High‐Rate and Selective CO2 Electrolysis to Ethylene via Metal–Organic‐Framework‐Augmented CO2 Availability

• Published in: Advanced materials (Weinheim) Vol. 34; no. 51; pp. e2207088 - n/a
• Main Authors: Nam, Dae‐Hyun, Shekhah, Osama, Ozden, Adnan, McCallum, Christopher, Li, Fengwang, Wang, Xue, Lum, Yanwei, Lee, Taemin, Li, Jun, Wicks, Joshua, Johnston, Andrew, Sinton, David, Eddaoudi, Mohamed, Sargent, Edward H.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.12.2022
• Subjects: Absorption spectroscopy; Aqueous electrolytes; Carbon dioxide; Carbon dioxide concentration; Carbon monoxide; Catalysts; Chemical reduction; Current density; electrochemical CO 2 reduction; Electrodes; Electrolysis; Electrolytic analysis; Electrolytic cells; Ethylene; ethylene production; Gaseous diffusion; gas‐diffusion electrodes; Materials science; Metal-organic frameworks; Polytetrafluoroethylene; reticular chemistry; Substrates
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202207088

High‐rate conversion of carbon dioxide (CO2) to ethylene (C2H4) in the CO2 reduction reaction (CO2RR) requires fine control over the phase boundary of the gas diffusion electrode (GDE) to overcome the limit of CO2 solubility in aqueous electrolytes. Here, a metal–organic framework (MOF)‐functionalized GDE design is presented, based on a catalysts:MOFs:hydrophobic substrate materials layered architecture, that leads to high‐rate and selective C2H4 production in flow cells and membrane electrode assembly (MEA) electrolyzers. It is found that using electroanalysis and operando X‐ray absorption spectroscopy (XAS), MOF‐induced organic layers in GDEs augment the local CO2 concentration near the active sites of the Cu catalysts. MOFs with different CO2 adsorption abilities are used, and the stacking ordering of MOFs in the GDE is varied. While sputtering Cu on poly(tetrafluoroethylene) (PTFE) (Cu/PTFE) exhibits 43% C2H4 Faradaic efficiency (FE) at a current density of 200 mA cm−2 in a flow cell, 49% C2H4 FE at 1 A cm−2 is achieved on MOF‐augmented GDEs in CO2RR. MOF‐augmented GDEs are further evaluated in an MEA electrolyzer, achieving a C2H4 partial current density of 220 mA cm−2 for CO2RR and 121 mA cm−2 for the carbon monoxide reduction reaction (CORR), representing 2.7‐fold and 15‐fold improvement in C2H4 production rate, compared to those obtained on bare Cu/PTFE. Efficient electrochemical carbon dioxide (CO2) conversion into value‐added chemicals requires gas diffusion electrode (GDE)‐based electrolyzers. For high‐rate ethylene (C2H4) production with *CO dimerization, a microenvironment with high CO2 availability near the active sites is essential. Metal–organic‐framework‐induced organic layers in the GDE enable augmentation of the local CO2 concentration and promotion of electrochemical CO2 reduction at high current densities.