High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation

Single-atom catalysts (SACs) offer high efficiency and selectivity in chemical reactions but face challenges in converting CO2 to CO via the reverse water gas shift (RWGS) reactions. This study addresses these challenges by anchoring three noble metals (Ir, Pd, and Ru) onto titania (TiO2) and analyz...

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Main Authors: Moshood O. Bolarinwa, Aasif A. Dabbawala, Shamraiz Hussain Talib, Georgian Melinte, Thomas Delclos, Abdulmuizz Adamson, Abbas Khaleel, Kyriaki Polychronopoulou, Dalaver H. Anjum
Format: Article
Language:English
Published: Elsevier 2024-12-01
Series:Journal of CO2 Utilization
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Online Access:http://www.sciencedirect.com/science/article/pii/S2212982024003238
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author Moshood O. Bolarinwa
Aasif A. Dabbawala
Shamraiz Hussain Talib
Georgian Melinte
Thomas Delclos
Abdulmuizz Adamson
Abbas Khaleel
Kyriaki Polychronopoulou
Dalaver H. Anjum
author_facet Moshood O. Bolarinwa
Aasif A. Dabbawala
Shamraiz Hussain Talib
Georgian Melinte
Thomas Delclos
Abdulmuizz Adamson
Abbas Khaleel
Kyriaki Polychronopoulou
Dalaver H. Anjum
author_sort Moshood O. Bolarinwa
collection DOAJ
description Single-atom catalysts (SACs) offer high efficiency and selectivity in chemical reactions but face challenges in converting CO2 to CO via the reverse water gas shift (RWGS) reactions. This study addresses these challenges by anchoring three noble metals (Ir, Pd, and Ru) onto titania (TiO2) and analyzing their performance. Comprehensive characterization techniques, including electron microscopy, confirmed the uniform dispersion of metal atoms on TiO2. Among the catalysts, Ir/TiO2 exhibited the best results, achieving an 84 % CO2 conversion rate and ∼98 % CO selectivity, surpassing Pd/TiO2 and Ru/TiO2, which gained 56 % and 52 % conversion, respectively. In-situ gas transmission electron microscopy revealed the catalytic behavior of Ir/TiO2, showing Ir atom mobility and the formation of ∼1 nm nanoclusters. Density functional theory (DFT) and in-situ diffuse reflectance infrared spectroscopy (DRIFTs) further explained that the atomically dispersed Ir sites in Ir/TiO2 follow a hydrogen-assisted mechanism, with the COOH* intermediate desorbing and dissociating into CO. These findings suggest SACs' potential to facilitate greener chemical processes and reduce greenhouse gas emissions.
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spelling doaj-art-0084fc935be1448d8fe43355ee2fb5882025-08-20T01:58:08ZengElsevierJournal of CO2 Utilization2212-98392024-12-019010298810.1016/j.jcou.2024.102988High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigationMoshood O. Bolarinwa0Aasif A. Dabbawala1Shamraiz Hussain Talib2Georgian Melinte3Thomas Delclos4Abdulmuizz Adamson5Abbas Khaleel6Kyriaki Polychronopoulou7Dalaver H. Anjum8Department of Physics, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates; Center for Catalysis and Separation (CeCaS), Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab EmiratesCenter for Catalysis and Separation (CeCaS), Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates; Department of Mechanical Engineering, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab EmiratesCenter for Catalysis and Separation (CeCaS), Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates; Department of Chemistry, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab EmiratesKing Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi ArabiaMaterials and Surface Core Labs, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab EmiratesDepartment of Chemistry, United Arab Emirates University, Al-Ain, United Arab EmiratesDepartment of Chemistry, United Arab Emirates University, Al-Ain, United Arab EmiratesCenter for Catalysis and Separation (CeCaS), Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates; Department of Mechanical Engineering, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates; Corresponding authors at: Center for Catalysis and Separation (CeCaS), Khalifa University of Science and Technology Abu Dhabi 127788, United Arab EmiratesDepartment of Physics, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates; Center for Catalysis and Separation (CeCaS), Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates; Corresponding authors at: Center for Catalysis and Separation (CeCaS), Khalifa University of Science and Technology Abu Dhabi 127788, United Arab EmiratesSingle-atom catalysts (SACs) offer high efficiency and selectivity in chemical reactions but face challenges in converting CO2 to CO via the reverse water gas shift (RWGS) reactions. This study addresses these challenges by anchoring three noble metals (Ir, Pd, and Ru) onto titania (TiO2) and analyzing their performance. Comprehensive characterization techniques, including electron microscopy, confirmed the uniform dispersion of metal atoms on TiO2. Among the catalysts, Ir/TiO2 exhibited the best results, achieving an 84 % CO2 conversion rate and ∼98 % CO selectivity, surpassing Pd/TiO2 and Ru/TiO2, which gained 56 % and 52 % conversion, respectively. In-situ gas transmission electron microscopy revealed the catalytic behavior of Ir/TiO2, showing Ir atom mobility and the formation of ∼1 nm nanoclusters. Density functional theory (DFT) and in-situ diffuse reflectance infrared spectroscopy (DRIFTs) further explained that the atomically dispersed Ir sites in Ir/TiO2 follow a hydrogen-assisted mechanism, with the COOH* intermediate desorbing and dissociating into CO. These findings suggest SACs' potential to facilitate greener chemical processes and reduce greenhouse gas emissions.http://www.sciencedirect.com/science/article/pii/S2212982024003238Single atom catalyst (SACs)Reverse water gas shift (RWGS) reactionCO2 conversionNanoclusters (NCs)In-situ TEM
spellingShingle Moshood O. Bolarinwa
Aasif A. Dabbawala
Shamraiz Hussain Talib
Georgian Melinte
Thomas Delclos
Abdulmuizz Adamson
Abbas Khaleel
Kyriaki Polychronopoulou
Dalaver H. Anjum
High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation
Journal of CO2 Utilization
Single atom catalyst (SACs)
Reverse water gas shift (RWGS) reaction
CO2 conversion
Nanoclusters (NCs)
In-situ TEM
title High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation
title_full High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation
title_fullStr High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation
title_full_unstemmed High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation
title_short High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation
title_sort high performance single atom m tio2 catalysts in the reverse water gas shift reaction a comprehensive experimental and theoretical investigation
topic Single atom catalyst (SACs)
Reverse water gas shift (RWGS) reaction
CO2 conversion
Nanoclusters (NCs)
In-situ TEM
url http://www.sciencedirect.com/science/article/pii/S2212982024003238
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