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

合成了4-甲基-4‘-乙烯-2，2’-联吡啶(Vbpy)、乙烯基二茂铁、乙烯基吡啶、苯乙烯和顺丁烯二酸酐的均聚物和共聚物。随后与各种试剂的络合和反应得到了各种光氧化还原聚合物，其中包括三联吡啶(Ru(Bpy)_3^&lt；2+&gt；)、百草枯(紫精，V^&lt；2+&gt；)、敌草枯(dq^&lt；2+&gt；)和二茂铁。建立了用Vbpy残基在聚合物中同时引入Ru(Bpy)3^&lt；2+&gt；和DQ^&lt；2+&gt；基团的方法。在牺牲剂存在下，电子受体/继电器V^&lt；2+&gt；和Dq^&lt；2+&gt；对Ru(Bpy)_3^&lt；2+&gt；发射的猝灭以及自由基阳离子V^+和DQ^+的形成，揭示了电子受体/继电器在聚合物中或在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。由Ru(Bpy)_3和Ru(Bpy)_3~(2+)层组成的双层膜也进行了类似的研究。将聚合物涂覆在镀铂的氧化钛光催化剂上，以检测可见光照射下导致氢气产生的光谱敏化。调节聚合物的亲水性以及适当安排氧化还原基团导致聚合物中的电位梯度，对于开发高效的光谱敏化光催化剂和光器件是重要的。

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.