Zhang Zhuanfang, Gómez-García Carlos J, Wu Qiong, Xin Jianjiao, Pang Haijun, Ma Huiyuan, Chai Dongfeng, Li Shaobin, Zhao Chunyan
The School of Material Science and Chemical Engineering, Harbin University of Science and Technology, Harbin 150040, P. R. China.
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, P. R. China.
Inorg Chem. 2022 Aug 1;61(30):11830-11836. doi: 10.1021/acs.inorgchem.2c01579. Epub 2022 Jul 19.
molecular transformation under hydrothermal conditions is a feasible method to introduce distinct organic ligands and suppress competitive reactions between different synthons. However, this strategy has not yet been explored for the preparation of polyoxometalate (POM)-encapsulated metal-organic frameworks (MOFs). In this work, we designed and prepared a new compound, Co(3,3'-bpy)(3,5'-bpp)(4,3'-bpy)[SiWO] () (4,3'-bpy = 4,3'-dipyridine, 3,5'-bpp = 3,5'-bis(pyrid-4-yl)pyridine, and 3,3'-bpy = 3,3'-bis(pyrid-4-yl) dipyridine), an ligand synthesis route. The compound shows a novel POM-encapsulated MOF structure with two pairs of left- and right-handed double helixes. These left- and right-handed helical chains further lead to triangular and rhombus-like channels, respectively. Moreover, the as-synthesized title compound shows superior electrocatalytic activity toward the hydrogen evolution reaction (HER) in 1 M KOH aqueous solution with a low overpotential and Tafel slope of 92 mV and 92.1 mV dec, respectively, under a current density of 10 cm. Also, the compound exhibits a high activity for the photocatalytic degradation of the dye rhodamine B. The excellent performance of the compound may be attributed to the synergistic effect between W and Co elements and the presence of encapsulated POMs. The title compound proves that it is possible to prepare multifunctional MOFs with POMs and transition metals showing HER activity and dye degradation activity.
水热条件下的分子转化是引入独特有机配体并抑制不同合成子之间竞争反应的一种可行方法。然而,这种策略尚未用于制备多金属氧酸盐(POM)封装的金属有机框架(MOF)。在本工作中,我们设计并制备了一种新化合物,Co(3,3'-联吡啶)(3,5'-联吡啶基吡啶)(4,3'-联吡啶)[SiW₁₂O₄₀] ()(4,3'-联吡啶 = 4,3'-二吡啶,3,5'-联吡啶基吡啶 = 3,5'-双(吡啶-4-基)吡啶,3,3'-联吡啶 = 3,3'-双(吡啶-4-基)二吡啶),一种配体合成路线。该化合物呈现出一种新颖的POM封装MOF结构,具有两对左手和右手双螺旋。这些左手和右手螺旋链分别进一步形成三角形和菱形通道。此外,所合成的标题化合物在1 M KOH水溶液中对析氢反应(HER)表现出优异的电催化活性,在电流密度为10 mA cm⁻²时,过电位低,塔菲尔斜率分别为92 mV和92.1 mV dec⁻¹。而且,该化合物对染料罗丹明B的光催化降解具有高活性。该化合物的优异性能可能归因于W和Co元素之间的协同效应以及封装的POM的存在。标题化合物证明了用POM和过渡金属制备具有HER活性和染料降解活性的多功能MOF是可能的。