Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to Oxalate
The strong binding energy of CO on iron surfaces has rendered Fe electrodes as poor electrochemical CO2 reduction (eCO2R) catalysts, predominantly producing hydrogen. Recent studies on tuning the microenvironment near the catalyst surfaces by tuning the local electric field in nonaqueous environment...
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Wiley-VCH
2025-07-01
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| Series: | ChemElectroChem |
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| Online Access: | https://doi.org/10.1002/celc.202500093 |
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| author | Rohan Sartape Rohit Chauhan Venkata S. R. P. Yadavalli Ishita Goyal Ishaku Amos Yancun Qi Vamsi V. Gande Abdul M. Sarkar Ksenija D. Glusac Meenesh R. Singh |
| author_facet | Rohan Sartape Rohit Chauhan Venkata S. R. P. Yadavalli Ishita Goyal Ishaku Amos Yancun Qi Vamsi V. Gande Abdul M. Sarkar Ksenija D. Glusac Meenesh R. Singh |
| author_sort | Rohan Sartape |
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| description | The strong binding energy of CO on iron surfaces has rendered Fe electrodes as poor electrochemical CO2 reduction (eCO2R) catalysts, predominantly producing hydrogen. Recent studies on tuning the microenvironment near the catalyst surfaces by tuning the local electric field in nonaqueous environments have been shown to promote eCO2R by facilitating the CO2 activation step. Herein, the use of tetraethylammonium (TEA) cation to tune the electric field on Fe surfaces, such that it leads to the formation of industrially relevant oxalates (C2 products), is reported. At optimal cation concentrations, the developed eCO2R system achieves 25 mA cm−2 of current density and Faradaic Efficiencies up to 75% toward oxalate. Furthermore, in situ attenuated total reflectance Fourier transform infrared spectroscopy indicates the presence of surface‐adsorbed TEA cations and other species on the Fe surfaces, leading to the well‐known outer‐sphere mechanism of electron transfer during eCO2R. The employment of Fe, along with microenvironment tuning, not only demonstrates high catalytic performance but also provides a safer and more sustainable alternative to toxic catalysts such as Pb that dominate the nonaqueous eCO2R literature. These findings pave the way for further optimization and scale‐up of the process, offering a viable route for sustainable chemical production and CO2 mitigation. |
| format | Article |
| id | doaj-art-8d9b6a274dcb4ff4a92a476ff2c4c8b2 |
| institution | Kabale University |
| issn | 2196-0216 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley-VCH |
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| series | ChemElectroChem |
| spelling | doaj-art-8d9b6a274dcb4ff4a92a476ff2c4c8b22025-08-20T03:32:19ZengWiley-VCHChemElectroChem2196-02162025-07-011215n/an/a10.1002/celc.202500093Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to OxalateRohan Sartape0Rohit Chauhan1Venkata S. R. P. Yadavalli2Ishita Goyal3Ishaku Amos4Yancun Qi5Vamsi V. Gande6Abdul M. Sarkar7Ksenija D. Glusac8Meenesh R. Singh9Department of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemistry University of Illinois Chicago 845 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemistry University of Illinois Chicago 845 W. Taylor St. Chicago Illinois 60607 USADepartment of Chemical Engineering University of Illinois Chicago 929 W. Taylor St. Chicago Illinois 60607 USAThe strong binding energy of CO on iron surfaces has rendered Fe electrodes as poor electrochemical CO2 reduction (eCO2R) catalysts, predominantly producing hydrogen. Recent studies on tuning the microenvironment near the catalyst surfaces by tuning the local electric field in nonaqueous environments have been shown to promote eCO2R by facilitating the CO2 activation step. Herein, the use of tetraethylammonium (TEA) cation to tune the electric field on Fe surfaces, such that it leads to the formation of industrially relevant oxalates (C2 products), is reported. At optimal cation concentrations, the developed eCO2R system achieves 25 mA cm−2 of current density and Faradaic Efficiencies up to 75% toward oxalate. Furthermore, in situ attenuated total reflectance Fourier transform infrared spectroscopy indicates the presence of surface‐adsorbed TEA cations and other species on the Fe surfaces, leading to the well‐known outer‐sphere mechanism of electron transfer during eCO2R. The employment of Fe, along with microenvironment tuning, not only demonstrates high catalytic performance but also provides a safer and more sustainable alternative to toxic catalysts such as Pb that dominate the nonaqueous eCO2R literature. These findings pave the way for further optimization and scale‐up of the process, offering a viable route for sustainable chemical production and CO2 mitigation.https://doi.org/10.1002/celc.202500093carboxylic acidC‐C couplingCCUSCO2 reductionelectrocatalysismicroenvironment engineering |
| spellingShingle | Rohan Sartape Rohit Chauhan Venkata S. R. P. Yadavalli Ishita Goyal Ishaku Amos Yancun Qi Vamsi V. Gande Abdul M. Sarkar Ksenija D. Glusac Meenesh R. Singh Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to Oxalate ChemElectroChem carboxylic acid C‐C coupling CCUS CO2 reduction electrocatalysis microenvironment engineering |
| title | Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to Oxalate |
| title_full | Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to Oxalate |
| title_fullStr | Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to Oxalate |
| title_full_unstemmed | Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to Oxalate |
| title_short | Tetraethylammonium Cation Activates Fe for Selective Electroreduction of CO2 to Oxalate |
| title_sort | tetraethylammonium cation activates fe for selective electroreduction of co2 to oxalate |
| topic | carboxylic acid C‐C coupling CCUS CO2 reduction electrocatalysis microenvironment engineering |
| url | https://doi.org/10.1002/celc.202500093 |
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