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Title: Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures

Abstract

We report solar-to-fuel conversion reaction often requires multiple proton-coupled electron transfer (PCET) processes powered by the energetic electrons and/or holes generated by the absorption of multiple photons. The effective coupling of multiple electron transfer from the light absorber with the multiple PCET reactions at the catalytic center is one of the key challenges in efficient and selective conversion of solar energy to chemical fuels. In this paper, we examine the dynamics of multiple electron transfer in quantum confined CdS nanorods with a Pt tip, in which the CdS rod functions as the light absorber and the Pt tip the catalytic center. By excitation-fluence-dependent transient absorption spectroscopic measurements, we show that the multiexciton Auger recombination rate in CdS rods follows a carrier-collision model, knA = n2(n – 1)/4k2A, with a biexciton lifetime (1/k2A) of 2.0 ± 0.2 ns. In CdS–Pt nanorods, electron transfer kinetics from the CdS conduction band edge to the Pt show negligible dependence on the excitation fluence, occurring with a half-life time of 5.6 ± 0.6 ps. The efficiency of multiple exciton dissociation by multiple electron transfer to Pt decreases from 100% in biexciton states to ~41% at 22 exciton state due to the competition with Auger recombination.more » The half-lifetime of the n-charge separated state recombination (with n electrons in the Pt and n holes in the CdS) decreases from 10 μs in the single charge separated state to 42 ns in nine charge separated states. Our findings suggest the possibility of driving multielectron photocatalytic reactions under intense illumination and controlling product selectivity through multielectron transfer.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Emory Univ., Atlanta, GA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1871108
Grant/Contract Number:  
AC05-00OR22725; SC0008798
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 143; Journal Issue: 48; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; multiple electron transfer; multiple charge recombination; proton-coupled electron transfer; solar fuels; CdS nanorods; CdS-Pt nanorods; photocatalysis

Citation Formats

Liu, Yawei, Cullen, David A., and Lian, Tianquan. Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures. United States: N. p., 2021. Web. doi:10.1021/jacs.1c09125.
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Liu, Yawei, Cullen, David A., & Lian, Tianquan. Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures. United States. https://doi.org/10.1021/jacs.1c09125
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Liu, Yawei, Cullen, David A., and Lian, Tianquan. Fri . "Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures". United States. https://doi.org/10.1021/jacs.1c09125. https://www.osti.gov/servlets/purl/1871108.
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@article{osti_1871108,
title = {Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures},
author = {Liu, Yawei and Cullen, David A. and Lian, Tianquan},
abstractNote = {We report solar-to-fuel conversion reaction often requires multiple proton-coupled electron transfer (PCET) processes powered by the energetic electrons and/or holes generated by the absorption of multiple photons. The effective coupling of multiple electron transfer from the light absorber with the multiple PCET reactions at the catalytic center is one of the key challenges in efficient and selective conversion of solar energy to chemical fuels. In this paper, we examine the dynamics of multiple electron transfer in quantum confined CdS nanorods with a Pt tip, in which the CdS rod functions as the light absorber and the Pt tip the catalytic center. By excitation-fluence-dependent transient absorption spectroscopic measurements, we show that the multiexciton Auger recombination rate in CdS rods follows a carrier-collision model, knA = n2(n – 1)/4k2A, with a biexciton lifetime (1/k2A) of 2.0 ± 0.2 ns. In CdS–Pt nanorods, electron transfer kinetics from the CdS conduction band edge to the Pt show negligible dependence on the excitation fluence, occurring with a half-life time of 5.6 ± 0.6 ps. The efficiency of multiple exciton dissociation by multiple electron transfer to Pt decreases from 100% in biexciton states to ~41% at 22 exciton state due to the competition with Auger recombination. The half-lifetime of the n-charge separated state recombination (with n electrons in the Pt and n holes in the CdS) decreases from 10 μs in the single charge separated state to 42 ns in nine charge separated states. Our findings suggest the possibility of driving multielectron photocatalytic reactions under intense illumination and controlling product selectivity through multielectron transfer.},
doi = {10.1021/jacs.1c09125},
journal = {Journal of the American Chemical Society},
number = 48,
volume = 143,
place = {United States},
year = {Fri Nov 19 00:00:00 EST 2021},
month = {Fri Nov 19 00:00:00 EST 2021}
}
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