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

Nat Commun. 2020 Mar 16;11(1):1409. doi: 10.1038/s41467-020-15141-y.

Authors

Haixia Zhong^#¹, Mahdi Ghorbani-Asl^#², Khoa Hoang Ly^#¹, Jichao Zhang^#³, Jin Ge², Mingchao Wang¹, Zhongquan Liao⁴, Denys Makarov², Ehrenfried Zschech⁴, Eike Brunner¹, Inez M Weidinger¹, Jian Zhang^{1

5}, Arkady V Krasheninnikov^{2

6}, Stefan Kaskel¹, Renhao Dong⁷, Xinliang Feng⁸

Affiliations

¹ Center for Advancing Electronics Dresden (Cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany.
² Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of Ion Beam Physics and Materials Research, 01328, Dresden, Germany.
³ Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, 201204, Shanghai, China.
⁴ Fraunhofer Institute for Ceramic Technologies and Systems (IKTS), Maria-Reiche-Strasse 2, 01109, Dresden, Germany.
⁵ Department of Applied Chemistry, School of Applied and Natural Sciences, Northwestern Polytechnical University, 710129, Xi'an, China.
⁶ Department of Applied Physics, Aalto University, P.O. Box 11100, FI-00076, Aalto, Finland.
⁷ Center for Advancing Electronics Dresden (Cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany. renhaodong@tu-dresden.de.
⁸ Center for Advancing Electronics Dresden (Cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany. xinliang.feng@tu-dresden.de.

^# Contributed equally.

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.