY
Wu
†State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China.
Bin
B
Ren
†State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China.
Zhong-Qun
ZQ
Tian
catalysis; density functional theory; photochemistry; potential energy surface; surface plasmon resonance