Preparation of polymers having photo-induced eletron transmitting capabilities and their application for photocatalysis

制备了4-甲基-4 '-乙烯基-2，2'-联吡啶（Vbpy）、乙烯基二茂铁、乙烯基吡啶、苯乙烯和马来酸酐的均聚物和共聚物。随后与各种试剂的络合和反应提供了具有钌三联吡啶（Ru（bpy）_3^<2+>）、百草枯（紫精，V^<2+>）、敌草快（DQ^<2+>）和二茂铁的各种光氧化还原聚合物。建立了一种利用Vbpy残基同时引入Ru（bpy）_3^<2+>和DQ^<2+>基团到聚合物中的方法。Ru（bpy）_3^<2+>发射被电子受体/中继V^<2+>和DQ^<2+>猝灭，以及在牺牲剂存在下自由基阳离子V^+和Dq^+的形成，揭示了电子受体/中继在聚合物区域或聚合物膜表面的浓度和吸附对有效的电子转移和电荷积累是重要的。用由中继层和Ru（bpy）_3^<2+>层组成的双层膜进行了类似的研究。将聚合物涂覆到镀铂的氧化钛光催化剂上，以检查导致通过可见光照射产生氢的光谱敏化。调节聚合物的亲水性以及氧化还原基团的适当排列导致聚合物中的电位梯度被认为是开发高效光谱敏化光催化剂和光器件的重要因素。

Homopolymers and copolymers of 4-methyl-4'-vinyl-2,2'-bipyridine(Vbpy), vinylferrocene, vinylpyridine, styrene, and maleic anhydride were prepared. Subsequent complexation and reactions with various reagents afforded a variety of photoredox polymers having ruthenium trisbipyridyl(Ru(bpy)_3^<2+>), paraquat (viologen,V^<2+>), diquat(DQ^<2+>), and ferrocene. A method of introducing both Ru(bpy)_3^<2+> and DQ^<2+> groups to polymers using Vbpy residues was established. Quenching of Ru(bpy)_3^<2+> emission by electron acceptor/relays V^<2+> and DQ^<2+> as well as formation of radical cations V^+ and Dq^+ in the presence of a sacrificial agent, revealed that concentration and adsorption of electron acceptor/relays in the polymer domain or on the polymer membrane surface are important for efficient electron transfer and charge accumulaton. A similar investigation with a two-layered membrane composed of relay and Ru(bpy)_3^<2+> layer. The polymers were coated onto the platinized titanium oxide photocatalyst to examine spectral sensitization leading to hydrogen production by visible light irradiation. Adjustment of the polymer hydrophilicity as well as proper arrangement of redox groups leading to a potential gradient in the polymer was suggested to be important in developing high-efficiency spectrally-sensitized photocatalysts and photodevices.