Selectivity control of CO versus HCOO− production in the visible-light-driven catalytic reduction of CO2 with two cooperative metal sites

Zhenguo Guo; Gui Chen; Claudio Cometto; Bing Ma; Hongyan Zhao; Thomas Groizard; Lingjing Chen; Hongbo Fan; Wai Lun MAN; Shek Man Yiu; Kai Chung Lau; Tai Chu Lau; Marc Robert

doi:10.1038/s41929-019-0331-6

Selectivity control of CO versus HCOO⁻ production in the visible-light-driven catalytic reduction of CO₂ with two cooperative metal sites

Zhenguo Guo, Gui Chen, Claudio Cometto, Bing Ma, Hongyan Zhao, Thomas Groizard, Lingjing Chen, Hongbo Fan, Wai Lun MAN, Shek Man Yiu, Kai Chung Lau^*, Tai Chu Lau, Marc Robert

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

106 Citations (Scopus)

Abstract

It is highly desirable to discover molecular catalysts with controlled selectivity for visible-light-driven CO₂ reduction to fuels. In the design of catalysts employing earth-abundant metals, progress has been made for CO production, but formate generation has been observed more rarely. Here, we report a binuclear Co complex bearing a bi-quaterpyridine ligand that can selectively reduce CO₂ to HCOO⁻ or CO under visible light irradiation. Selective formate production (maximum of 97%) was obtained with a turnover number of up to 821 in basic acetonitrile solution. Conversely, in the presence of a weak acid, CO₂ reduction affords CO with high selectivity (maximum of 99%) and a maximum turnover number of 829. The catalytic process is controlled by the two Co atoms acting synergistically, and the selectivity can be steered towards the desired product by simply changing the acid co-substrate.

Original language	English
Pages (from-to)	801-808
Number of pages	8
Journal	Nature Catalysis
Volume	2
Issue number	9
DOIs	https://doi.org/10.1038/s41929-019-0331-6 https://doi.org/10.1038/s41929-019-0349-9
Publication status	Published - Sept 2019

Scopus Subject Areas

Catalysis
Bioengineering
Biochemistry
Process Chemistry and Technology

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Guo, Z., Chen, G., Cometto, C., Ma, B., Zhao, H., Groizard, T., Chen, L., Fan, H., MAN, W. L., Yiu, S. M., Lau, K. C., Lau, T. C., & Robert, M. (2019). Selectivity control of CO versus HCOO⁻ production in the visible-light-driven catalytic reduction of CO₂ with two cooperative metal sites. Nature Catalysis, 2(9), 801-808. https://doi.org/10.1038/s41929-019-0331-6, https://doi.org/10.1038/s41929-019-0349-9

@article{b1ce2a8072a4488bbb6365f9b1654b9a,

title = "Selectivity control of CO versus HCOO− production in the visible-light-driven catalytic reduction of CO2 with two cooperative metal sites",

abstract = "It is highly desirable to discover molecular catalysts with controlled selectivity for visible-light-driven CO2 reduction to fuels. In the design of catalysts employing earth-abundant metals, progress has been made for CO production, but formate generation has been observed more rarely. Here, we report a binuclear Co complex bearing a bi-quaterpyridine ligand that can selectively reduce CO2 to HCOO− or CO under visible light irradiation. Selective formate production (maximum of 97%) was obtained with a turnover number of up to 821 in basic acetonitrile solution. Conversely, in the presence of a weak acid, CO2 reduction affords CO with high selectivity (maximum of 99%) and a maximum turnover number of 829. The catalytic process is controlled by the two Co atoms acting synergistically, and the selectivity can be steered towards the desired product by simply changing the acid co-substrate.",

author = "Zhenguo Guo and Gui Chen and Claudio Cometto and Bing Ma and Hongyan Zhao and Thomas Groizard and Lingjing Chen and Hongbo Fan and MAN, {Wai Lun} and Yiu, {Shek Man} and Lau, {Kai Chung} and Lau, {Tai Chu} and Marc Robert",

note = "A Publisher Correction to this article was published on 28 August 2019 In the version of this Article originally published, the affiliation for author Shek-Man Yiu was mistakenly given as Dongguan University of Technology, but it should have been Department of Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Kowloon Tong, Hong Kong, China. This has now been corrected. Funding Information: The work described in this project was supported by the National Science Foundation of China (grant no. 21703034), Hong Kong University Grants Committee Area of Excellence Scheme (grant no. AoE/P-03–08), Hong Kong Research Grants Council (N_CityU115/18) and the French National Agency for Research (ANR-16-CE05-0010-01). G.C. acknowledges start-up grants from Dongguan University of Technology for high-level talents (grant nos G200906-47, GC200109-17 and KCYKYQD2017016). K.C.L. and M.R. acknowledge partial financial support from CityU Strategic Research Grant no. 7004819 and from the Institut Universitaire de France (IUF), respectively. PhD fellowships to C.C. from Universit{\'e} Sorbonne Paris Cit{\'e} (USPC) and to B.M. from the China Scholarship Council (CSC student no. 201707040042) are acknowledged. G. Thoraval (Universit{\'e} Paris Diderot) is thanked for the design and preparation of the glassy carbon electrode (3mm diameter) used during CV experiments. Finally, we thank G. Miyake (Colorado State University) for the sample gift of phenoxazine (Pheno).",

year = "2019",

month = sep,

doi = "10.1038/s41929-019-0331-6",

language = "English",

volume = "2",

pages = "801--808",

journal = "Nature Catalysis",

issn = "2520-1158",

publisher = "Nature Publishing Group",

number = "9",

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Guo, Z, Chen, G, Cometto, C, Ma, B, Zhao, H, Groizard, T, Chen, L, Fan, H, MAN, WL, Yiu, SM, Lau, KC, Lau, TC & Robert, M 2019, 'Selectivity control of CO versus HCOO⁻ production in the visible-light-driven catalytic reduction of CO₂ with two cooperative metal sites', Nature Catalysis, vol. 2, no. 9, pp. 801-808. https://doi.org/10.1038/s41929-019-0331-6, https://doi.org/10.1038/s41929-019-0349-9

TY - JOUR

T1 - Selectivity control of CO versus HCOO− production in the visible-light-driven catalytic reduction of CO2 with two cooperative metal sites

AU - Guo, Zhenguo

AU - Chen, Gui

AU - Cometto, Claudio

AU - Ma, Bing

AU - Zhao, Hongyan

AU - Groizard, Thomas

AU - Chen, Lingjing

AU - Fan, Hongbo

AU - MAN, Wai Lun

AU - Yiu, Shek Man

AU - Lau, Kai Chung

AU - Lau, Tai Chu

AU - Robert, Marc

N1 - A Publisher Correction to this article was published on 28 August 2019 In the version of this Article originally published, the affiliation for author Shek-Man Yiu was mistakenly given as Dongguan University of Technology, but it should have been Department of Chemistry and Institute of Molecular Functional Materials, City University of Hong Kong, Kowloon Tong, Hong Kong, China. This has now been corrected. Funding Information: The work described in this project was supported by the National Science Foundation of China (grant no. 21703034), Hong Kong University Grants Committee Area of Excellence Scheme (grant no. AoE/P-03–08), Hong Kong Research Grants Council (N_CityU115/18) and the French National Agency for Research (ANR-16-CE05-0010-01). G.C. acknowledges start-up grants from Dongguan University of Technology for high-level talents (grant nos G200906-47, GC200109-17 and KCYKYQD2017016). K.C.L. and M.R. acknowledge partial financial support from CityU Strategic Research Grant no. 7004819 and from the Institut Universitaire de France (IUF), respectively. PhD fellowships to C.C. from Université Sorbonne Paris Cité (USPC) and to B.M. from the China Scholarship Council (CSC student no. 201707040042) are acknowledged. G. Thoraval (Université Paris Diderot) is thanked for the design and preparation of the glassy carbon electrode (3mm diameter) used during CV experiments. Finally, we thank G. Miyake (Colorado State University) for the sample gift of phenoxazine (Pheno).

PY - 2019/9

Y1 - 2019/9

N2 - It is highly desirable to discover molecular catalysts with controlled selectivity for visible-light-driven CO2 reduction to fuels. In the design of catalysts employing earth-abundant metals, progress has been made for CO production, but formate generation has been observed more rarely. Here, we report a binuclear Co complex bearing a bi-quaterpyridine ligand that can selectively reduce CO2 to HCOO− or CO under visible light irradiation. Selective formate production (maximum of 97%) was obtained with a turnover number of up to 821 in basic acetonitrile solution. Conversely, in the presence of a weak acid, CO2 reduction affords CO with high selectivity (maximum of 99%) and a maximum turnover number of 829. The catalytic process is controlled by the two Co atoms acting synergistically, and the selectivity can be steered towards the desired product by simply changing the acid co-substrate.

AB - It is highly desirable to discover molecular catalysts with controlled selectivity for visible-light-driven CO2 reduction to fuels. In the design of catalysts employing earth-abundant metals, progress has been made for CO production, but formate generation has been observed more rarely. Here, we report a binuclear Co complex bearing a bi-quaterpyridine ligand that can selectively reduce CO2 to HCOO− or CO under visible light irradiation. Selective formate production (maximum of 97%) was obtained with a turnover number of up to 821 in basic acetonitrile solution. Conversely, in the presence of a weak acid, CO2 reduction affords CO with high selectivity (maximum of 99%) and a maximum turnover number of 829. The catalytic process is controlled by the two Co atoms acting synergistically, and the selectivity can be steered towards the desired product by simply changing the acid co-substrate.

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U2 - 10.1038/s41929-019-0331-6

DO - 10.1038/s41929-019-0331-6

M3 - Article

AN - SCOPUS:85070823167

SN - 2520-1158

VL - 2

SP - 801

EP - 808

JO - Nature Catalysis

JF - Nature Catalysis

IS - 9

ER -

Selectivity control of CO versus HCOO⁻ production in the visible-light-driven catalytic reduction of CO₂ with two cooperative metal sites

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