氧空位构筑受阻路易斯酸碱对催化剂用于乙二醇电氧化制甲酸

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

催化学报 ›› 2026, Vol. 91: 315-326.DOI: 10.1016/S1872-2067(26)65200-X

氧空位构筑受阻路易斯酸碱对催化剂用于乙二醇电氧化制甲酸

杨烜睿, 黄文轩, 沈建华^*(), 李春忠^*(), 朱以华^*()

华东理工大学材料科学与工程学院, 上海多级结构纳米材料工程技术研究中心, 超细材料制备与应用教育部重点实验室, 上海 200237

收稿日期:2025-12-09 接受日期:2026-02-21 出版日期:2026-12-18 发布日期:2026-10-13
通讯作者: ^*电子信箱: jianhuashen@ecust.edu.cn (沈建华),
czli@ecust.edu.cn (李春忠),
基金资助:
国家自然科学基金(U22B20143);国家自然科学基金(22178106);国家自然科学基金(22278136);上海市科学技术委员会(23ZR1416400);上海市科学技术委员会(22dz1205900);上海市高等学校特聘教授(东方学者)项目;中央高校基础研究基金(222201718002)

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

Xuanrui Yang, Wenxuan Huang, Jianhua Shen^*(), Chunzhong Li^*(), Yihua Zhu^*()

Shanghai Engineering Research Centre of Hierarchical Nanomaterials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2025-12-09 Accepted:2026-02-21 Online:2026-12-18 Published:2026-10-13
Supported by:
National Natural Science Foundation of China(U22B20143);National Natural Science Foundation of China(22178106);National Natural Science Foundation of China(22278136);Science and Technolo-gy Commission of Shanghai Municipality(23ZR1416400);Science and Technolo-gy Commission of Shanghai Municipality(22dz1205900);Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutes of High Learning;Fundamental Research Funds for the Central Universities(222201718002)

摘要/Abstract

摘要：

碱性电解水技术是绿氢制备的核心路径之一, 但阳极析氧反应(OER)动力学迟缓、能耗高, 严重限制了其规模化应用. 为突破该瓶颈, 开发低能耗且兼具高附加值产物生成的替代阳极反应极具研究意义. 乙二醇氧化反应(EGOR)因理论电位低于OER, 且可定向转化为甲酸盐/甲酸(FA)等重要化工原料, 成为极具潜力的替代阳极方案. 然而, EGOR中C-C键的高效断裂是实现高选择性生成FA的关键挑战, 亟需通过催化剂结构设计与电子调控构建高效反应路径.
本文提出一种水热辅助自蚀刻组装策略, 以钴/镍泡沫为三维导电基底, 原位生长系列层状双氢氧化物(LDH)电催化剂, 通过镍掺杂调控CoNiFe-LDH的组成与电子结构. 所制镍掺杂钴镍铁LDH/泡沫钴电极催化剂展现出卓越的EGOR催化性能: 起始电位显著低于传统贵金属催化剂, 在100 mA cm^-2的高电流密度下, 电位仅为1.37 V(vs. RHE), 且生成FA的法拉第效率(FE)稳定维持在88%, 循环使用50 h后性能无明显衰减, 表现出优异的活性与稳定性. 通过X-射线光电子能谱、原位拉曼光谱等表征技术结合密度泛函理论(DFT)计算, 系统揭示了催化机制: 催化剂中的钴位点为EGOR提供了低能垒的反应起始活性中心, 有效降低了反应的起始电位; 而镍元素的掺杂不仅重构了催化剂的电子结构, 还成功诱导了氧空位的形成. 氧空位与表面金属位点协同作用, 构建了受阻路易斯酸碱对(FLPs), 该结构能够精准吸附并活化乙二醇分子中的C-C键, 显著降低其断裂能垒, 从而同步提升催化活性与FA选择性. 此外, 该催化剂在聚对苯二甲酸乙二醇酯降解反应中表现出优异的兼容性, 可实现PET的电化学降解与乙二醇氧化、低能耗产氢的耦合过程, 在处理白色污染的同时完成资源回收与绿氢制备, 为可持续能源生产与环境治理的协同发展提供了创新技术路径.
综上, 本研究通过催化剂活性位的精准制备与DFT计算相结合, 系统性的揭示了氧空位与表面金属位点构建的FLPs与催化活性之间的关系, 为设计高活性、高选择性的EGOR电催化剂提供了新的思路, 也为碱性电解水技术的低能耗化与多功能化升级奠定了基础.

关键词: 乙二醇氧化, 层状双羟基氢氧化物, 电催化, 缺陷工程, 受阻路易斯酸碱对, 塑料废物增值利用

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

杨烜睿, 黄文轩, 沈建华, 李春忠, 朱以华. 氧空位构筑受阻路易斯酸碱对催化剂用于乙二醇电氧化制甲酸[J]. 催化学报, 2026, 91: 315-326.

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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图/表 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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氧空位构筑受阻路易斯酸碱对催化剂用于乙二醇电氧化制甲酸

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

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