Unraveling the potential-dependent structure evolution in CuO for electrocatalytic biomass valorization

Ye Wang; Ming Xu; Xi Wang; Ruixiang Ge; Yu-Quan Zhu; An-Zhen Li; Hua Zhou; Fengen Chen; Lirong Zheng; Haohong Duan

doi:10.1016/j.scib.2023.09.033

Unraveling the potential-dependent structure evolution in CuO for electrocatalytic biomass valorization

Sci Bull (Beijing). 2023 Dec 15;68(23):2982-2992. doi: 10.1016/j.scib.2023.09.033. Epub 2023 Sep 25.

Authors

Ye Wang¹, Ming Xu², Xi Wang³, Ruixiang Ge¹, Yu-Quan Zhu², An-Zhen Li⁴, Hua Zhou⁵, Fengen Chen¹, Lirong Zheng⁶, Haohong Duan⁷

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing 100084, China.
² State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
³ Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
⁴ Department of Chemistry, Tsinghua University, Beijing 100084, China; Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
⁵ Department of Chemistry, Tsinghua University, Beijing 100084, China; State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
⁶ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
⁷ Department of Chemistry, Tsinghua University, Beijing 100084, China; Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China. Electronic address: hhduan@mail.tsinghua.edu.cn.

PMID: 37798176
DOI: 10.1016/j.scib.2023.09.033

Abstract

Electrocatalytic oxidation of renewable biomass (such as glucose) into high-value-added chemicals provides an effective approach to achieving carbon neutrality. CuO-derived materials are among the most promising electrocatalysts for biomass electrooxidation, but the identification of their active sites under electrochemical conditions remains elusive. Herein, we report a potential-dependent structure evolution over CuO in the glucose oxidation reaction (GOR). Through systematic electrochemical and spectroscopic characterizations, we unveil that CuO undergoes Cu²⁺/Cu⁺ and Cu³⁺/Cu²⁺ redox processes at increased potentials with successive generation of Cu(OH)₂ and CuOOH as the active phases. In addition, these two structures have distinct activities in the GOR, with Cu(OH)₂ being favorable for aldehyde oxidation, and CuOOH showed faster kinetics in carbon-carbon cleavage and alcohol/aldehyde oxidation. This work deepens our understanding of the dynamic reconstruction of Cu-based catalysts under electrochemical conditions and may guide rational material design for biomass valorization.

Keywords: Biomass upcycling; Copper oxide; Electrocatalysis; Glucose electrooxidation; Potential dependency.