Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks

Haixia Zhong; Mahdi Ghorbani-Asl; Khoa Hoang Ly; Jichao Zhang; Jin Ge; Mingchao Wang; Zhongquan Liao; Denys Makarov; Ehrenfried Zschech; Eike Brunner; Inez M. Weidinger; Jian Zhang; Arkady V. Krasheninnikov; Stefan Kaskel; Renhao Dong; Xinliang Feng

doi:10.1038/s41467-020-15141-y

Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks

Haixia Zhong, Mahdi Ghorbani-Asl, Khoa Hoang Ly, Jichao Zhang, Jin Ge, Mingchao Wang, Zhongquan Liao, Denys Makarov, Ehrenfried Zschech, Eike Brunner, Inez M. Weidinger, Jian Zhang, Arkady V. Krasheninnikov, Stefan Kaskel, Renhao Dong, Xinliang Feng^*

^*Corresponding author for this work

Department of Applied Physics

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Abstract

Highly effective electrocatalysts promoting CO₂ reduction reaction (CO₂RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN₄) and zinc-bis(dihydroxy) complex (ZnO₄) as linkage (PcCu-O₈-Zn). The PcCu-O₈-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s⁻¹ and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H₂/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO₄ complexes act as CO₂RR catalytic sites while CuN₄ centers promote the protonation of adsorbed CO₂ during CO₂RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO₂RR toward syngas synthesis.

Original language	English
Article number	1409
Number of pages	10
Journal	Nature Communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-15141-y
Publication status	Published - 16 Mar 2020
MoE publication type	A1 Journal article-refereed

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Zhong, H., Ghorbani-Asl, M., Ly, K. H., Zhang, J., Ge, J., Wang, M., Liao, Z., Makarov, D., Zschech, E., Brunner, E., Weidinger, I. M., Zhang, J., Krasheninnikov, A. V., Kaskel, S., Dong, R., & Feng, X. (2020). Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks. Nature Communications, 11(1), [1409]. https://doi.org/10.1038/s41467-020-15141-y

Zhong, Haixia ; Ghorbani-Asl, Mahdi ; Ly, Khoa Hoang ; Zhang, Jichao ; Ge, Jin ; Wang, Mingchao ; Liao, Zhongquan ; Makarov, Denys ; Zschech, Ehrenfried ; Brunner, Eike ; Weidinger, Inez M. ; Zhang, Jian ; Krasheninnikov, Arkady V. ; Kaskel, Stefan ; Dong, Renhao ; Feng, Xinliang. / Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks. In: Nature Communications. 2020 ; Vol. 11, No. 1.

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title = "Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks",

abstract = "Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s−1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis.",

author = "Haixia Zhong and Mahdi Ghorbani-Asl and Ly, {Khoa Hoang} and Jichao Zhang and Jin Ge and Mingchao Wang and Zhongquan Liao and Denys Makarov and Ehrenfried Zschech and Eike Brunner and Weidinger, {Inez M.} and Jian Zhang and Krasheninnikov, {Arkady V.} and Stefan Kaskel and Renhao Dong and Xinliang Feng",

year = "2020",

month = mar,

day = "16",

doi = "10.1038/s41467-020-15141-y",

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Zhong, H, Ghorbani-Asl, M, Ly, KH, Zhang, J, Ge, J, Wang, M, Liao, Z, Makarov, D, Zschech, E, Brunner, E, Weidinger, IM, Zhang, J, Krasheninnikov, AV, Kaskel, S, Dong, R & Feng, X 2020, 'Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks', Nature Communications, vol. 11, no. 1, 1409. https://doi.org/10.1038/s41467-020-15141-y

Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks. / Zhong, Haixia; Ghorbani-Asl, Mahdi; Ly, Khoa Hoang; Zhang, Jichao; Ge, Jin; Wang, Mingchao; Liao, Zhongquan; Makarov, Denys; Zschech, Ehrenfried; Brunner, Eike; Weidinger, Inez M.; Zhang, Jian; Krasheninnikov, Arkady V.; Kaskel, Stefan; Dong, Renhao; Feng, Xinliang.

In: Nature Communications, Vol. 11, No. 1, 1409, 16.03.2020.

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

TY - JOUR

T1 - Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks

AU - Zhong, Haixia

AU - Ghorbani-Asl, Mahdi

AU - Ly, Khoa Hoang

AU - Zhang, Jichao

AU - Ge, Jin

AU - Wang, Mingchao

AU - Liao, Zhongquan

AU - Makarov, Denys

AU - Zschech, Ehrenfried

AU - Brunner, Eike

AU - Weidinger, Inez M.

AU - Zhang, Jian

AU - Krasheninnikov, Arkady V.

AU - Kaskel, Stefan

AU - Dong, Renhao

AU - Feng, Xinliang

PY - 2020/3/16

Y1 - 2020/3/16

N2 - Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s−1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis.

AB - Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s−1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis.

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JF - Nature Communications

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Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks

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