Proton‐Coupled Electron Transfer on Cu2O/Ti3C2Tx MXene for Propane (C3H8) Synthesis from Electrochemical CO2 Reduction

• Published in: Advanced science 2024-10, Vol.11 (39), p.e2405154-n/a
• Main Authors: Kim, Jun Young, Hong, Won Tae, Phu, Thi Kim Cuong, Cho, Seong Chan, Kim, Byeongkyu, Baeck, Unbeom, Oh, Hyung‐Suk, Koh, Jai Hyun, Yu, Xu, Choi, Chang Hyuck, Park, Jongwook, Lee, Sang Uck, Chung, Chan‐Hwa, Kim, Jung Kyu
• Format: Article
• Language: English
• Subjects: C2‐C1 coupling; Carbon; electrochemical CO2 reduction; Electrolytes; Energy; Fourier transforms; Hydrocarbons; in‐situ ATR‐FTIR; Oxidation; propane production; proton‐coupled electron transfer
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.202405154

Electrochemical CO2 reduction reaction (CO2RR) to produce value‐added multi‐carbon chemicals has been an appealing approach to achieving environmentally friendly carbon neutrality in recent years. Despite extensive research focusing on the use of CO2 to produce high‐value chemicals like high‐energy‐density hydrocarbons, there have been few reports on the production of propane (C3H8), which requires carbon chain elongation and protonation. A rationally designed 0D/2D hybrid Cu2O anchored‐Ti3C2Tx MXene catalyst (Cu2O/MXene) is demonstrated with efficient CO2RR activity in an aqueous electrolyte to produce C3H8. As a result, a significantly high Faradaic efficiency (FE) of 3.3% is achieved for the synthesis of C3H8 via the CO2RR with Cu2O/MXene, which is ≈26 times higher than that of Cu/MXene prepared by the same hydrothermal process without NH4OH solution. Based on in‐situ attenuated total reflection‐Fourier transform infrared spectroscopy (ATR‐FTIR) and density functional theory (DFT) calculations, it is proposed that the significant electrocatalytic conversion originated from the synergistic behavior of the Cu2O nanoparticles, which bound the *C2 intermediates, and the MXene that bound the *CO coupling to the C3 intermediate. The results disclose that the rationally designed MXene‐based hybrid catalyst facilitates multi‐carbon coupling as well as protonation, thereby manipulating the CO2RR pathway. A rational design of Cu2O/Ti3C2Tx MXene catalyst presents an excellent activity for saturated hydrocarbon C3H8 from electrochemical CO2 reduction, providing *C2‐*C1 coupling sites and facilitating further protonation. Based on in‐situ attenuated total reflection‐Fourier transform infrared spectroscopy and density functional theory calculations, results offer insights into green electrochemical carbon utilization for achieving carbon neutrality as well as lowering global warming potential.