Zhu Dongdong, Liu Jinlong, Zhao Yongqiang, Zheng Yao, Qiao Shi-Zhang
School of Chemical Engineering, The University of Adelaide, Adelaide, SA, 5005, Australia.
Small. 2019 Apr;15(14):e1805511. doi: 10.1002/smll.201805511. Epub 2019 Mar 3.
2D metal-organic frameworks (MOFs) have been widely investigated for electrocatalysis because of their unique characteristics such as large specific surface area, tunable structures, and enhanced conductivity. However, most of the works are focused on oxygen evolution reaction. There are very limited numbers of reports on MOFs for hydrogen evolution reaction (HER), and generally these reported MOFs suffer from unsatisfactory HER activities. In this contribution, novel 2D Co-BDC/MoS (BDC stands for 1,4-benzenedicarboxylate, C H O ) hybrid nanosheets are synthesized via a facile sonication-assisted solution strategy. The introduction of Co-BDC induces a partial phase transfer from semiconducting 2H-MoS to metallic 1T-MoS . Compared with 2H-MoS , 1T-MoS can activate the inert basal plane to provide more catalytic active sites, which contributes significantly to improving HER activity. The well-designed Co-BDC/MoS interface is vital for alkaline HER, as Co-BDC makes it possible to speed up the sluggish water dissociation (rate-limiting step for alkaline HER), and modified MoS is favorable for the subsequent hydrogen generation step. As expected, the resultant 2D Co-BDC/MoS hybrid nanosheets demonstrate remarkable catalytic activity and good stability toward alkaline HER, outperforming those of bare Co-BDC, MoS , and almost all the previously reported MOF-based electrocatalysts.
二维金属有机框架材料(MOFs)因其具有大比表面积、可调控结构和增强的导电性等独特特性,已被广泛用于电催化研究。然而,大多数研究工作都集中在析氧反应上。关于用于析氢反应(HER)的MOFs的报道数量非常有限,而且一般来说,这些报道的MOFs的析氢活性并不理想。在本研究中,通过一种简便的超声辅助溶液策略合成了新型二维Co-BDC/MoS(BDC代表1,4-苯二甲酸,C₆H₄O₄)混合纳米片。Co-BDC的引入导致了从半导体性的2H-MoS向金属性的1T-MoS的部分相转移。与2H-MoS相比,1T-MoS可以激活惰性基面以提供更多的催化活性位点,这对提高析氢活性有显著贡献。精心设计的Co-BDC/MoS界面对于碱性析氢反应至关重要,因为Co-BDC能够加速缓慢的水离解(碱性析氢反应的速率限制步骤),而改性的MoS有利于随后的析氢步骤。正如预期的那样,所得的二维Co-BDC/MoS混合纳米片对碱性析氢反应表现出显著的催化活性和良好的稳定性,优于裸Co-BDC、MoS以及几乎所有先前报道的基于MOF的电催化剂。