DEVELOPMENT OF NEW NONLINEAR OPTICAL MATERIALS BY USING ORGANIC-INORGANIC COMPLEXES-FOR SYNTHESIS OF METHANOL FROM CO_2 AND H_2O-

1.合成了邻硝基苯胺与无机酸（HCl、HBr、HNO_3、H_2SO_4）的配合物，并通过X射线衍射、元素分析、红外光谱、核磁共振氢谱等手段对其结构进行了表征。其中，对硝基苯胺氢溴酸晶体具有非中心对称结构，并表现出二次谐波.合成了对硝基苯胺与金属氯化物、金属氧化物如AlCl_3、沸石等的配合物，并测定了配合物的倍频强度。其中，对硝基苯胺-AlCl_3化合物的SHG强度最强（约为100 nm）。40相对于尿素）。实验结果表明，该催化剂对水和CO_2生成甲醇的反应没有催化活性。3.在各种金属氧化物修饰的SnO_2和In_2O_3元素中，SnO_2和In_2O_3的催化活性最高，而SnO_2和In_2O_3的催化活性最低。CaO负载的In_2O_3元件对2080 ppm的CO_2气体具有良好的敏感性能，在水蒸气体积分数为0，1.1和1.8%时，其敏感系数分别为12.9，9.9和6.6。对CO_2的灵敏度与工作温度和金属氧化物的负载量有关。另外，用程序升温脱附法研究了La_2O_3负载的SnO_2的CO_2气敏机理，认为传感器电阻的降低是由于β-CO_2的吸附和O_-或O_2的脱<2->附产生氧分子和自由电子的结果。

1. Several complexes of rho-nitroaniline with inorganic acids such as HCl, HBr, HNO_3, and H_2SO_4 were synthesized and characterized by X-ray and elemental analyzes and IR and ^1H-NMR measurements. Among them, the rho-nitroaniline-hydrobromic acid crystal had a noncentrosymmetric structure and showed second harmonic generation (SHG).2. Several complexes of rho-nitroaniline with metal chloride or metal oxides such as AlCl_3 and zeolite were synthesized and the SHG intensity was measured. Among them, the rho-nitroaniline-AlCl_3 compound showed the strongest SHG intensity (ca. 40 relative to urea). The intensity was changed with the rho-nitroaniline/AlCl_3 ratio, solvent, reaction time, content of water molecules, etc. The rho-nitroaniline-AlCl_3 compound did not show the catalytic activity for the formation of methanol from water and carbon dioxide.3.Among SnO_2 and In_2O_3 elements modified by various metal oxides, CaO-loaded In_2O_3 element was found to show promising sensing properties to 2080 ppm CO_2 in air as high as 12.9, 9.9, and 6.6 in the presence of 0,1.1, and 1.8 vol% water vapor, respectively. The sensitivity to CO_2 depended on the operation temperature and the amounts of metal oxides loaded. In addition, the CO_2 sensing mechanism of La_2O_3-loaded SnO_2 was investigated by temperature programd desorption and it was suggested that the decrease in the resistance of the sensor results from the adsorption of beta-CO_2 and the desorption of O_- or O^<2-> to generate oxygen molecules and free electrons.