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Vol. 15 (2023)

Optimized Electronic Modification of S-Doped CuO Induced by Oxidative Reconstruction for Coupling Glycerol Electrooxidation with Hydrogen Evolution

https://doi.org/10.1007/s40820-023-01159-6
Ruo‑Yao Fan
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Xue‑Jun Zhai
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Wei‑Zhen Qiao
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Yu‑Sheng Zhang
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Ning Yu
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Na Xu
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Qian‑Xi Lv
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Yong‑Ming Chai
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Bin Dong
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China

Corresponding Author: Bin Dong

dongbin@upc.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 190

Abstract

Glycerol (electrochemical) oxidation reaction (GOR) producing organic small molecule acid and coupling with hydrogen evolution reaction is a critical aspect of ensuring balanced glycerol capacity and promoting hydrogen generation on a large scale. However, the development of highly efficient and selective non-noble metal-based GOR electrocatalysts is still a key problem. Here, an S-doped CuO nanorod array catalyst (S-CuO/CF) constructed by sulfur leaching and oxidative remodeling is used to drive GOR at low potentials: It requires potentials of only 1.23 and 1.33 V versus RHE to provide currents of 100 and 500 mA cm−2, respectively. Moreover, it shows satisfactory comprehensive performance (at 100 mA cm−2, Vcell = 1.37 V) when assembled as the anode in asymmetric coupled electrolytic cell. Furthermore, we propose a detailed cycle reaction pathway (in alkaline environment) of S-doped CuO surface promoting GOR to produce formic acid and glycolic acid. Among them, the C–C bond breaking and lattice oxygen deintercalation steps frequently involved in the reaction pathway are the key factors to determine the catalytic performance and product selectivity. This research provides valuable guidance for the development of transition metal-based electrocatalysts for GOR and valuable insights into the glycerol oxidation cycle reaction pathway.


Highlights:
1 S-doped CuO nanorod arrays (S-CuO/CF) constructed by sulfur leaching and oxidative remodeling strategy require only 1.23 and 1.33 V versus hydrogen evolution reaction (HER) to provide glycerol oxidation currents of 100 and 500 mA cm−2.
2 S-CuO/CF shows satisfactory performance (at 100 mA cm−2, Vcell = 1.37 V) assembled as the anode in asymmetric coupled electrolytic cell of glycerol oxidation reaction and HER.
3 The study identifies the key factors involved in the GOR reaction pathway, which include the C–C bond breaking and lattice oxygen deintercalation steps.

Keywords

Glycerol oxidation reaction (GOR) Hydrogen evolution reaction (HER) CuO Oxidative reconstruction Electronic modification
Fan, Ruo‑Yao, Xue‑Jun Zhai, Wei‑Zhen Qiao, Yu‑Sheng Zhang, Ning Yu, Na Xu, Qian‑Xi Lv, Yong‑Ming Chai, and Bin Dong. 2023. “Optimized Electronic Modification of S-Doped CuO Induced by Oxidative Reconstruction for Coupling Glycerol Electrooxidation With Hydrogen Evolution”. Nano-Micro Letters 15 (July):190. https://doi.org/10.1007/s40820-023-01159-6.
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