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本文进一步研究了Co~(2+)·nbpy-Ru(bpy)_3~(2+)-抗坏血酸的体系光照放氢以及乙炔等底物的还原反应。发现C_2H_2和C_2H_4都是放氢反应的抑制剂,C_2H_2则几乎全抑制了体系的放氢。因此,可以认为乙炔等底物的还原以及放氢是在同一活性中心上发生的。C_3D_3的加氢实验指出,C_2H_3侧配位于Co~I上发生顺位加氢反应。由动力学实验得知,乙烯生成的初速与溶液的pH值的关系呈高斯型;对乙炔分压为一级反应;对Co(bPy)~(2+)浓度为零级反应。初步讨论了光助单电子转移反应以及乙炔加氢的可能机理。
In this paper, we further studied the photocatalytic hydrogen desorption and the reduction reaction of acetylene and other substrates with Co 2+, Nbpy-Ru (bpy) 3 ~ (2 +) - ascorbic acid. It was found that both C_2H_2 and C_2H_4 were inhibitors of the hydrogen evolution reaction while C_2H_2 almost completely inhibited the hydrogen evolution of the system. Therefore, it is considered that the reduction of acetylene and other substrates and the release of hydrogen occur at the same active site. Hydrogenation experiment of C_3D_3 indicated that the cis-position hydrogenation occurred on the side of C_2H_3 coordinated with Co ~ I. Kinetic experiments show that the initial velocity of ethylene produced by the solution has a Gaussian relationship with the pH of the solution, the partial pressure of acetylene is the first order reaction, and the concentration of Co (bPy) 2+ is zero order. The possible mechanisms of photo-assisted single-electron transfer reaction and acetylene hydrogenation were discussed preliminarily.