In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogen

In this work, key factors that affect catalytic activity of Ni/La-doped ceria catalysts for the reverse water gas shift reaction (RWGS) have been revealed by applying in situ advanced synchrotron techniques, such as X-ray Absorption Spectroscopy (XAS) and Near-ambient pressure X-ray Photoelectron sp...

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Main Authors: Belén Bachiller-Baeza, João Elias F.S. Rodrigues, Maricarmen Capel-Sanchez, Javier Gainza, Victoria E. García-Sánchez, Ignacio J. Villar-García, Virginia Perez-Dieste, Carlo Marini, M. Teresa Fernández-Diaz, José A. Alonso, Consuelo Álvarez-Galván
Format: Article
Language:English
Published: Elsevier 2024-11-01
Series:Journal of CO2 Utilization
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Online Access:http://www.sciencedirect.com/science/article/pii/S2212982024003044
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author Belén Bachiller-Baeza
João Elias F.S. Rodrigues
Maricarmen Capel-Sanchez
Javier Gainza
Victoria E. García-Sánchez
Ignacio J. Villar-García
Virginia Perez-Dieste
Carlo Marini
M. Teresa Fernández-Diaz
José A. Alonso
Consuelo Álvarez-Galván
author_facet Belén Bachiller-Baeza
João Elias F.S. Rodrigues
Maricarmen Capel-Sanchez
Javier Gainza
Victoria E. García-Sánchez
Ignacio J. Villar-García
Virginia Perez-Dieste
Carlo Marini
M. Teresa Fernández-Diaz
José A. Alonso
Consuelo Álvarez-Galván
author_sort Belén Bachiller-Baeza
collection DOAJ
description In this work, key factors that affect catalytic activity of Ni/La-doped ceria catalysts for the reverse water gas shift reaction (RWGS) have been revealed by applying in situ advanced synchrotron techniques, such as X-ray Absorption Spectroscopy (XAS) and Near-ambient pressure X-ray Photoelectron spectroscopy (NAP-XPS). Complementary ex situ characterization techniques have been also used, adding valuable insights on different physicochemical properties of the catalysts. Lanthanum incorporates into the ceria lattice, increasing oxygen mobility, which has a role in the formation of H2O during the reaction. The optimum substitution degree of Ce by La that maximizes CO yield is close to 10 %. It is found that both bulk and surface Ce3+ proportions depend on the proportion of La, increasing with La content. At a reaction temperature of 873 K, bulk Ce3+ proportions are higher than surface ones. These differences are due to oxidative phenomena, associated to the reactive mixture that take place on the surface, such as CO2 adsorption and H2O formation. Concerning Ni phase, NiO bulk reduction to metallic Ni is very fast (in the range 573–623 K), however, Ni0 and Ni2+ species coexist on the surface during the reaction. It is found that a higher proportion of surface metallic Ni promotes the selectivity towards the RWGS, inhibiting the competing methanation reaction. On the other hand, La doping is relevant for the formation of lanthanum oxycarbonate, which has a role gasifying carbon deposits.
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spelling doaj-art-d2835d639b4b413f8c98839eb8f5ec542024-11-18T04:33:10ZengElsevierJournal of CO2 Utilization2212-98392024-11-0189102969In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogenBelén Bachiller-Baeza0João Elias F.S. Rodrigues1Maricarmen Capel-Sanchez2Javier Gainza3Victoria E. García-Sánchez4Ignacio J. Villar-García5Virginia Perez-Dieste6Carlo Marini7M. Teresa Fernández-Diaz8José A. Alonso9Consuelo Álvarez-Galván10Instituto de Catálisis y Petroleoquímica (CSIC), Cantoblanco, Madrid 28049, Spain; Corresponding authors.European Synchrotron Radiation Facility (ESRF), 71 Av. des Martyrs, Grenoble 38000, France; ALBA Synchrotron, Carrer de la Llum No. 2-26, Cerdanyola del Vallès, Barcelona 08290, SpainInstituto de Catálisis y Petroleoquímica (CSIC), Cantoblanco, Madrid 28049, SpainInstituto de Ciencia de Materiales de Madrid (CSIC), Cantoblanco, Madrid 28049, SpainInstituto de Catálisis y Petroleoquímica (CSIC), Cantoblanco, Madrid 28049, SpainALBA Synchrotron, Carrer de la Llum No. 2-26, Cerdanyola del Vallès, Barcelona 08290, SpainALBA Synchrotron, Carrer de la Llum No. 2-26, Cerdanyola del Vallès, Barcelona 08290, SpainALBA Synchrotron, Carrer de la Llum No. 2-26, Cerdanyola del Vallès, Barcelona 08290, SpainInstitut Laue Langevin ILL, BP 156X, Grenoble F-38042, FranceInstituto de Ciencia de Materiales de Madrid (CSIC), Cantoblanco, Madrid 28049, SpainInstituto de Catálisis y Petroleoquímica (CSIC), Cantoblanco, Madrid 28049, Spain; Corresponding authors.In this work, key factors that affect catalytic activity of Ni/La-doped ceria catalysts for the reverse water gas shift reaction (RWGS) have been revealed by applying in situ advanced synchrotron techniques, such as X-ray Absorption Spectroscopy (XAS) and Near-ambient pressure X-ray Photoelectron spectroscopy (NAP-XPS). Complementary ex situ characterization techniques have been also used, adding valuable insights on different physicochemical properties of the catalysts. Lanthanum incorporates into the ceria lattice, increasing oxygen mobility, which has a role in the formation of H2O during the reaction. The optimum substitution degree of Ce by La that maximizes CO yield is close to 10 %. It is found that both bulk and surface Ce3+ proportions depend on the proportion of La, increasing with La content. At a reaction temperature of 873 K, bulk Ce3+ proportions are higher than surface ones. These differences are due to oxidative phenomena, associated to the reactive mixture that take place on the surface, such as CO2 adsorption and H2O formation. Concerning Ni phase, NiO bulk reduction to metallic Ni is very fast (in the range 573–623 K), however, Ni0 and Ni2+ species coexist on the surface during the reaction. It is found that a higher proportion of surface metallic Ni promotes the selectivity towards the RWGS, inhibiting the competing methanation reaction. On the other hand, La doping is relevant for the formation of lanthanum oxycarbonate, which has a role gasifying carbon deposits.http://www.sciencedirect.com/science/article/pii/S2212982024003044RWGSNickelLa-doped CeO2Near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS)In situ X-ray absorption spectroscopy (in situ XAS)
spellingShingle Belén Bachiller-Baeza
João Elias F.S. Rodrigues
Maricarmen Capel-Sanchez
Javier Gainza
Victoria E. García-Sánchez
Ignacio J. Villar-García
Virginia Perez-Dieste
Carlo Marini
M. Teresa Fernández-Diaz
José A. Alonso
Consuelo Álvarez-Galván
In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogen
Journal of CO2 Utilization
RWGS
Nickel
La-doped CeO2
Near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS)
In situ X-ray absorption spectroscopy (in situ XAS)
title In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogen
title_full In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogen
title_fullStr In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogen
title_full_unstemmed In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogen
title_short In situ evolution of surface and bulk properties of Ni/La-doped CeO2 catalysts for CO2 reduction with hydrogen
title_sort in situ evolution of surface and bulk properties of ni la doped ceo2 catalysts for co2 reduction with hydrogen
topic RWGS
Nickel
La-doped CeO2
Near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS)
In situ X-ray absorption spectroscopy (in situ XAS)
url http://www.sciencedirect.com/science/article/pii/S2212982024003044
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