The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2 ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100 ps) and electron (∼1 ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures.
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21 May 2024
Research Article|
May 15 2024
Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures
Special Collection:
Festschrift in honor of Louis E. Brus
Jaime R. Ayala
;
Jaime R. Ayala
(Conceptualization, Data curation, Formal analysis, Writing – original draft, Writing – review & editing)
1
Department of Chemistry and Department of Material Science and Engineering, Texas A&M University
, College Station, Texas 77843, USA
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Karoline E. García-Pedraza
;
Karoline E. García-Pedraza
(Conceptualization, Data curation, Formal analysis, Writing – original draft, Writing – review & editing)
2
Department of Chemistry, University at Buffalo
, Buffalo, New York 14260, USA
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Alice R. Giem
;
Alice R. Giem
(Data curation, Formal analysis, Methodology)
1
Department of Chemistry and Department of Material Science and Engineering, Texas A&M University
, College Station, Texas 77843, USA
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Udani Wijethunga
;
Udani Wijethunga
(Formal analysis, Investigation, Methodology)
2
Department of Chemistry, University at Buffalo
, Buffalo, New York 14260, USA
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Shruti Hariyani
;
Shruti Hariyani
(Formal analysis, Investigation, Visualization)
1
Department of Chemistry and Department of Material Science and Engineering, Texas A&M University
, College Station, Texas 77843, USA
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Luis Carrillo
;
Luis Carrillo
(Formal analysis, Investigation)
1
Department of Chemistry and Department of Material Science and Engineering, Texas A&M University
, College Station, Texas 77843, USA
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Cherno Jaye;
Cherno Jaye
(Investigation, Methodology, Resources)
3
Material Measurement Laboratory, National Institute of Standards and Technology
, Gaithersburg, Maryland 20899, USA
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Conan Weiland
;
Conan Weiland
(Formal analysis, Resources)
3
Material Measurement Laboratory, National Institute of Standards and Technology
, Gaithersburg, Maryland 20899, USA
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Daniel A. Fischer
;
Daniel A. Fischer
(Methodology, Resources, Supervision)
3
Material Measurement Laboratory, National Institute of Standards and Technology
, Gaithersburg, Maryland 20899, USA
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David F. Watson
;
David F. Watson
a)
(Conceptualization, Funding acquisition, Supervision, Writing – original draft)
2
Department of Chemistry, University at Buffalo
, Buffalo, New York 14260, USA
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Sarbajit Banerjee
Sarbajit Banerjee
a)
(Conceptualization, Project administration, Resources, Writing – original draft, Writing – review & editing)
1
Department of Chemistry and Department of Material Science and Engineering, Texas A&M University
, College Station, Texas 77843, USA
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Jaime R. Ayala
1
Karoline E. García-Pedraza
2
Alice R. Giem
1
Udani Wijethunga
2
Shruti Hariyani
1
Luis Carrillo
1
Cherno Jaye
3
Conan Weiland
3
Daniel A. Fischer
3
David F. Watson
2,a)
Sarbajit Banerjee
1,a)
1
Department of Chemistry and Department of Material Science and Engineering, Texas A&M University
, College Station, Texas 77843, USA
2
Department of Chemistry, University at Buffalo
, Buffalo, New York 14260, USA
3
Material Measurement Laboratory, National Institute of Standards and Technology
, Gaithersburg, Maryland 20899, USA
J. Chem. Phys. 160, 194703 (2024)
Article history
Received:
January 31 2024
Accepted:
April 25 2024
Citation
Jaime R. Ayala, Karoline E. García-Pedraza, Alice R. Giem, Udani Wijethunga, Shruti Hariyani, Luis Carrillo, Cherno Jaye, Conan Weiland, Daniel A. Fischer, David F. Watson, Sarbajit Banerjee; Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures. J. Chem. Phys. 21 May 2024; 160 (19): 194703. https://doi.org/10.1063/5.0201550
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