title: Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2over Nanostructured Pd@Nb2O5.
abstract: The reverse water gas shift (RWGS) reaction driven by Nb2O5nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5hybrid catalyst that efficiently hydrogenates CO2to CO at an impressive rate as high as 1.8 mmol gcat-1h-1is developed. The mechanism of this photothermal reaction involves H2dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5nanorods whereupon adsorbed CO2is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2to valuable chemicals and fuels.
authors.affiliation: Department of Materials Science & Engineering University of Toronto 184 College Street Toronto Ontario M5S 3E4 Canada.
authors.forename: Jia
authors.initials: J
authors.lastname: Jia
authors.affiliation: Materials Chemistry and Nanochemistry Research Group Solar Fuels Cluster Department of Chemistry University of Toronto 80 St. George Street Toronto Ontario M5S 3H6 Canada.
authors.forename: Paul G
authors.initials: PG
authors.lastname: O'Brien
authors.affiliation: Institute of Functional Nano and Soft Materials (FUNSOM) Jiangsu Key Laboratory of Carbon-Based Functional Materials and Devices, and Collaborative Innovation Center of Suzhou Nano Science and Technology Soochow University 215123 Suzhou Jiangsu China.
authors.forename: Le
authors.initials: L
authors.lastname: He
authors.affiliation: Materials Science and Technology Department Oak Ridge National Laboratory Oak Ridge TN 37831 USA.
authors.forename: Qiao
authors.initials: Q
authors.lastname: Qiao
authors.affiliation: Materials Chemistry and Nanochemistry Research Group Solar Fuels Cluster Department of Chemistry University of Toronto 80 St. George Street Toronto Ontario M5S 3H6 Canada.
authors.forename: Teng
authors.initials: T
authors.lastname: Fei
authors.affiliation: Materials Chemistry and Nanochemistry Research Group Solar Fuels Cluster Department of Chemistry University of Toronto 80 St. George Street Toronto Ontario M5S 3H6 Canada.
authors.forename: Laura M
authors.initials: LM
authors.lastname: Reyes
authors.affiliation: Materials Chemistry and Nanochemistry Research Group Solar Fuels Cluster Department of Chemistry University of Toronto 80 St. George Street Toronto Ontario M5S 3H6 Canada.
authors.forename: Timothy E
authors.initials: TE
authors.lastname: Burrow
authors.affiliation: Materials Chemistry and Nanochemistry Research Group Solar Fuels Cluster Department of Chemistry University of Toronto 80 St. George Street Toronto Ontario M5S 3H6 Canada.
authors.forename: Yuchan
authors.initials: Y
authors.lastname: Dong
authors.affiliation: Materials Chemistry and Nanochemistry Research Group Solar Fuels Cluster Department of Chemistry University of Toronto 80 St. George Street Toronto Ontario M5S 3H6 Canada.
authors.forename: Kristine
authors.initials: K
authors.lastname: Liao
authors.affiliation: GFMC & Instituto Pluridisciplinar Universidad Complutense de Madrid Madrid 28040 Spain.
authors.forename: Maria
authors.initials: M
authors.lastname: Varela
authors.affiliation: National University of Singapore Department of Materials Science and Engineering Block EA #07-14, 9 Engineering Drive 1 117575 Singapore Singapore.
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Pennycook
authors.affiliation: Department of Chemistry American University of Beirut Beirut 11-0236 Lebanon.
authors.forename: Mohamad
authors.initials: M
authors.lastname: Hmadeh
authors.affiliation: Department of Electrical and Computing Engineering University of Toronto 10 King's College Road Toronto Ontario M5S 3G4 Canada.
authors.forename: Amr S
authors.initials: AS
authors.lastname: Helmy
authors.affiliation: Department of Materials Science & Engineering University of Toronto 184 College Street Toronto Ontario M5S 3E4 Canada; Department of Electrical and Computing Engineering University of Toronto 10 King's College Road Toronto Ontario M5S 3G4 Canada.
authors.forename: Nazir P
authors.initials: NP
authors.lastname: Kherani
authors.affiliation: Department of Materials Science & Engineering University of Toronto 184 College Street Toronto Ontario M5S 3E4 Canada.
authors.forename: Doug D
authors.initials: DD
authors.lastname: Perovic
authors.affiliation: Materials Chemistry and Nanochemistry Research Group Solar Fuels Cluster Department of Chemistry University of Toronto 80 St. George Street Toronto Ontario M5S 3H6 Canada.
authors.forename: Geoffrey A
authors.initials: GA
authors.lastname: Ozin
keywords: carbon dioxide; niobium oxide nanostructure; palladium catalysts; photothermal catalysis; solar fuels