Effect of Stacking Interactions on the Translation of Structurally Related Bis(thiosemicarbazonato)nickel(II) HER Catalysts to Modified Electrode Surfaces
Effect of Stacking Interactions on the Translation of Structurally Related Bis(thiosemicarbazonato)nickel(II) HER Catalysts to Modified Electrode Surfaces
复制标题
堆积相互作用对结构相关的双(氨基硫脲)镍(II) HER催化剂向修饰电极表面转化的影响
DOI：
10.1021/acs.inorgchem.9b01209
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发表时间：
2019
影响因子：
4.6
通讯作者：
Gupta, Gautam
中科院分区：
文献类型：
--
作者：
Gupta, Alexander J.;Vishnosky, Nicholas S.;Hietsoi, Oleksandr;Losovyj, Yaroslav;Strain, Jacob;Spurgeon, Joshua;Mashuta, Mark S.;Jain, Rahul;Buchanan, Robert M.;Gupta, Gautam
一系列基于廉价的双金属镍（II）的结晶镍（II）配合物（1-3），（缩氨基硫脲）配体（4-甲基-3-缩氨基硫脲）（H2 ATSM），二乙酰双（4，4-二甲基-3-缩氨基硫脲）（H2 ATSDM）和二乙酰基双[4-（2-氨基-2-甲氧基苯基）氨基]-3-甲基-N-（2-甲氧基苯基）-2-（三氟甲基）氨基）-2-甲基-N-（三氟甲基）-2-（三氟甲基）-2-（三氟甲基）-2-（三氟甲基）氨基）苯甲酸酯（2，4-diacetylbis[4-（三氟甲基）氨基]苯甲酸酯）。（2，2，2-三氟乙基）-3-缩氨基硫脲]（H2 ATSM-F6）进行了合成，并通过单晶X射线衍射、核磁共振、紫外可见光谱和傅里叶变换红外光谱进行了表征。将1 - 3修饰在玻碳上，制备了GC-1-GC-3修饰电极，并评价了它们作为析氢反应（HER）催化剂的性能。HER的研究在0.5 M的H2SO 4水溶液（10 mA cm-2）显示，在0.740至0.450 V的过电位的显着变化后，延长循环1和2。GC-1-GC-3的电荷转移电阻分别为270、160和630 Ω。通过扫描电子显微镜和拉曼光谱对GC-1和GC-2的改性表面进行表征，发现HER前的类似结晶涂层在调节后变为表面改性的微晶。GC-3的表面在HER之前具有初始的玻璃状外观，HER之后分层。表面形态和调节效果的差异与晶体堆积效应相关。配合物1和2在晶体学方向上排列成相互作用的配合物柱，晶面间距在3.37和3.54 μ m之间。配合物3在晶体学方向上以孤立分子的柱状堆积，长程晶面间距为9.40 μ m。
A series of crystalline nickel(II) complexes (1–3) based on inexpensive bis(thiosemicarbazone) ligands diacetylbis(4-methyl-3-thiosemicarbazone) (H2ATSM), diacetylbis(4,4-dimethyl-3-thiosemicarbazone) (H2ATSDM), and diacetylbis[4-(2,2,2-trifluoroethyl)-3-thiosemicarbazone] (H2ATSM-F6) were synthesized and characterized by single-crystal X-ray diffraction and NMR, UV–visible, and Fourier transform infrared spectroscopies. Modified electrodesGC-1–GC-3were prepared with films of1–3deposited on glassy carbon and evaluated as potential hydrogen evolution reaction (HER) catalysts. HER studies in 0.5 M aqueous H2SO4(10 mA cm–2) revealed dramatic shifts in the overpotential from 0.740 to 0.450 V after extended cycling for1and2. The charge-transfer resistances forGC-1–GC-3were determined to be 270, 160, and 630 Ω, respectively. Characterization of the modified surfaces forGC-1andGC-2by scanning electron microscopy and Raman spectroscopy revealed similar crystalline coatings before HER that changed to surface-modified crystallites after conditioning. The surface ofGC-3had an initial glasslike appearance before HER that delaminated after HER. The differences in the surface morphology and the effect of conditioning are correlated with crystal-packing effects. Complexes1and2pack as columns of interacting complexes in the crystallographicadirection with short interplanar spacings between 3.37 and 3.54 Å. Complex3packs as columns of isolated molecules in the crystallographicbdirection with long-range interplanar spacings of 9.40 Å.