DESIGN OF CATALYST FOR UTILIZATION OF CO2 WITH HIGH PRESSURE-HIGH TEMPERATURE IN SITU INFRARED METHOD

1) ApparatusA不锈钢高压高温红外电池，使用温度为lMPa， 600K。在高压连续流反应系统中用作反应釜。利用该原位红外电池进行了二氧化碳和氢气的甲醇合成。对所得数据的分析表明，该反应的中间体应为铜上的甲酸类。这与我们先前关于反应机制的建议是一致的。在“Kagakukougaku”中概述了原位红外电池的设计和运行。2)甲醇合成催化剂的设计作为该方法的应用之一，研究了CO2和H2合成甲醇催化剂的设计。为了控制甲酸酯对铜的反应性，研究了载体的影响。工作假设如下：随着铜表面电子密度的增加，中间体的数量增加，而电子密度的降低使甲酸酯对加氢反应敏感。TiO2的增强效果最好，并讨论了甲酸酯对TiO2的作用。这些结果发表在Res.Chem.Intermed上。3)控制CO2加氢产物分布结果表明控制甲酸对铜的影响十分重要。然后对二氧化碳加氢反应产物的控制进行了尝试：(1)设计酸碱组分等助催化剂，控制甲醇合成反应。(2)通过添加金属来形成C-C键或氢化来设计双功能活性。可以产生碳氢化合物和含氧碳氢化合物。（日本共同体第67次会议）。

1) ApparatusA stainless steal high pressure-high temperature infrared cell was designed to be used under lMPa, 600K.It was used as a reactor in the high pressure coutinuous flow reaction system. Mthanol synthesis from carbon dioxide and hydrogen was conducted using this in situ infrared cell. The analysis of obtained data suggested that the reaction intermediates of this reaction should be the formate species on copper. This agreed with our previous proposal on the reaction mechanism. The design and operation of the in situ IR cell were summarized in "Kagakukougaku".2) Design of methanol synthesis catalystAs one the applications of this method, design of the catalyst for methanol synthsis from CO2 and H2 was studied. In order to control the reactivity of formate on copper, effect of support was investigated. The working hypothesis was as follows ; the number of intermediates should be enhanced with increasing the electron density on copper then decreasing the electron density made the formate species sensitive for hydrogenation reaction. TiO2 showed the highest enhancement effect, and the role of formate on titania was discussed. These results were published on Res.Chem.Intermed.3) Control of product distribution of CO2 hydrogenationThe results showed the importance of control of formate on copper. Then the control of reaction products of hydrogenation of carbon dioxide was tried as follows :(1) Desing of co-catalyst such as acid-base components, to control the methanol synthesis reaction.(2) Design of bi-functional activity by adding metals for C-C bond formation or for hydrogenation. which could porduce hydrocarons and oxygenated hydrocarbons. (67th meeting of Catal.Soc.of Japan).