Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties

Fernández-Villanueva, Estefanía; Pérez-Bailac, Patricia; Lustemberg, Pablo G.; Hungría, Ana B.; Pascual, Laura; Cataluña, Renato; Vidal-Moya, J.A.; Blasco, Teresa; Ganduglia-Pirovano, M. V.; Martínez Arias, Arturo

Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties

Understanding how oxide nanomorphology directs metal–support interactions is key to designing selective, low-cost catalysts. The preferential oxidation of CO (CO-PROX) is vital for purifying H<inf>2</inf>streams for fuel cell applications, as even trace amounts of CO strongly poison the...

Descripción completa

Detalles Bibliográficos
Autores:	Fernández-Villanueva, Estefanía, Pérez-Bailac, Patricia, Lustemberg, Pablo G., Hungría, Ana B., Pascual, Laura, Cataluña, Renato, Vidal-Moya, J.A., Blasco, Teresa, Ganduglia-Pirovano, M. V., Martínez Arias, Arturo
Tipo de recurso:	artículo
Estado:	Versión publicada
Fecha de publicación:	2025
País:	España
Institución:	Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:	DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:	oai:digital.csic.es:10261/413997
Acceso en línea:	http://hdl.handle.net/10261/413997 https://www.scopus.com/inward/record.uri?eid=2-s2.0-105022798273&doi=10.1021%2Facscatal.5c06552&partnerID=40&md5=d3f812ae2dd8cd3fb99ffe8f438a6c9e
Access Level:	acceso abierto
Palabra clave:	carbonyls infrared CO-PROX Cu/CeO2catalysts DFT electron microscopy hydrogen

id	ES_6604b8408e2e02da4cf9668e08f22285
oai_identifier_str	oai:digital.csic.es:10261/413997
network_acronym_str	ES
network_name_str	España
repository_id_str
dc.title.none.fl_str_mv	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties
title	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties
spellingShingle	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties Fernández-Villanueva, Estefanía carbonyls infrared CO-PROX Cu/CeO2catalysts DFT electron microscopy hydrogen
title_short	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties
title_full	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties
title_fullStr	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties
title_full_unstemmed	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties
title_sort	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties
dc.creator.none.fl_str_mv	Fernández-Villanueva, Estefanía Pérez-Bailac, Patricia Lustemberg, Pablo G. Hungría, Ana B. Pascual, Laura Cataluña, Renato Vidal-Moya, J.A. Blasco, Teresa Ganduglia-Pirovano, M. V. Martínez Arias, Arturo
author	Fernández-Villanueva, Estefanía
author_facet	Fernández-Villanueva, Estefanía Pérez-Bailac, Patricia Lustemberg, Pablo G. Hungría, Ana B. Pascual, Laura Cataluña, Renato Vidal-Moya, J.A. Blasco, Teresa Ganduglia-Pirovano, M. V. Martínez Arias, Arturo
author_role	author
author2	Pérez-Bailac, Patricia Lustemberg, Pablo G. Hungría, Ana B. Pascual, Laura Cataluña, Renato Vidal-Moya, J.A. Blasco, Teresa Ganduglia-Pirovano, M. V. Martínez Arias, Arturo
author2_role	author author author author author author author author author
dc.contributor.none.fl_str_mv	Consejo Superior de Investigaciones Científicas (España) Agencia Estatal de Investigación (España) Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv	carbonyls infrared CO-PROX Cu/CeO2catalysts DFT electron microscopy hydrogen
topic	carbonyls infrared CO-PROX Cu/CeO2catalysts DFT electron microscopy hydrogen
description	Understanding how oxide nanomorphology directs metal–support interactions is key to designing selective, low-cost catalysts. The preferential oxidation of CO (CO-PROX) is vital for purifying H<inf>2</inf>streams for fuel cell applications, as even trace amounts of CO strongly poison the electrode catalysts. Cu/CeO<inf>2</inf>systems provide a cost-effective alternative to noble metals, yet the influence of ceria morphology on the performance remains unclear. Here, we compare low-loaded Cu catalysts supported on CeO<inf>2</inf>nanospheres and nanocubes. Although distinct in shape, electron microscopy, low-temperature CO adsorption infrared spectroscopy, and DFT calculations reveal surface reconstructions in nanocubes that diminish structural differences between the two supports. Nevertheless, the Cu/nanosphere catalyst shows higher CO oxidation activity, while the Cu/nanocube catalyst offers superior CO<inf>2</inf>selectivity and a broader full-conversion temperature window. In situ DRIFTS and DFT spectra attribute these contrasts to stronger CO adsorption sites in the nanocube system. Copper speciation and the nature of surface carbonyls were resolved through complementary techniques, including STEM-HAADF imaging, XEDS mapping, EPR, and CO adsorption IR spectroscopy, together with DFT. These results demonstrate that subtle variations in ceria morphology steer interfacial chemistry and reaction pathways, providing design principles for next-generation Cu-based catalysts for CO-PROX and related oxidation reactions. © 2025 The Authors. Published by American Chemical Society
publishDate	2025
dc.date.none.fl_str_mv	2025 2026 2026
dc.type.none.fl_str_mv	info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion
format	article
status_str	publishedVersion
dc.identifier.none.fl_str_mv	http://hdl.handle.net/10261/413997 https://www.scopus.com/inward/record.uri?eid=2-s2.0-105022798273&doi=10.1021%2Facscatal.5c06552&partnerID=40&md5=d3f812ae2dd8cd3fb99ffe8f438a6c9e
url	http://hdl.handle.net/10261/413997 https://www.scopus.com/inward/record.uri?eid=2-s2.0-105022798273&doi=10.1021%2Facscatal.5c06552&partnerID=40&md5=d3f812ae2dd8cd3fb99ffe8f438a6c9e
dc.language.none.fl_str_mv	Inglés
language_invalid_str_mv	Inglés
dc.relation.none.fl_str_mv	#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# MMT-24-ICP-01 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-128915NB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-142312NB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2024-162810NB-I00 ACS Catalysis https://doi.org/10.1021/acscatal.5c06552 Sí
dc.rights.none.fl_str_mv	info:eu-repo/semantics/openAccess
eu_rights_str_mv	openAccess
dc.publisher.none.fl_str_mv	American Chemical Society
publisher.none.fl_str_mv	American Chemical Society
dc.source.none.fl_str_mv	reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str	Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str	DIGITAL.CSIC. Repositorio Institucional del CSIC
collection	DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_	1869409785401573376
spelling	Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX PropertiesFernández-Villanueva, EstefaníaPérez-Bailac, PatriciaLustemberg, Pablo G.Hungría, Ana B.Pascual, LauraCataluña, RenatoVidal-Moya, J.A.Blasco, TeresaGanduglia-Pirovano, M. V.Martínez Arias, Arturocarbonyls infraredCO-PROXCu/CeO2catalystsDFTelectron microscopyhydrogenUnderstanding how oxide nanomorphology directs metal–support interactions is key to designing selective, low-cost catalysts. The preferential oxidation of CO (CO-PROX) is vital for purifying H<inf>2</inf>streams for fuel cell applications, as even trace amounts of CO strongly poison the electrode catalysts. Cu/CeO<inf>2</inf>systems provide a cost-effective alternative to noble metals, yet the influence of ceria morphology on the performance remains unclear. Here, we compare low-loaded Cu catalysts supported on CeO<inf>2</inf>nanospheres and nanocubes. Although distinct in shape, electron microscopy, low-temperature CO adsorption infrared spectroscopy, and DFT calculations reveal surface reconstructions in nanocubes that diminish structural differences between the two supports. Nevertheless, the Cu/nanosphere catalyst shows higher CO oxidation activity, while the Cu/nanocube catalyst offers superior CO<inf>2</inf>selectivity and a broader full-conversion temperature window. In situ DRIFTS and DFT spectra attribute these contrasts to stronger CO adsorption sites in the nanocube system. Copper speciation and the nature of surface carbonyls were resolved through complementary techniques, including STEM-HAADF imaging, XEDS mapping, EPR, and CO adsorption IR spectroscopy, together with DFT. These results demonstrate that subtle variations in ceria morphology steer interfacial chemistry and reaction pathways, providing design principles for next-generation Cu-based catalysts for CO-PROX and related oxidation reactions. © 2025 The Authors. Published by American Chemical SocietyE.F.V. acknowledges support from the Margarita Salas postdoctoral fellowship (Spanish MIU and European Union─NextGenerationEU) and the MOMENTUM Program (MMT-24-ICP-01, Plan de Recuperación, Transformación y Resiliencia─European Union─NextGenerationEU). We gratefully acknowledge funding from projects PID2021-128915NB-I00, PID2022-142312NB-I00, and PID2024-162810NB-I00 financed by Ministerio de Ciencia, Innovación y Universidades, and ERDF, EU. Computational resources were provided by the Red Española de Supercomputación (RES) at MareNostrum 4 and 5 (BSC, Barcelona) as well as the Centro de Computación Científica at the Universidad Autónoma de Madrid (CCC-UAM). This research also benefited from access to the Galician Supercomputing Center (CESGA) infrastructure, including the FinisTerrae III supercomputer and its permanent data storage system, funded by the Spanish Ministerio de Ciencia, Innovación y Universidades, the Galician Government, and ERDF.Peer reviewedAmerican Chemical SocietyConsejo Superior de Investigaciones Científicas (España)Agencia Estatal de Investigación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202620262025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/413997https://www.scopus.com/inward/record.uri?eid=2-s2.0-105022798273&doi=10.1021%2Facscatal.5c06552&partnerID=40&md5=d3f812ae2dd8cd3fb99ffe8f438a6c9ereponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#MMT-24-ICP-01info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-128915NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-142312NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2024-162810NB-I00ACS Catalysishttps://doi.org/10.1021/acscatal.5c06552Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/4139972026-05-22T06:33:51Z
score	15,812429

Fine-Tuning Catalysts: The Role of Support Nanomorphology in Shaping Cu/CeO2CO-PROX Properties

Similares en LA Referencia