Long-Lived Triplet Excited State in a Heterogeneous Modified Carbon Nitride Photocatalyst

Rieth, Adam J.; Qin, Yangzhong; Martindale, Benjamin C. M.; Nocera, Daniel G.

doi:10.1021/jacs.0c12958

Long-Lived Triplet Excited State in a Heterogeneous Modified Carbon Nitride Photocatalyst

Journal Article · Thu Mar 18 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c12958· OSTI ID:1775533

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Harvard Univ., Cambridge, MA (United States); PRESIDENT AND FELLOWS OF HARVARD COLLEGE
Harvard Univ., Cambridge, MA (United States)

Heterogeneous carbon nitrides have numerous advantages as photocatalysts, including strong light absorption, tunable band edges, and scalability, but their performance and continued development are limited by fast charge recombination and an under-developed mechanistic understanding of photodriven interfacial electron transfer. These shortcomings are a result of complex photophysics, leading to rate asynchrony between oxidation and reduction, as well as redox processes driven out of electronic trap states rather than excited states. We show that a well-defined triplet excited state in cyanamide-modified carbon nitride is realized with appropriately sized particles. The utility of this long-lived excited state is demonstrated by its ability to drive a hydroamidation photoredox cycle. By the tuning of the particle size of CN_x, the oxidation–reduction photochemistry of carbon nitride may be balanced to achieve a redox-neutral closed photocatalytic cycle. Here, these results uncover a triplet excited state chemistry for appropriately sized CNx particles that preludes a rich energy and electron transfer photochemistry for these materials.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States); Harvard University, Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017619

OSTI ID:: 1775533

Alternate ID(s):: OSTI ID: 1992653

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Long-Lived Triplet Excited State in a Heterogeneous Modified Carbon Nitride Photocatalyst

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