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Catalyst Aggregation Matters for Immobilized Molecular CO 2 RR Electrocatalysts
Here, we detail how the catalytic behavior of immobilized molecular electrocatalysts for the CO reduction reaction (CO RR) can be impacted by catalyst aggregation. Raman spectroscopy was used to study the CO RR mediated by a layer of cobalt phthalocyanine (CoPc) immobilized on the cathode of an elec...
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| Published in: | Journal of the American Chemical Society 2023-03, Vol.145 (8), p.4414-4420 |
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| Main Authors: | , , , , , , , , , , |
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| Language: | English |
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| cites | cdi_FETCH-LOGICAL-c1032-c394ffee1b7e0f93e0c730e4c30324e97f99f1e06738f8730b0e257262da43333 |
| container_end_page | 4420 |
| container_issue | 8 |
| container_start_page | 4414 |
| container_title | Journal of the American Chemical Society |
| container_volume | 145 |
| creator | Ren, Shaoxuan Lees, Eric W Hunt, Camden Jewlal, Andrew Kim, Yongwook Zhang, Zishuai Mowbray, Benjamin A W Fink, Arthur G Melo, Luke Grant, Edward R Berlinguette, Curtis P |
| description | Here, we detail how the catalytic behavior of immobilized molecular electrocatalysts for the CO
reduction reaction (CO
RR) can be impacted by catalyst aggregation.
Raman spectroscopy was used to study the CO
RR mediated by a layer of cobalt phthalocyanine (CoPc) immobilized on the cathode of an electrochemical flow reactor. We demonstrate that during electrolysis, the oxidation state of CoPc in the catalyst layer is dependent upon the degree of catalyst aggregation. Our data indicate that immobilized molecular catalysts must be dispersed on conductive supports to mitigate the formation of aggregates and produce meaningful performance data. We leveraged insights from this mechanistic study to engineer an improved CO-forming immobilized molecular catalyst─cobalt octaethoxyphthalocyanine (EtO
-CoPc)─that exhibited high selectivity (FE
≥ 95%), high partial current density (
≥ 300 mA/cm
), and high durability (ΔFE
< 0.1%/h at 150 mA/cm
) in a flow cell. This work demonstrates how to accurately identify CO
RR active species of molecular catalysts using
Raman spectroscopy and how to use this information to implement improved molecular electrocatalysts into flow cells. This work also shows that the active site of CoPc during CO
RR catalysis in a flow cell is the metal center. |
| doi_str_mv | 10.1021/jacs.2c08380 |
| format | article |
| fullrecord | <record><control><sourceid>pubmed_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1021_jacs_2c08380</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>36799452</sourcerecordid><originalsourceid>FETCH-LOGICAL-c1032-c394ffee1b7e0f93e0c730e4c30324e97f99f1e06738f8730b0e257262da43333</originalsourceid><addsrcrecordid>eNo9kLFOwzAQhi0EoqGwMSM_AClnO4njsYpaqNQqUgVz5DjnKFVCKjsdytOTqoFbTnf_p3_4CHlmsGDA2dtBG7_gBlKRwg0JWMwhjBlPbkkAADyUaSJm5MH7w3hGPGX3ZCYSqVQU84DkmR50e_YDXda1w1oPTf9Nd3oY0Hlqe0c3XdeXTdv8YEV3fYvm1GpHs5xyut_T1fgYXG-mFv9I7qxuPT5Ne06-1qvP7CPc5u-bbLkNDQPBQyNUZC0iKyWCVQLBSAEYGTGmESpplbIMIZEitekYlYA8ljzhlY7EOHPyeu01rvfeoS2Orum0OxcMiouX4uKlmLyM-MsVP57KDqt_-E-E-AUt713z</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Catalyst Aggregation Matters for Immobilized Molecular CO 2 RR Electrocatalysts</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)</source><creator>Ren, Shaoxuan ; Lees, Eric W ; Hunt, Camden ; Jewlal, Andrew ; Kim, Yongwook ; Zhang, Zishuai ; Mowbray, Benjamin A W ; Fink, Arthur G ; Melo, Luke ; Grant, Edward R ; Berlinguette, Curtis P</creator><creatorcontrib>Ren, Shaoxuan ; Lees, Eric W ; Hunt, Camden ; Jewlal, Andrew ; Kim, Yongwook ; Zhang, Zishuai ; Mowbray, Benjamin A W ; Fink, Arthur G ; Melo, Luke ; Grant, Edward R ; Berlinguette, Curtis P</creatorcontrib><description>Here, we detail how the catalytic behavior of immobilized molecular electrocatalysts for the CO
reduction reaction (CO
RR) can be impacted by catalyst aggregation.
Raman spectroscopy was used to study the CO
RR mediated by a layer of cobalt phthalocyanine (CoPc) immobilized on the cathode of an electrochemical flow reactor. We demonstrate that during electrolysis, the oxidation state of CoPc in the catalyst layer is dependent upon the degree of catalyst aggregation. Our data indicate that immobilized molecular catalysts must be dispersed on conductive supports to mitigate the formation of aggregates and produce meaningful performance data. We leveraged insights from this mechanistic study to engineer an improved CO-forming immobilized molecular catalyst─cobalt octaethoxyphthalocyanine (EtO
-CoPc)─that exhibited high selectivity (FE
≥ 95%), high partial current density (
≥ 300 mA/cm
), and high durability (ΔFE
< 0.1%/h at 150 mA/cm
) in a flow cell. This work demonstrates how to accurately identify CO
RR active species of molecular catalysts using
Raman spectroscopy and how to use this information to implement improved molecular electrocatalysts into flow cells. This work also shows that the active site of CoPc during CO
RR catalysis in a flow cell is the metal center.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.2c08380</identifier><identifier>PMID: 36799452</identifier><language>eng</language><publisher>United States</publisher><ispartof>Journal of the American Chemical Society, 2023-03, Vol.145 (8), p.4414-4420</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1032-c394ffee1b7e0f93e0c730e4c30324e97f99f1e06738f8730b0e257262da43333</citedby><cites>FETCH-LOGICAL-c1032-c394ffee1b7e0f93e0c730e4c30324e97f99f1e06738f8730b0e257262da43333</cites><orcidid>0000-0002-2381-4379 ; 0000-0001-5264-2644 ; 0000-0001-6875-849X ; 0000-0001-9452-2931 ; 0000-0003-4875-7558</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,783,787,27936,27937</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36799452$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Ren, Shaoxuan</creatorcontrib><creatorcontrib>Lees, Eric W</creatorcontrib><creatorcontrib>Hunt, Camden</creatorcontrib><creatorcontrib>Jewlal, Andrew</creatorcontrib><creatorcontrib>Kim, Yongwook</creatorcontrib><creatorcontrib>Zhang, Zishuai</creatorcontrib><creatorcontrib>Mowbray, Benjamin A W</creatorcontrib><creatorcontrib>Fink, Arthur G</creatorcontrib><creatorcontrib>Melo, Luke</creatorcontrib><creatorcontrib>Grant, Edward R</creatorcontrib><creatorcontrib>Berlinguette, Curtis P</creatorcontrib><title>Catalyst Aggregation Matters for Immobilized Molecular CO 2 RR Electrocatalysts</title><title>Journal of the American Chemical Society</title><addtitle>J Am Chem Soc</addtitle><description>Here, we detail how the catalytic behavior of immobilized molecular electrocatalysts for the CO
reduction reaction (CO
RR) can be impacted by catalyst aggregation.
Raman spectroscopy was used to study the CO
RR mediated by a layer of cobalt phthalocyanine (CoPc) immobilized on the cathode of an electrochemical flow reactor. We demonstrate that during electrolysis, the oxidation state of CoPc in the catalyst layer is dependent upon the degree of catalyst aggregation. Our data indicate that immobilized molecular catalysts must be dispersed on conductive supports to mitigate the formation of aggregates and produce meaningful performance data. We leveraged insights from this mechanistic study to engineer an improved CO-forming immobilized molecular catalyst─cobalt octaethoxyphthalocyanine (EtO
-CoPc)─that exhibited high selectivity (FE
≥ 95%), high partial current density (
≥ 300 mA/cm
), and high durability (ΔFE
< 0.1%/h at 150 mA/cm
) in a flow cell. This work demonstrates how to accurately identify CO
RR active species of molecular catalysts using
Raman spectroscopy and how to use this information to implement improved molecular electrocatalysts into flow cells. This work also shows that the active site of CoPc during CO
RR catalysis in a flow cell is the metal center.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNo9kLFOwzAQhi0EoqGwMSM_AClnO4njsYpaqNQqUgVz5DjnKFVCKjsdytOTqoFbTnf_p3_4CHlmsGDA2dtBG7_gBlKRwg0JWMwhjBlPbkkAADyUaSJm5MH7w3hGPGX3ZCYSqVQU84DkmR50e_YDXda1w1oPTf9Nd3oY0Hlqe0c3XdeXTdv8YEV3fYvm1GpHs5xyut_T1fgYXG-mFv9I7qxuPT5Ne06-1qvP7CPc5u-bbLkNDQPBQyNUZC0iKyWCVQLBSAEYGTGmESpplbIMIZEitekYlYA8ljzhlY7EOHPyeu01rvfeoS2Orum0OxcMiouX4uKlmLyM-MsVP57KDqt_-E-E-AUt713z</recordid><startdate>20230301</startdate><enddate>20230301</enddate><creator>Ren, Shaoxuan</creator><creator>Lees, Eric W</creator><creator>Hunt, Camden</creator><creator>Jewlal, Andrew</creator><creator>Kim, Yongwook</creator><creator>Zhang, Zishuai</creator><creator>Mowbray, Benjamin A W</creator><creator>Fink, Arthur G</creator><creator>Melo, Luke</creator><creator>Grant, Edward R</creator><creator>Berlinguette, Curtis P</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-2381-4379</orcidid><orcidid>https://orcid.org/0000-0001-5264-2644</orcidid><orcidid>https://orcid.org/0000-0001-6875-849X</orcidid><orcidid>https://orcid.org/0000-0001-9452-2931</orcidid><orcidid>https://orcid.org/0000-0003-4875-7558</orcidid></search><sort><creationdate>20230301</creationdate><title>Catalyst Aggregation Matters for Immobilized Molecular CO 2 RR Electrocatalysts</title><author>Ren, Shaoxuan ; Lees, Eric W ; Hunt, Camden ; Jewlal, Andrew ; Kim, Yongwook ; Zhang, Zishuai ; Mowbray, Benjamin A W ; Fink, Arthur G ; Melo, Luke ; Grant, Edward R ; Berlinguette, Curtis P</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1032-c394ffee1b7e0f93e0c730e4c30324e97f99f1e06738f8730b0e257262da43333</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ren, Shaoxuan</creatorcontrib><creatorcontrib>Lees, Eric W</creatorcontrib><creatorcontrib>Hunt, Camden</creatorcontrib><creatorcontrib>Jewlal, Andrew</creatorcontrib><creatorcontrib>Kim, Yongwook</creatorcontrib><creatorcontrib>Zhang, Zishuai</creatorcontrib><creatorcontrib>Mowbray, Benjamin A W</creatorcontrib><creatorcontrib>Fink, Arthur G</creatorcontrib><creatorcontrib>Melo, Luke</creatorcontrib><creatorcontrib>Grant, Edward R</creatorcontrib><creatorcontrib>Berlinguette, Curtis P</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ren, Shaoxuan</au><au>Lees, Eric W</au><au>Hunt, Camden</au><au>Jewlal, Andrew</au><au>Kim, Yongwook</au><au>Zhang, Zishuai</au><au>Mowbray, Benjamin A W</au><au>Fink, Arthur G</au><au>Melo, Luke</au><au>Grant, Edward R</au><au>Berlinguette, Curtis P</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Catalyst Aggregation Matters for Immobilized Molecular CO 2 RR Electrocatalysts</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J Am Chem Soc</addtitle><date>2023-03-01</date><risdate>2023</risdate><volume>145</volume><issue>8</issue><spage>4414</spage><epage>4420</epage><pages>4414-4420</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Here, we detail how the catalytic behavior of immobilized molecular electrocatalysts for the CO
reduction reaction (CO
RR) can be impacted by catalyst aggregation.
Raman spectroscopy was used to study the CO
RR mediated by a layer of cobalt phthalocyanine (CoPc) immobilized on the cathode of an electrochemical flow reactor. We demonstrate that during electrolysis, the oxidation state of CoPc in the catalyst layer is dependent upon the degree of catalyst aggregation. Our data indicate that immobilized molecular catalysts must be dispersed on conductive supports to mitigate the formation of aggregates and produce meaningful performance data. We leveraged insights from this mechanistic study to engineer an improved CO-forming immobilized molecular catalyst─cobalt octaethoxyphthalocyanine (EtO
-CoPc)─that exhibited high selectivity (FE
≥ 95%), high partial current density (
≥ 300 mA/cm
), and high durability (ΔFE
< 0.1%/h at 150 mA/cm
) in a flow cell. This work demonstrates how to accurately identify CO
RR active species of molecular catalysts using
Raman spectroscopy and how to use this information to implement improved molecular electrocatalysts into flow cells. This work also shows that the active site of CoPc during CO
RR catalysis in a flow cell is the metal center.</abstract><cop>United States</cop><pmid>36799452</pmid><doi>10.1021/jacs.2c08380</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-2381-4379</orcidid><orcidid>https://orcid.org/0000-0001-5264-2644</orcidid><orcidid>https://orcid.org/0000-0001-6875-849X</orcidid><orcidid>https://orcid.org/0000-0001-9452-2931</orcidid><orcidid>https://orcid.org/0000-0003-4875-7558</orcidid></addata></record> |
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| recordid | cdi_crossref_primary_10_1021_jacs_2c08380 |
| source | American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list) |
| title | Catalyst Aggregation Matters for Immobilized Molecular CO 2 RR Electrocatalysts |
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