Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks
Haixia Zhong, Mahdi Ghorbani‐Asl, Khoa H. Ly, Jichao Zhang, Ge Jin, Mingchao Wang, Zhongquan Liao, Denys Makarov, Ehrenfried Zschech, Eike Brunner, Inez M. Weidinger, Jian Zhang, Arkady V. Krasheninnikov, Stefan Kaskel, Renhao Dong⧫, Xinliang Feng
Abstract
Abstract Highly effective electrocatalysts promoting CO 2 reduction reaction (CO 2 RR) 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 (CuN 4 ) and zinc-bis(dihydroxy) complex (ZnO 4 ) as linkage (PcCu-O 8 -Zn). The PcCu-O 8 -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 H 2 /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; ZnO 4 complexes act as CO 2 RR catalytic sites while CuN 4 centers promote the protonation of adsorbed CO 2 during CO 2 RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO 2 RR toward syngas synthesis.