CO2-H2O co-electrolysis to CO/O2 for safe oxidative double carbonylation of ethylene/acetylene

doi:10.1016/S1872-2067(25)64739-5

Chinese Journal of Catalysis ›› 2025, Vol. 74: 202-210.DOI: 10.1016/S1872-2067(25)64739-5

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CO₂-H₂O co-electrolysis to CO/O₂ for safe oxidative double carbonylation of ethylene/acetylene

Yanwei Cao^a^,¹, Yunhao Qu^b^,^d^,¹, Bin Su^c^,¹, Gongwei Wang^b^,^d^,^*(), Yang Huang^a, Zhenmin Luo^c^,^*(), Lin Zhuang^b^,^d^,^*(), Lin He^a^,^*()

^aState Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
^bThe Institute for Advanced Studies, Wuhan University, Wuhan 430072, Hubei, China
^cSchool of Safety Science & Engineering, Xi’an University of Science and Technology, Xi’an 710054, Shaanxi, China
^bCollege of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, Hubei, China

Received:2025-02-17 Accepted:2025-03-17 Online:2025-07-18 Published:2025-07-20
Contact: *E-mail: wwang@whu.edu.cn (G. Wang), zmluo@xust.edu.cn (Z. Luo), lzhuang@whu.edu.cn (L. Zhuang), helin@licp.cas.cn (L. He).
About author:¹Contributed equally to this work.
Supported by:
Strategic Priority Research Program of the Chinese Academy of Sciences(XDC0180202);National Key Research and Development Program of Ministry of Science and Technology(2022YFA1504602);National Natural Science Foundation of China(U22B20137);National Natural Science Foundation of China(22302214);National Natural Science Foundation of China(22202222);National Natural Science Foundation of China(21972152);National Natural Science Foundation of China(21991154);National Natural Science Foundation of China(52304252);National Natural Science Foundation of China(52174200);National Natural Science Foundation of China(21991150);National Natural Science Foundation of China(22172115);Major Science and Technology Projects in Gansu Province(22ZD6GA003);Major Science and Technology Projects in Gansu Province(23ZDFA016);Gansu Province Basic Innovation Group(24JRRA043);LICP Cooperation Foundation for Young Scholars(LHJJ-20240103);Xiaomi Young Talents Program

Abstract

Abstract:

Upgrading carbon dioxide (CO₂) into value-added bulk chemicals offers a dual-benefit strategy for the carbon neutrality and circular carbon economy. Herein, we develop an integrated CO₂ valorization strategy that synergizes CO₂-H₂O co-electrolysis (producing CO/O₂ feeds) with oxidative double carbonylation of ethylene/acetylene to synthesize CO₂-derived C4 diesters (dimethyl succinate, fumarate, and maleate). A group of versatile building blocks for manufacturing plasticizers, biodegradable polymers, and pharmaceutical intermediates. Remarkably, CO₂ exhibits dual functionality: serving simultaneously as a CO/O₂ source and an explosion suppressant during the oxidative carbonylation process. We systematically investigated the explosion-suppressing efficacy of CO₂ in flammable gas mixtures (CO/O₂, C₂H₄/CO/O₂, and C₂H₂/CO/O₂) across varying concentrations. Notably, the mixed gas stream from CO₂/H₂O co-electrolysis at an industrial-scale current densities of 400 mA/cm², enabling direct utilization in oxidative double carbonylation reactions with exceptional compatibility and inherent safety. Extended applications were demonstrated through substrate scope expansion and gram-scale synthesis. This study establishes not only a safe protocol for oxidative carbonylation processes, but also opens an innovative pathway for sustainable CO₂ valorization, including CO surrogate and explosion suppressant.

Key words: Carbon dioxide, Electrolysis, Explosion suppressant, Double Carbonylation, Explosion limits, Ethylene, Acetylene

Yanwei Cao, Yunhao Qu, Bin Su, Gongwei Wang, Yang Huang, Zhenmin Luo, Lin Zhuang, Lin He. CO₂-H₂O co-electrolysis to CO/O₂ for safe oxidative double carbonylation of ethylene/acetylene[J]. Chinese Journal of Catalysis, 2025, 74: 202-210.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64739-5

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Figures/Tables 5

Scheme 1. CO2/H2O co-electrolysis for the safe oxidative double carbonylation of ethylene/acetylene.

Fig. 1. (a) Gaseous product Faradaic efficiency (FE) and full-cell voltage of the MEA electrolyzer for the CO2/pure water co-electrolysis. CO partial current density (b) and CO production energy efficiency (c) as a function of the applied current density. The gray open circles indicate representative results in the literature (Details in Table S1). (d) Gaseous product (CO, and O2) volume concentration and full-cell voltage in a prolonged test.

Fig. 2. Relationship between CO2 content and characteristic parameters of explosion pressure. (a) Simplified diagram of experiment device. (b) Photograph of 20 L spherical explosion test. (c) The maximum explosion pressure of CO2/CO/O2 mixture. (d) The maximum explosion pressure of C2H4/CO2/CO/O2 mixture. (e) The maximum explosion pressure of C2H2/CO2/CO/O2 mixture. Pentagram in figure: the content of CO2 in our oxidative double carbonylation reaction.

Fig. 3. Coupling CO2 electrolyzer with oxidative double carbonylation. (a) Schematic illustration of the CO2 to C4 oxygenates pathway. (b) Oxidative double carbonylation of ethylene. Reaction conditions: 0.1 MPa of ethylene (~1 mmol) and 1.0 MPa of outlet gas, Pd(acac)2 5 mol%, CuCl 10 mol%, 3 mL methanol, 40 °C 24 h; control groups: simulated gas, 0.1 MPa of ethylene (~1 mmol) and 0.3 MPa of simulated gas without CO2 or CO2/H2, Pd(acac)2 5 mol%, CuCl 10 mol%, methanol 3 mL, 40 °C. (c) Oxidative carbonylation of acetylene. Reaction conditions: 0.1 MPa of acetylene (~1 mmol) and 1.0 MPa of outlet gas, PdI2 (0.01 mmol), KI (0.1 mmol), 2 mL of MeOH and 3 mL of THF, 40 °C, 24 h; control groups: simulated gas, 0.1 MPa of acetylene (~1 mmol) and 0.3 MPa of simulated gas without CO2 or CO2/H2, PdI2 (0.01 mmol), KI (0.1 mmol), 2 mL of MeOH and 3 mL of THF, 40 °C, 24 h.

Fig. 4. Further extended applications. (a) The substrates scopes of olefins. Reaction conditions: alkenes (1 mmol) and 1.0 MPa of outlet gas, Pd(acac)2 5 mol%, CuCl 10 mol%, methanol 3 mL, 40 °C, 72 h. (b) Gram scale preparation of dimethyl fumarate and dimethyl maleate mixture. Reaction conditions: 0.3 MPa of acetylene (~0.9 g) and ~2 MPa of outlet gas, PdI2 (0.05 mmol), KI (0.5 mmol), 20 mL of MeOH and 30 mL of THF, 40 °C, 48 h.

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CO₂-H₂O co-electrolysis to CO/O₂ for safe oxidative double carbonylation of ethylene/acetylene

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