Electrochemical Conversion of CO2 to Ethyl Formate in Ethanol

Electrochemical reduction of CO2 to valuable chemicals using renewable energy is a promising approach to economically incentivizing lower greenhouse gas emissions. CO2 electroreduction in ethanol is unprecedented despite ethanol being a sustainable and relatively safe solvent. Here, we demonstrate t...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:ACS sustainable chemistry & engineering 2024-01, Vol.12 (2), p.882-892
Hauptverfasser: Hofsommer, Dillon T., Zamborini, Isabella R., Uttarwar, Sandesh S., Phipps, Christine A., Gautam, Manu, Nkurunziza, Francois, Grapperhaus, Craig A., Spurgeon, Joshua M.
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 892
container_issue 2
container_start_page 882
container_title ACS sustainable chemistry & engineering
container_volume 12
creator Hofsommer, Dillon T.
Zamborini, Isabella R.
Uttarwar, Sandesh S.
Phipps, Christine A.
Gautam, Manu
Nkurunziza, Francois
Grapperhaus, Craig A.
Spurgeon, Joshua M.
description Electrochemical reduction of CO2 to valuable chemicals using renewable energy is a promising approach to economically incentivizing lower greenhouse gas emissions. CO2 electroreduction in ethanol is unprecedented despite ethanol being a sustainable and relatively safe solvent. Here, we demonstrate that electrochemical CO2 reduction in acidic ethanol on Pb and Sn cathodes can lead to the production of ethyl formate, a novel and valuable three-carbon ester product. Combining the production of formic acid in these solvents with an in situ acid-catalyzed Fischer esterification reaction leads to sustained ethyl formate production. The effects of pH, anolyte composition, current density, membrane hydration, and supporting electrolyte choice on ethyl formate synthesis were investigated. In particular, durable electrochemical performance was enabled using tetraethylammonium chloride supporting electrolyte in ethanol catholyte with an acidic aqueous anolyte at a selectivity for ethyl formate of 44% faradaic efficiency.
doi_str_mv 10.1021/acssuschemeng.3c05853
format Article
fullrecord <record><control><sourceid>acs</sourceid><recordid>TN_cdi_acs_journals_10_1021_acssuschemeng_3c05853</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>a70938914</sourcerecordid><originalsourceid>FETCH-LOGICAL-a197t-df65d85604b31b090bd2f4af1fe4ca83f19bec8c659bebb9e8bee5856bd7d5cf3</originalsourceid><addsrcrecordid>eNpVkM1qwzAQhEVpoSHNIxT0Ak61lqVIhx6KcdpCIJf2bPSzahwcCSyn0LevTXNo5jLDHmaZj5BHYGtgJTwZl_M5uwOeMH6tuWNCCX5DFiVIVbBKidt_-Z6scj6ySVrzUsGCPDc9unFIc0HnTE_rFL9xyF2KNAVa70s6JtqMh5-ebtNwMiPSLs4HE1P_QO6C6TOuLr4kn9vmo34rdvvX9_plVxjQm7HwQQqvhGSV5WCZZtaXoTIBAlbOKB5AW3TKSTG5tRqVRZx2SOs3XrjAlwT-eqe17TGdhzh9a4G1M4L2CkF7QcB_Ad0gVEI</addsrcrecordid><sourcetype>Publisher</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Electrochemical Conversion of CO2 to Ethyl Formate in Ethanol</title><source>ACS Publications</source><creator>Hofsommer, Dillon T. ; Zamborini, Isabella R. ; Uttarwar, Sandesh S. ; Phipps, Christine A. ; Gautam, Manu ; Nkurunziza, Francois ; Grapperhaus, Craig A. ; Spurgeon, Joshua M.</creator><creatorcontrib>Hofsommer, Dillon T. ; Zamborini, Isabella R. ; Uttarwar, Sandesh S. ; Phipps, Christine A. ; Gautam, Manu ; Nkurunziza, Francois ; Grapperhaus, Craig A. ; Spurgeon, Joshua M.</creatorcontrib><description>Electrochemical reduction of CO2 to valuable chemicals using renewable energy is a promising approach to economically incentivizing lower greenhouse gas emissions. CO2 electroreduction in ethanol is unprecedented despite ethanol being a sustainable and relatively safe solvent. Here, we demonstrate that electrochemical CO2 reduction in acidic ethanol on Pb and Sn cathodes can lead to the production of ethyl formate, a novel and valuable three-carbon ester product. Combining the production of formic acid in these solvents with an in situ acid-catalyzed Fischer esterification reaction leads to sustained ethyl formate production. The effects of pH, anolyte composition, current density, membrane hydration, and supporting electrolyte choice on ethyl formate synthesis were investigated. In particular, durable electrochemical performance was enabled using tetraethylammonium chloride supporting electrolyte in ethanol catholyte with an acidic aqueous anolyte at a selectivity for ethyl formate of 44% faradaic efficiency.</description><identifier>ISSN: 2168-0485</identifier><identifier>EISSN: 2168-0485</identifier><identifier>DOI: 10.1021/acssuschemeng.3c05853</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>ACS sustainable chemistry &amp; engineering, 2024-01, Vol.12 (2), p.882-892</ispartof><rights>2024 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0003-4924-7488 ; 0000-0001-8638-2465 ; 0000-0002-2061-4646 ; 0000-0002-2987-0865 ; 0000-0003-4889-2645</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acssuschemeng.3c05853$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acssuschemeng.3c05853$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,27074,27922,27923,56736,56786</link.rule.ids></links><search><creatorcontrib>Hofsommer, Dillon T.</creatorcontrib><creatorcontrib>Zamborini, Isabella R.</creatorcontrib><creatorcontrib>Uttarwar, Sandesh S.</creatorcontrib><creatorcontrib>Phipps, Christine A.</creatorcontrib><creatorcontrib>Gautam, Manu</creatorcontrib><creatorcontrib>Nkurunziza, Francois</creatorcontrib><creatorcontrib>Grapperhaus, Craig A.</creatorcontrib><creatorcontrib>Spurgeon, Joshua M.</creatorcontrib><title>Electrochemical Conversion of CO2 to Ethyl Formate in Ethanol</title><title>ACS sustainable chemistry &amp; engineering</title><addtitle>ACS Sustainable Chem. Eng</addtitle><description>Electrochemical reduction of CO2 to valuable chemicals using renewable energy is a promising approach to economically incentivizing lower greenhouse gas emissions. CO2 electroreduction in ethanol is unprecedented despite ethanol being a sustainable and relatively safe solvent. Here, we demonstrate that electrochemical CO2 reduction in acidic ethanol on Pb and Sn cathodes can lead to the production of ethyl formate, a novel and valuable three-carbon ester product. Combining the production of formic acid in these solvents with an in situ acid-catalyzed Fischer esterification reaction leads to sustained ethyl formate production. The effects of pH, anolyte composition, current density, membrane hydration, and supporting electrolyte choice on ethyl formate synthesis were investigated. In particular, durable electrochemical performance was enabled using tetraethylammonium chloride supporting electrolyte in ethanol catholyte with an acidic aqueous anolyte at a selectivity for ethyl formate of 44% faradaic efficiency.</description><issn>2168-0485</issn><issn>2168-0485</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNpVkM1qwzAQhEVpoSHNIxT0Ak61lqVIhx6KcdpCIJf2bPSzahwcCSyn0LevTXNo5jLDHmaZj5BHYGtgJTwZl_M5uwOeMH6tuWNCCX5DFiVIVbBKidt_-Z6scj6ySVrzUsGCPDc9unFIc0HnTE_rFL9xyF2KNAVa70s6JtqMh5-ebtNwMiPSLs4HE1P_QO6C6TOuLr4kn9vmo34rdvvX9_plVxjQm7HwQQqvhGSV5WCZZtaXoTIBAlbOKB5AW3TKSTG5tRqVRZx2SOs3XrjAlwT-eqe17TGdhzh9a4G1M4L2CkF7QcB_Ad0gVEI</recordid><startdate>20240115</startdate><enddate>20240115</enddate><creator>Hofsommer, Dillon T.</creator><creator>Zamborini, Isabella R.</creator><creator>Uttarwar, Sandesh S.</creator><creator>Phipps, Christine A.</creator><creator>Gautam, Manu</creator><creator>Nkurunziza, Francois</creator><creator>Grapperhaus, Craig A.</creator><creator>Spurgeon, Joshua M.</creator><general>American Chemical Society</general><scope/><orcidid>https://orcid.org/0000-0003-4924-7488</orcidid><orcidid>https://orcid.org/0000-0001-8638-2465</orcidid><orcidid>https://orcid.org/0000-0002-2061-4646</orcidid><orcidid>https://orcid.org/0000-0002-2987-0865</orcidid><orcidid>https://orcid.org/0000-0003-4889-2645</orcidid></search><sort><creationdate>20240115</creationdate><title>Electrochemical Conversion of CO2 to Ethyl Formate in Ethanol</title><author>Hofsommer, Dillon T. ; Zamborini, Isabella R. ; Uttarwar, Sandesh S. ; Phipps, Christine A. ; Gautam, Manu ; Nkurunziza, Francois ; Grapperhaus, Craig A. ; Spurgeon, Joshua M.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a197t-df65d85604b31b090bd2f4af1fe4ca83f19bec8c659bebb9e8bee5856bd7d5cf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hofsommer, Dillon T.</creatorcontrib><creatorcontrib>Zamborini, Isabella R.</creatorcontrib><creatorcontrib>Uttarwar, Sandesh S.</creatorcontrib><creatorcontrib>Phipps, Christine A.</creatorcontrib><creatorcontrib>Gautam, Manu</creatorcontrib><creatorcontrib>Nkurunziza, Francois</creatorcontrib><creatorcontrib>Grapperhaus, Craig A.</creatorcontrib><creatorcontrib>Spurgeon, Joshua M.</creatorcontrib><jtitle>ACS sustainable chemistry &amp; engineering</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hofsommer, Dillon T.</au><au>Zamborini, Isabella R.</au><au>Uttarwar, Sandesh S.</au><au>Phipps, Christine A.</au><au>Gautam, Manu</au><au>Nkurunziza, Francois</au><au>Grapperhaus, Craig A.</au><au>Spurgeon, Joshua M.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electrochemical Conversion of CO2 to Ethyl Formate in Ethanol</atitle><jtitle>ACS sustainable chemistry &amp; engineering</jtitle><addtitle>ACS Sustainable Chem. Eng</addtitle><date>2024-01-15</date><risdate>2024</risdate><volume>12</volume><issue>2</issue><spage>882</spage><epage>892</epage><pages>882-892</pages><issn>2168-0485</issn><eissn>2168-0485</eissn><abstract>Electrochemical reduction of CO2 to valuable chemicals using renewable energy is a promising approach to economically incentivizing lower greenhouse gas emissions. CO2 electroreduction in ethanol is unprecedented despite ethanol being a sustainable and relatively safe solvent. Here, we demonstrate that electrochemical CO2 reduction in acidic ethanol on Pb and Sn cathodes can lead to the production of ethyl formate, a novel and valuable three-carbon ester product. Combining the production of formic acid in these solvents with an in situ acid-catalyzed Fischer esterification reaction leads to sustained ethyl formate production. The effects of pH, anolyte composition, current density, membrane hydration, and supporting electrolyte choice on ethyl formate synthesis were investigated. In particular, durable electrochemical performance was enabled using tetraethylammonium chloride supporting electrolyte in ethanol catholyte with an acidic aqueous anolyte at a selectivity for ethyl formate of 44% faradaic efficiency.</abstract><pub>American Chemical Society</pub><doi>10.1021/acssuschemeng.3c05853</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0003-4924-7488</orcidid><orcidid>https://orcid.org/0000-0001-8638-2465</orcidid><orcidid>https://orcid.org/0000-0002-2061-4646</orcidid><orcidid>https://orcid.org/0000-0002-2987-0865</orcidid><orcidid>https://orcid.org/0000-0003-4889-2645</orcidid></addata></record>
fulltext fulltext
identifier ISSN: 2168-0485
ispartof ACS sustainable chemistry & engineering, 2024-01, Vol.12 (2), p.882-892
issn 2168-0485
2168-0485
language eng
recordid cdi_acs_journals_10_1021_acssuschemeng_3c05853
source ACS Publications
title Electrochemical Conversion of CO2 to Ethyl Formate in Ethanol
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-13T20%3A34%3A37IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Electrochemical%20Conversion%20of%20CO2%20to%20Ethyl%20Formate%20in%20Ethanol&rft.jtitle=ACS%20sustainable%20chemistry%20&%20engineering&rft.au=Hofsommer,%20Dillon%20T.&rft.date=2024-01-15&rft.volume=12&rft.issue=2&rft.spage=882&rft.epage=892&rft.pages=882-892&rft.issn=2168-0485&rft.eissn=2168-0485&rft_id=info:doi/10.1021/acssuschemeng.3c05853&rft_dat=%3Cacs%3Ea70938914%3C/acs%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true