Oxygen-Bridged Long-Range Dual Sites Boost Ethanol Electrooxidation by Facilitating C-C Bond Cleavage

Yao Wang; Meng Zheng; Yunrui Li; Juan Chen; Jinyu Ye; Chenliang Ye; Shuna Li; Jin Wang; Yongfa Zhu; Shi-Gang Sun; Dingsheng Wang

doi:10.1021/acs.nanolett.3c02319

Oxygen-Bridged Long-Range Dual Sites Boost Ethanol Electrooxidation by Facilitating C-C Bond Cleavage

Nano Lett. 2023 Sep 13;23(17):8194-8202. doi: 10.1021/acs.nanolett.3c02319. Epub 2023 Aug 25.

Authors

Yao Wang¹, Meng Zheng², Yunrui Li³, Juan Chen⁴, Jinyu Ye⁵, Chenliang Ye², Shuna Li⁴, Jin Wang², Yongfa Zhu^{6

7}, Shi-Gang Sun⁵, Dingsheng Wang⁷

Affiliations

¹ Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, International Joint Research Center for Photoresponsive Molecules and Materials, Jiangnan University, Wuxi 214122, China.
² College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, China.
³ Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
⁴ State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering and Environment, China University of Petroleum, Beijing 102249, China.
⁵ State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
⁶ International Joint Research Center for Photoresponsive Molecules and Materials, Jiangnan University, Wuxi, Jiangsu 214122, China.
⁷ Department of Chemistry, Tsinghua University, Beijing 100084, China.

PMID: 37624651
DOI: 10.1021/acs.nanolett.3c02319

Abstract

Optimizing the interatomic distance of dual sites to realize C-C bond breaking of ethanol is critical for the commercialization of direct ethanol fuel cells. Herein, the concept of holding long-range dual sites is proposed to weaken the reaction barrier of C-C cleavage during the ethanol oxidation reaction (EOR). The obtained long-range Rh-O-Pt dual sites achieve a high current density of 7.43 mA/cm² toward EOR, which is 13.3 times that of Pt/C, as well as remarkable stability. Electrochemical in situ Fourier transform infrared spectroscopy indicates that long-range Rh-O-Pt dual sites can increase the selectivity of C1 products and suppress the generation of a CO intermediate. Theoretical calculations further disclose that redistribution of the surface-localized electron around Rh-O-Pt can promote direct oxidation of -OH, accelerating C-C bond cleavage. This work provides a promising strategy for designing oxygen-bridged long-range dual sites to tune the activity and selectivity of complicated catalytic reactions.

Keywords: C−C bond cleavage; Rh−O−Pt dual sites; ethanol oxidation; long-range interactions; oxygen bridge.