Enhancing Catalytic Activity and Selectivity by Plasmon-Induced Hot Carriers

Xiao-Qing Liu; Fei-Fei Meng; Xing Chen; Yu-Hang Li; Hao Yang; Feng Peng; Xi-Hong Lu; Ye-Xiang Tong; Zhong-Qun Tian; Jian-Feng Li; Ping-Ping Fang

doi:10.1016/j.isci.2020.101107

Enhancing Catalytic Activity and Selectivity by Plasmon-Induced Hot Carriers

iScience. 2020 May 22;23(5):101107. doi: 10.1016/j.isci.2020.101107. Epub 2020 Apr 27.

Authors

Affiliations

¹ MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, The Key Lab of Low-carbon Chem & Energy Conservation of Guangdong Province, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China.
² State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Xiamen University, Xiamen 361005, China.
³ Guangzhou Key Laboratory for New Energy and Green Catalysis, School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China.
⁴ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Xiamen University, Xiamen 361005, China. Electronic address: li@xmu.edu.cn.
⁵ MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, The Key Lab of Low-carbon Chem & Energy Conservation of Guangdong Province, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China. Electronic address: fangpp3@mail.sysu.edu.cn.

Abstract

Plasmon-assisted chemical transformation holds great potential for solar energy conversion. However, simultaneous enhancement of reactivity and selectivity is still challenging and the mechanism remains mysterious. Herein, we elucidate the localized surface plasmon resonance (LSPR)-induced principles underlying the enhanced activity (∼70%) and selectivity of photoelectrocatalytic redox of nitrobenzene (NB) on Au nanoparticles. Hot carriers selectively accelerate the conversion rate from NB to phenylhydroxylamine (PHA) by ∼14% but suppress the transformation rate from PHA to nitrosobenzene (NSB) by ∼13%. By adding an electron accepter, the as-observed suppression ratio is substantially enlarged up to 43%. Our experiments, supported by in situ surface-enhanced Raman spectroscopy and density functional theory simulations, reveal such particular hot-carrier-induced selectivity is conjointly contributed by the accelerated hot electron transfer and the corresponding residual hot holes. This work will help expand the applications of renewable sunlight in the directional production of value-added chemicals under mild conditions.

Keywords: Catalysis; Inorganic Chemistry; Materials Science.