Preparation of composite thin films of macrocyclic metal complex-solid axial ligand and their function

研究了大环金属络合物与固体轴向配体金属氧化物复合薄膜的制备方法，发现四苯基钴卟啉(CoTPP)在473K抽空后与二氧化钛发生强烈的相互作用，生成阴离子自由基。Co-TPP不与其他金属氧化物相互作用。在373K时，CoTPP/二氧化钛对一氧化氮和一氧化碳仍表现出较强的吸附能力，在20Torr以上的氮氧化物压力下，该复合体系在373K时对一氧化氮的分解表现出显著的催化活性。在该反应中，氮气和一氧化二氮的摩尔比为1：2，但在气相中没有检测到氧气，表明生成的氧气被捕获在二氧化钛表面。通过473K的疏散，被困的氧气被移除。根据综合体的计算，总周转次数超过3000次。Thi…更多的S体系在373K时对500ppm的低浓度一氧化氮的分解表现出较高的催化活性，而在423K时被氧化分解。合成了四丙氧基酞菁钴(CoTPPC)，因为人们希望它对氧化反应具有更高的稳定性，但它们不溶于有机溶剂。CoTPPC易溶于苯等常规溶剂。在423K下，CoTPPC/二氧化钛体系对低浓度(500ppm)一氧化氮的分解具有很高的催化活性，在反应过程中选择性地生成氮气，不产生二氧化碳。该体系在氧气的共同存在下表现出稳定性。在如此低的反应温度下，一氧化氮的这种催化分解是该反应的第一个例子。在该体系中，ESR测量证实了二氧化钛向络合物的电子转移。进一步提高该体系的催化活性和稳定性的研究正在进行中。较少

Preparation of composite thin films of macrocyclic metal complex and solid axial ligand, i.e. metal oxide, was investigated in order to induce new functions which come from the chemical interaction between the components.Cobalt-tetraphenylporphyrin(CoTPP) was found to interact strongly with titania after evacuation at 473 K and to form anion radicals. Co-TPP did not interact with other metal oxides. CoTPP/titania exhibited large adsorption abilities for nitric oxide and carbon monoxide even at 373 K. This composite system was found to exhibit remarkable catalytic activity for the decomposition of nitric oxide at 373 K under the pressure of nitric oxide of above 20 Torr. In this reaction, nitrogen and nitrous oxide were produced at the molar ratio of 1/2, however no oxygen was detected in the gas phase, indicating that the produced oxygen was trapped on titania surface. The trapped oxygen was removed by the evacuation at 473 K. Total turn over number exceeded 3 based on the complex. Thi … More s system failed to show a high catalytic activity for decomposition of low concentration of nitric oxide, 500 ppm, at 373 K and to be decomposed oxidatively at 423 K.Cobalt tetrapropoxyphthalocyanine(CoTPPC) was synthesized because phthalocyanine compounds are expected to show much higher stability for oxidation reaction, however they are insoluble in organic solvents. CoTPPC was very soluble in conventional solvents such as benzene. CoTPPC /titania system was found to provide high catalytic activities for the decomposition of nitric oxide of low concentration(500 ppm) at 423 K. Nitrogen was produced selectively and no carbon dioxide was produced during the reaction. This system showed stability against the copresence of oxygen. Such a catlytic decomposition of nitric oxide at such a low reaction temperature is the first example for this reaction. In this system, the electron transfer from titania to the complex was confirmed by ESR measurements. Further investigation on increasing the catalytic activity and stability of this system is now on progress. Less