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Origin of the Activity Trend in the Oxidative Dehydrogenation of Ethanol over VOx/CeO2
Supported vanadia (VOx) is a versatile catalyst for various redox processes where ceria‐supported VOx have shown to be particularly active in the oxidative dehydrogenation (ODH) of alcohols. In this work, we clarify the origin of the volcano‐shaped ethanol ODH activity trend for VOx/CeOx catalysts u...
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Published in: | Angewandte Chemie 2023-04, Vol.135 (18), p.n/a |
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description | Supported vanadia (VOx) is a versatile catalyst for various redox processes where ceria‐supported VOx have shown to be particularly active in the oxidative dehydrogenation (ODH) of alcohols. In this work, we clarify the origin of the volcano‐shaped ethanol ODH activity trend for VOx/CeOx catalysts using operando quick V K‐ and Ce L3‐ edge XAS experiments performed under transient conditions. We quantitatively demonstrate that both vanadium and cerium are synergistically involved in alcohol ODH. The concentration of reversible Ce4+/Ce3+ species was identified as the main descriptor of the alcohol ODH activity. The activity drop in the volcano plot, observed at above ca. 3 V nm−2 surface loading (ca. 30 % of VOx monolayer coverage), is related to the formation of spectator V4+ and Ce3+ species, which were identified here for the first time. These results might prove to be helpful for the rational optimization of VOx/CeO2 catalysts and the refinement of the theoretical models.
Using operando time‐resolved X‐ray absorption spectroscopy, we investigated the origin of the volcano‐shaped activity trend in the oxidative dehydrogenation of ethanol over VOx/CeO2 catalysts as a function of VOx surface coverage. Vanadium and cerium synergistically change their oxidation states during the catalytic cycle. The catalytic activity correlates with the concentration of reversible Ce4+/3+ species. |
doi_str_mv | 10.1002/ange.202301297 |
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Using operando time‐resolved X‐ray absorption spectroscopy, we investigated the origin of the volcano‐shaped activity trend in the oxidative dehydrogenation of ethanol over VOx/CeO2 catalysts as a function of VOx surface coverage. Vanadium and cerium synergistically change their oxidation states during the catalytic cycle. The catalytic activity correlates with the concentration of reversible Ce4+/3+ species.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.202301297</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Alcohols ; Catalysts ; Cerium ; Cerium oxides ; Chemistry ; Dehydrogenation ; Ethanol ; Heterogeneous Catalysis ; Optimization ; Oxidative Dehydrogenation ; Reaction Mechanisms ; Supported Catalysts ; Vanadium ; X-Ray Absorption Spectroscopy</subject><ispartof>Angewandte Chemie, 2023-04, Vol.135 (18), p.n/a</ispartof><rights>2023 The Authors. Angewandte Chemie published by Wiley-VCH GmbH</rights><rights>2023. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0002-6772-1414 ; 0000-0003-1549-4771 ; 0000-0002-5478-9639 ; 0000-0003-0572-5214 ; 0000-0003-1895-9626 ; 0000-0003-2351-0751 ; 0000-0002-7268-7257</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Zabilska, Anna</creatorcontrib><creatorcontrib>Zabilskiy, Maxim</creatorcontrib><creatorcontrib>Nuguid, Rob Jeremiah G.</creatorcontrib><creatorcontrib>Clark, Adam H.</creatorcontrib><creatorcontrib>Sadykov, Ilia I.</creatorcontrib><creatorcontrib>Nachtegaal, Maarten</creatorcontrib><creatorcontrib>Kröcher, Oliver</creatorcontrib><creatorcontrib>Safonova, Olga V.</creatorcontrib><title>Origin of the Activity Trend in the Oxidative Dehydrogenation of Ethanol over VOx/CeO2</title><title>Angewandte Chemie</title><description>Supported vanadia (VOx) is a versatile catalyst for various redox processes where ceria‐supported VOx have shown to be particularly active in the oxidative dehydrogenation (ODH) of alcohols. In this work, we clarify the origin of the volcano‐shaped ethanol ODH activity trend for VOx/CeOx catalysts using operando quick V K‐ and Ce L3‐ edge XAS experiments performed under transient conditions. We quantitatively demonstrate that both vanadium and cerium are synergistically involved in alcohol ODH. The concentration of reversible Ce4+/Ce3+ species was identified as the main descriptor of the alcohol ODH activity. The activity drop in the volcano plot, observed at above ca. 3 V nm−2 surface loading (ca. 30 % of VOx monolayer coverage), is related to the formation of spectator V4+ and Ce3+ species, which were identified here for the first time. These results might prove to be helpful for the rational optimization of VOx/CeO2 catalysts and the refinement of the theoretical models.
Using operando time‐resolved X‐ray absorption spectroscopy, we investigated the origin of the volcano‐shaped activity trend in the oxidative dehydrogenation of ethanol over VOx/CeO2 catalysts as a function of VOx surface coverage. Vanadium and cerium synergistically change their oxidation states during the catalytic cycle. The catalytic activity correlates with the concentration of reversible Ce4+/3+ species.</description><subject>Alcohols</subject><subject>Catalysts</subject><subject>Cerium</subject><subject>Cerium oxides</subject><subject>Chemistry</subject><subject>Dehydrogenation</subject><subject>Ethanol</subject><subject>Heterogeneous Catalysis</subject><subject>Optimization</subject><subject>Oxidative Dehydrogenation</subject><subject>Reaction Mechanisms</subject><subject>Supported Catalysts</subject><subject>Vanadium</subject><subject>X-Ray Absorption Spectroscopy</subject><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><recordid>eNo9kMFPwjAUxhujiYhePTfxPHjtunY9EkQ0Ie6CXJtuvMIIrtgNZP89Qwynl-9933tf8iPkmcGAAfChrVY44MBjYFyrG9JjCWdRrBJ1S3oAQkQpF_qePNT1BgAkV7pHFlkoV2VFvaPNGumoaMpD2bR0HrBa0s44b7NjubSdgfQV1-0y-BVWnfZ_Z5NmbSu_pf6AgS6y43CMGX8kd85ua3z6n33y9TaZj9-jWTb9GI9m0Y6xVEUqVQx0kdpE5C5HJzG2OkclsZDKIRa2UJBazcHmUmi0InG54i4XmgvHVdwnL5e_u-B_9lg3ZuP3oeoqDU-BQcykTLqUvqR-yy22ZhfKbxtaw8CcwZkzOHMFZ0af08lVxSc68WQX</recordid><startdate>20230424</startdate><enddate>20230424</enddate><creator>Zabilska, Anna</creator><creator>Zabilskiy, Maxim</creator><creator>Nuguid, Rob Jeremiah G.</creator><creator>Clark, Adam H.</creator><creator>Sadykov, Ilia I.</creator><creator>Nachtegaal, Maarten</creator><creator>Kröcher, Oliver</creator><creator>Safonova, Olga V.</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0002-6772-1414</orcidid><orcidid>https://orcid.org/0000-0003-1549-4771</orcidid><orcidid>https://orcid.org/0000-0002-5478-9639</orcidid><orcidid>https://orcid.org/0000-0003-0572-5214</orcidid><orcidid>https://orcid.org/0000-0003-1895-9626</orcidid><orcidid>https://orcid.org/0000-0003-2351-0751</orcidid><orcidid>https://orcid.org/0000-0002-7268-7257</orcidid></search><sort><creationdate>20230424</creationdate><title>Origin of the Activity Trend in the Oxidative Dehydrogenation of Ethanol over VOx/CeO2</title><author>Zabilska, Anna ; Zabilskiy, Maxim ; Nuguid, Rob Jeremiah G. ; Clark, Adam H. ; Sadykov, Ilia I. ; Nachtegaal, Maarten ; Kröcher, Oliver ; Safonova, Olga V.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p1187-787109c8a54bfbef6e3a9be76ec67feecac708a920ab649ea45fb72fb4924f273</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Alcohols</topic><topic>Catalysts</topic><topic>Cerium</topic><topic>Cerium oxides</topic><topic>Chemistry</topic><topic>Dehydrogenation</topic><topic>Ethanol</topic><topic>Heterogeneous Catalysis</topic><topic>Optimization</topic><topic>Oxidative Dehydrogenation</topic><topic>Reaction Mechanisms</topic><topic>Supported Catalysts</topic><topic>Vanadium</topic><topic>X-Ray Absorption Spectroscopy</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zabilska, Anna</creatorcontrib><creatorcontrib>Zabilskiy, Maxim</creatorcontrib><creatorcontrib>Nuguid, Rob Jeremiah G.</creatorcontrib><creatorcontrib>Clark, Adam H.</creatorcontrib><creatorcontrib>Sadykov, Ilia I.</creatorcontrib><creatorcontrib>Nachtegaal, Maarten</creatorcontrib><creatorcontrib>Kröcher, Oliver</creatorcontrib><creatorcontrib>Safonova, Olga V.</creatorcontrib><collection>Wiley Open Access</collection><collection>Wiley Online Library</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Angewandte Chemie</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zabilska, Anna</au><au>Zabilskiy, Maxim</au><au>Nuguid, Rob Jeremiah G.</au><au>Clark, Adam H.</au><au>Sadykov, Ilia I.</au><au>Nachtegaal, Maarten</au><au>Kröcher, Oliver</au><au>Safonova, Olga V.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Origin of the Activity Trend in the Oxidative Dehydrogenation of Ethanol over VOx/CeO2</atitle><jtitle>Angewandte Chemie</jtitle><date>2023-04-24</date><risdate>2023</risdate><volume>135</volume><issue>18</issue><epage>n/a</epage><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>Supported vanadia (VOx) is a versatile catalyst for various redox processes where ceria‐supported VOx have shown to be particularly active in the oxidative dehydrogenation (ODH) of alcohols. In this work, we clarify the origin of the volcano‐shaped ethanol ODH activity trend for VOx/CeOx catalysts using operando quick V K‐ and Ce L3‐ edge XAS experiments performed under transient conditions. We quantitatively demonstrate that both vanadium and cerium are synergistically involved in alcohol ODH. The concentration of reversible Ce4+/Ce3+ species was identified as the main descriptor of the alcohol ODH activity. The activity drop in the volcano plot, observed at above ca. 3 V nm−2 surface loading (ca. 30 % of VOx monolayer coverage), is related to the formation of spectator V4+ and Ce3+ species, which were identified here for the first time. These results might prove to be helpful for the rational optimization of VOx/CeO2 catalysts and the refinement of the theoretical models.
Using operando time‐resolved X‐ray absorption spectroscopy, we investigated the origin of the volcano‐shaped activity trend in the oxidative dehydrogenation of ethanol over VOx/CeO2 catalysts as a function of VOx surface coverage. Vanadium and cerium synergistically change their oxidation states during the catalytic cycle. The catalytic activity correlates with the concentration of reversible Ce4+/3+ species.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ange.202301297</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-6772-1414</orcidid><orcidid>https://orcid.org/0000-0003-1549-4771</orcidid><orcidid>https://orcid.org/0000-0002-5478-9639</orcidid><orcidid>https://orcid.org/0000-0003-0572-5214</orcidid><orcidid>https://orcid.org/0000-0003-1895-9626</orcidid><orcidid>https://orcid.org/0000-0003-2351-0751</orcidid><orcidid>https://orcid.org/0000-0002-7268-7257</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Alcohols Catalysts Cerium Cerium oxides Chemistry Dehydrogenation Ethanol Heterogeneous Catalysis Optimization Oxidative Dehydrogenation Reaction Mechanisms Supported Catalysts Vanadium X-Ray Absorption Spectroscopy |
title | Origin of the Activity Trend in the Oxidative Dehydrogenation of Ethanol over VOx/CeO2 |
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