CONSTRUCTION OF PHOTO-CATALYTIC REACTION SYSTEMS IN EFFICINENT CONVERSION OF CARBON DIOXIDE TO METHANOL BY UTILIZING SOLAR ENERGY

利用太阳能高效转化二氧化碳制甲醇的光催化反应系统的构建

• 批准号: 12650837
• 负责人: YOSHINAGA Kohji
• 金额: $ 2.37万
• 依托单位: KYUSHU INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650837/
• 关键词: Solar energy; Photo-catalyst; Titania; Carbon dioxide; Methanol; チタニア; 二酸化炭素変換

1. Preparation of chormophore / titania catalysts(1) Two-step polymer modification of colloidal titania of 100 nm size, with poly(maleic anhydride-styrene) (P(MA-ST)) and RuCl_2( 2,2' -bipyridyl)_3 (Ru(II)-bpy)-anchored poly(2-methyl-2-oxazoline), successfully gave chromophore-grafted titania composite particles (1) ; the maximum amounts of introduced Ru(II)- complex was 3.42 x 10^<-4> mol/g, i.e. 14.2 Ru-atom/nm^2.(2) In order to prepare stable titania composite particles in aqueous solution, incorporation of Ru(II)-(bpy)/silica, which was made from P(MA-ST)-modified colloidal silica of 20 nm size into titania resulted in photo-catalytically active Ru(II)(bpy)/silica/titania composite (2) of 40-70 nm size.2. Photocatalytic activity of the titania composite catalyst by visible light irradiation(1) Irradiation of visible light to the aqueous suspension containing Catalyst 1 led to efficient electron transfer from Ru(II)(bpy) to methyl viologen as a electron transfer in the presence of ethylenediaminetetraactic acid ; The maximum quantum yield was 1.5 %. Kinetic analysis of the photo-catalytic reaction showed the electron transfer took place via two rotes, one was direct one and another was indirect one via titania surface. The kinetic studies also showed the direct electron transfer was controlled by diffusion of the donor and involved with reverse electron transfer, and that the indirect electron transfer predominantly took place in low concentration of the donor.(2) Catalyst 2 was stably dispersible in aqueous solution and showed stable photo-catalytic activity by visible light, but 10% of the activity of Catalyst 1. It is required to improve the photo-catalytic activity of Catalyst 2, because of practically promising for photo-catalytic conversion of carbon dioxide to methanol.

1.发色团/二氧化钛催化剂的制备(1)用聚(马来酸酐-苯乙烯)(P(MA-St))和RuCl2(2，2‘-联吡啶)_3(Ru(II)-bpy)-锚定聚(2-甲基-2-恶唑啉)-聚(2-甲基-2-恶唑啉)对100 nm的二氧化钛胶体进行两步聚合物修饰，成功制备了生色团接枝二氧化钛复合粒子(1)，最大引入Ru(II)-配合物的量为3.42×10~(-1)；(2)为了在水溶液中制备稳定的二氧化钛复合粒子，用P(MA-St)改性的胶体二氧化硅制备了粒径为20 nm的Ru(II)-(Bpy)/二氧化硅，得到了尺寸为40-70 nm的光催化活性Ru(II)(Bpy)/二氧化硅/二氧化钛复合材料(2)。可见光照射二氧化钛复合催化剂的光催化活性(1)在乙二胺四乙酸存在下，可见光照射到含催化剂1的悬浮液中，使Ru(II)(Bpy)与甲基紫精发生电子转移，最大量子产率为1.5%。光催化反应的动力学分析表明，电子转移是通过两种途径进行的，一种是直接转移，另一种是间接转移。动力学研究还表明，直接电子转移受给体扩散控制，参与了反向电子转移，间接电子转移主要发生在低给电子体浓度下。(2)催化剂2在水溶液中分散稳定，在可见光下表现出稳定的光催化活性，但活性仅为催化剂1的10%。由于催化剂2在二氧化碳光催化转化为甲醇方面具有实用前景，因此需要提高催化剂2的光催化活性。

项目成果

R. Kakehashi: "Hydrogen Ion Titration of Long Alkyl Chain Amine Oxide Micelles"Journal of Colloid and Interface Science. Vol.243. 233-240 (2001)

R. Kakehashi：“长烷基链氧化胺胶束的氢离子滴定”胶体与界面科学杂志。

K.Yoshinaga: "Surface Modification of Fine Colloidal Silica with Copolymer Silane Coupling Agents Composed of Maleic Anhydride"Cofloid and Polymer Science. Vol.280. 85-89 (2002)

K.Yoshinaga：“用马来酸酐组成的共聚物硅烷偶联剂对细胶体二氧化硅进行表面改性”Cofloid 和聚合物科学。

K. Yoshinaga: "Marcel-Dekker (New York)"Particles Modified in Surface Properties, in "Fine Particles-Synthesis, Characterization, and Mechanism" ed. by T. Sugimoto. 21 (2000)

K. Yoshinaga：“Marcel-Dekker（纽约）”表面性质改性的颗粒，载于“细颗粒的合成、表征和机理”编辑。

K. Yoshinaga: "Photoinduced Electron Transfer Catalysis of Titania Particles Modified with a Ru(2,2'-bipyridyl)_3^<2+>-Grafted Polymer by Visible Light"Colloid and Polymer Science. Vol.278. 481-484 (2000)

K. Yoshinaga：“可见光下用 Ru(2,2-联吡啶)_3^<2>-接枝聚合物改性的二氧化钛颗粒的光诱导电子转移催化”胶体与聚合物科学。

Kohji Yoshinaga: "Particles Modified in Sunface Properties, in "Fine Particles-Synthesis, Characterization, and Mechanism" ed.T.Sugimoto"Marcel Dekker (New York). 21 (2000)

Kohji Yoshinaga：“在 Sunface 属性中修改的粒子，在“精细粒子的合成、表征和机制”ed.T.Sugimoto”Marcel Dekker（纽约）。