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Title: Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1];  [2];  [3]; ORCiD logo [3]
  1. Department of Chemistry and Biochemistry, University of Colorado at Boulder, 215 UCB Boulder Colorado 80309-0215 USA
  2. Department of Chemistry and Biochemistry, University of Colorado at Boulder, 215 UCB Boulder Colorado 80309-0215 USA, Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, College of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090 P. R. China
  3. Department of Chemistry and Biochemistry, University of Colorado at Boulder, 215 UCB Boulder Colorado 80309-0215 USA, Materials Science and Engineering Program, University of Colorado at Boulder, 596 UCB Boulder Colorado 80309-0596 USA
Publication Date:
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1375468
Grant/Contract Number:
AR0000683
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 46; Related Information: CHORUS Timestamp: 2017-08-17 03:26:19; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Du, Ya, Pearson, Ryan M., Lim, Chern-Hooi, Sartor, Steven M., Ryan, Matthew D., Yang, Haishen, Damrauer, Niels H., and Miyake, Garret M. Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals. Germany: N. p., 2017. Web. doi:10.1002/chem.201702926.
Du, Ya, Pearson, Ryan M., Lim, Chern-Hooi, Sartor, Steven M., Ryan, Matthew D., Yang, Haishen, Damrauer, Niels H., & Miyake, Garret M. Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals. Germany. doi:10.1002/chem.201702926.
Du, Ya, Pearson, Ryan M., Lim, Chern-Hooi, Sartor, Steven M., Ryan, Matthew D., Yang, Haishen, Damrauer, Niels H., and Miyake, Garret M. 2017. "Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals". Germany. doi:10.1002/chem.201702926.
@article{osti_1375468,
title = {Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals},
author = {Du, Ya and Pearson, Ryan M. and Lim, Chern-Hooi and Sartor, Steven M. and Ryan, Matthew D. and Yang, Haishen and Damrauer, Niels H. and Miyake, Garret M.},
abstractNote = {},
doi = {10.1002/chem.201702926},
journal = {Chemistry - A European Journal},
number = 46,
volume = 23,
place = {Germany},
year = 2017,
month = 8
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on August 1, 2018
Publisher's Accepted Manuscript

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  • The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity formore » the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.« less
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