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Improving Photocatalysis for the Reduction of CO_2 through non-Covalent Supramolecular Assembly

Cheung, Po Ling and Kapper, Savannah C. and Zeng, Tian and Thompson, Mark E. and Kubiak, Clifford P. (2019) Improving Photocatalysis for the Reduction of CO_2 through non-Covalent Supramolecular Assembly. Journal of the American Chemical Society, 141 (38). pp. 14961-14965. ISSN 0002-7863.

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We report the enhancement of photocatalytic performance by introduction of hydrogen-bonding interactions to a Re bipyridine catalyst and Ru photosensitizer system (ReDAC/RuDAC) by the addition of amide substituents, with carbon monoxide (CO) and carbonate/bicarbonate as products. This system demonstrates a more-than-3-fold increase in turnover number (TON_(CO) = 100 ± 4) and quantum yield (Φ_(CO) = 23.3 ± 0.8%) for CO formation compared to the control system using unsubstituted Ru photosensitizer (RuBPY) and ReDAC (TON_(CO) = 28 ± 4 and Φ_(CO) = 7 ± 1%) in acetonitrile (MeCN) with 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as sacrificial reductant. In dimethylformamide (DMF), a solvent that disrupts hydrogen bonds, the ReDAC/RuDAC system showed a decrease in catalytic performance while the control system exhibited an increase, indicating the role of hydrogen bonding in enhancing the photocatalysis for CO_2 reduction through supramolecular assembly. The similar properties of RuDAC and RuBPY demonstrated in lifetime measurements, spectroscopic analysis, and electrochemical and spectroelectrochemical studies revealed that the enhancement in photocatalysis is due not to differences in intrinsic properties of the catalyst or photosensitizer, but to hydrogen-bonding interactions between them.

Item Type:Article
Related URLs:
URLURL TypeDescription
Kapper, Savannah C.0000-0001-8222-8495
Zeng, Tian0000-0001-5957-3442
Thompson, Mark E.0000-0002-7764-4096
Kubiak, Clifford P.0000-0003-2186-488X
Alternate Title:Improving Photocatalysis for the Reduction of CO2 through non-Covalent Supramolecular Assembly
Additional Information:© 2019 American Chemical Society. Received: July 3, 2019; Published: September 6, 2019. A grant from the U.S. Air Force Office of Scientific Research (AFOSR), Basic Research Initiative (BRI) (FA9550-12-1-0414), supported P.L.C., T.Z., and C.P.K. A grant from the U.S. Department of Energy, Office of Basic Energy Sciences (DE-SC0016450), supported S.C.K. and M.E.T. The authors declare no competing financial interest.
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)FA9550-12-1-0414
Department of Energy (DOE)DE-SC0016450
Issue or Number:38
Record Number:CaltechAUTHORS:20190906-134149533
Persistent URL:
Official Citation:Improving Photocatalysis for the Reduction of CO2 through Non-covalent Supramolecular Assembly. Po Ling Cheung, Savannah C. Kapper, Tian Zeng, Mark E. Thompson, and Clifford P. Kubiak. Journal of the American Chemical Society 2019 141 (38), 14961-14965. DOI: 10.1021/jacs.9b07067
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:98493
Deposited By: George Porter
Deposited On:06 Sep 2019 21:33
Last Modified:03 Oct 2019 21:41

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