Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H2 Production
Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H2 Production
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DOI：
10.1002/chem.201605337
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发表时间：
2017-02-01
影响因子：
4.3
通讯作者：
Feng, Xinliang
中科院分区：
文献类型：
--
作者：
Dong, Renhao;Zheng, Zhikun;Feng, Xinliang
MNx或MSX等金属络合物组成的碳电催化剂在析氢反应(HER)中是一种很有前途的高成本铂催化剂替代品。然而，她的活动地点的确切位置仍然难以捉摸。其中，分子金属二硫代二胺(MS2N_2，M=Co和Ni)、金属双(二硫代烯)(MS4)和金属双(二胺)(Mn4)选择性地被引入富碳2D金属有机骨架(2D MOF)中作为模型碳电催化剂。由此制备了二维MOF单层、粉末和石墨烯复合材料，并显示了一定的生成H-2的活性中心。含不同金属络合物的二维MOF基催化剂的电催化HER活性顺序为MS2N2GT；MN4>；MS4。此外，质子化优先发生在金属原子上，伴随的H-2异解消除有利于MS2N活性中心的M-N单元发生。研究结果为金属络合物在富碳电极材料中的应用提供了深入了解催化活性中心的依据。
Carbon electrocatalysts consisting of metal complexes such as MNx or MSx are promising alternatives to high-cost Pt catalysts for the hydrogen evolution reaction (HER). However, the exact HER active sites remain elusive. Here, molecular metal dithiolene-diamine (MS2N2, M=Co and Ni), metal bis(dithiolene) (MS4), and metal bis(diamine) (MN4) complexes were selectively incorporated into carbon-rich 2D metal-organic frameworks (2D MOFs) as model carbon electrocatalysts. The 2D MOF single layers, powders, and composites with graphene were thus prepared and showed definite active sites for H-2 generation. The electrocatalytic HER activity of the 2D MOF-based catalysts with different metal complexes follow the order of MS2N2 > MN4 > MS4. Moreover, the protonation preferentially occurred on the metal atoms, and the concomitant heterolytic elimination of H-2 was favored on the M-N units in the MS2N2 active centers. The results provide an in-depth understanding of the catalytic active sites, thus making way for the future development of metal complexes in carbon-rich electrode materials for energy generation.