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
Center for Advancing Electronics Dresden (Cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany.
Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of Ion Beam Physics and Materials Research, 01328, Dresden, Germany.
Nat Commun. 2020 Mar 16;11(1):1409. doi: 10.1038/s41467-020-15141-y.
Highly effective electrocatalysts promoting CO reduction reaction (CORR) 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) and zinc-bis(dihydroxy) complex (ZnO) as linkage (PcCu-O-Zn). The PcCu-O-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H/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 complexes act as CORR catalytic sites while CuN centers promote the protonation of adsorbed CO during CORR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CORR toward syngas synthesis.
开发高效的电催化剂以促进一氧化碳还原反应（CORR）对于在应对当前环境挑战的同时生产增值化学品/燃料极为必要。在此，我们开发了一种层状堆叠的双金属二维共轭金属有机框架（2D c-MOF），它以铜酞菁为配体（CuN），以锌双（二羟基）配合物（ZnO）为连接体（PcCu-O-Zn）。PcCu-O-Zn表现出88%的高CO选择性、0.39 s的周转频率和长期耐久性（>10 h），因此超过了迄今为止报道的基于MOF的电催化剂。通过改变金属中心和施加电位，可以调节摩尔H/CO比（1:7至4:1），这使得二维c-MOF与合成气工业应用高度相关。对比实验结合原位光谱电化学和理论计算揭示了一种协同催化机制；ZnO配合物作为CORR催化位点，而CuN中心在CORR过程中促进吸附的CO的质子化。这项工作为开发用于协同催化CORR以合成合成气的双金属MOF电催化剂提供了一种策略。
