Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot

Journal of the American Chemical Society
Stephen C JensenEmily A Weiss

Abstract

This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6-4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ∼5 ps to form QD(•-); electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecond time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Nuclear magnetic resonance analysis of the QD-molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only e...Continue Reading

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Citations

Apr 26, 2016·Journal of the American Chemical Society·Ryan M YoungDick T Co
Aug 9, 2016·Chemical Reviews·Rachel D HarrisEmily A Weiss
Dec 3, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Lei-Lei LiuLin Liu
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Feb 28, 2019·Chemical Communications : Chem Comm·Andrea Pannwitz, Oliver S Wenger
Apr 19, 2019·Chemical Communications : Chem Comm·Dana E WestmorelandEmily A Weiss
Jul 5, 2019·Advanced Materials·Hao-Lin WuLi-Zhu Wu
Jan 17, 2020·Angewandte Chemie·Felix GlaserOliver S Wenger
Jan 10, 2018·Nature Communications·Cuibo LiuKian Ping Loh
May 13, 2020·Angewandte Chemie·Kaitlyn A PerezEmily A Weiss
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Aug 31, 2018·Frontiers in Chemistry·Pavel MorozMikhail Zamkov
Nov 3, 2020·Chemical Society Reviews·Xu-Bing LiLi-Zhu Wu
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Apr 23, 2021·ACS Applied Materials & Interfaces·Yin-Hua CuiHan-Qing Yu
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Mar 7, 2017·Chemistry of Materials : a Publication of the American Chemical Society·Raul CalzadaEmily A Weiss
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Aug 19, 2020·Journal of the American Chemical Society·Yishu Jiang, Emily A Weiss
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Mar 22, 2018·Inorganic Chemistry·Mohamad S KodaimatiEmily A Weiss
Dec 17, 2021·The Journal of Physical Chemistry Letters·Pin Lyu, Son C Nguyen

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