Electrocatalysts based on oxygen vacancy-induced frustrated Lewis pairs for selective electrooxidation of ethylene glycol to formic acid

doi:10.1016/S1872-2067(26)65200-X

Abstract

Abstract:

The sluggish oxygen evolution reaction (OER) limits alkaline water electrolysis efficiency, and replacing OER with ethylene glycol oxidation reaction (EGOR) is a promising strategy to reduce energy consumption while producing value-added chemicals. EGOR for formate/formic acid (FA) requires overcoming C-C bond breakage barriers, achievable via constructing frustrated Lewis pairs (FLPs) and tuning electron distribution. Herein, a series of layered double hydroxide (LDH) electrocatalysts were fabricated via hydrothermal-assisted self-etching assembly using Co/Ni foam as substrates. Ni-doped CoNiFe-LDH/CoFoam exhibited excellent EGOR performance, with a low onset potential, 1.37 V vs. RHE at 100 mA cm^-2, and 88% Faradaic efficiency (FE) for FA. The in-situ characterizations showed Co sites lower onset potential, while Ni doping modulates electronic structure and induces oxygen vacancies (O_v). The theoretical calculations confirmed O_v forms surface FLPs, facilitating C-C bond cleavage and enhancing activity/selectivity. Notably, the catalyst performs well in polyethylene terephthalate (PET) degradation, enabling simultaneous plastic valorization and low-energy hydrogen production, providing insights for designing high-performance electrocatalysts for sustainable energy and environmental applications.

Key words: Ethylene glycol oxidation, Layered double hydroxide, Electrocatalysis, Defect engineering, Frustrated Lewis pairs, Plastic waste valorization

Xuanrui Yang, Wenxuan Huang, Jianhua Shen, Chunzhong Li, Yihua Zhu. Electrocatalysts based on oxygen vacancy-induced frustrated Lewis pairs for selective electrooxidation of ethylene glycol to formic acid[J]. Chinese Journal of Catalysis, 2026, 91: 315-326.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65200-X

https://www.cjcatal.com/EN/Y2026/V91/I12/315

Figures/Tables 6

Fig. 1. Morphological and elemental characterization of CoNiFe-LDH/CoFoam. SEM image (a), TEM image (b), HRTEM image (c), HAADF-STEM image (d), SAED pattern (e), and elemental mapping images (f-i).

Fig. 2. XRD patterns (a) and smoothed XRD patterns (b) of CoFe-LDH/CoFoam and CoNiFe-LDH/CoFoam. High-resolution XPS spectra of Ni 2p (c), Co 2p (d), Fe 2p (e), and O 1s (f) for CoFe-LDH/CoFoam and CoNiFe-LDH/CoFoam.

Fig. 3. Comprehensive electrocatalytic performance and analysis of different samples. (a) SCV polarization curves for EGOR and OER of each sample. (b) Tafel plots for EGOR. (c) Tafel plots for OER. (d) Cdl of each sample. (e) ECSA-normalized SCV curves for EGOR. (f) Nyquist plots at 1.36 V vs. RHE for all samples. (g) FE distribution of CoNiFe-LDH/CoFoam at different current densities. (h) Chronopotentiometric stability test of CoNiFe-LDH/CoFoam at 100 mA cm-2.

Fig. 4. (a,b) Forward and reverse LSV curves of the samples in OER system at a scan rate of 2 mV s-1 without iR compensation. (c) In-situ Raman spectra of CoNiFe-LDH/CoFoam in OER and EGOR systems. (d,e) Forward and reverse LSV curves of the samples in EGOR system at a scan rate of 2 mV s-1 without iR compensation.

Fig. 5. (a) Schematic diagram of the activated process. Operando EIS of CoNiFe-LDH/CoFoam under EGOR (b) and OER (c) conditions. (d,e) In-situ ATR-SEIRAS spectra of CoNiFe-LDH/CoFoam during EGOR in 1 mol L-1 KOH + 0.1 mol L-1 EG.

Fig. 6. Bader charge analysis of CoFe(Ov)-LDH (a) and CoNiFe(Ov)-LDH (b). (c) Gibbs free energy profile of the EGOR pathway. (d) The TS calculation of the C-C bond breaking process from *CHOCHO to *CHO*CHO on the surface of different catalysts.

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