在交换了Fe~(2+),Co~(2+)或Cu~(2+)的Y型分子筛上,采用苯酐.尿素同相合成法制备了组装在Y型分子筛超笼中的金属酞菁类催化剂.以H_2O_2为氧化剂,考察了该金属酞菁/分子筛复合物上甲烷选择氧化制甲醇反应的性能,并优化了反应条件.结果表明,在室温下.金属酞菁/分子筛复合催化剂FePc/Y,CoPc/Y和CuPc/Y对H_2O_2氧化甲烷反应均有催化作用.在这些复合物上进一步担载可催化H_2O_2原位生成的Pd,Au或PdAu贵金属,并考察了其催化分子氧选择氧化甲烷反应的性能.贵金属与金属酞菁/分子筛复合催化剂的偶合实现了室温下分子氧对甲烷的活化.其中,Pd与CuPc/Y间的协同效应使得室温下甲烷选择氧化反应活性有了较大提高.
Imn(Ⅱ), cobolt(Ⅱ), and copper(Ⅱ) phthalocyanines encapsulated inside the supercage of zeolite-Y were prepared by the in situ ligand synthesis method via heating the solid mixture of iron(Ⅱ)-, cobolt(Ⅱ)-, and copper(Ⅱ)-exchanged NaY with phthalic anhydride and urea. Using hydrogen peroxide as the oxidant, the catalytic activity of these composite catalysts for methane selective oxidation was tested,and the reaction conditions were optimized. All these composite catalysts showed activity in selective oxidation of methane by hydrogen peroxide at room temperature. These composite catalysts were further loaded with Pd, Au, or PdAu, and their catalytic activity for methane oxidation with dioxygen as oxidant were examined. The coupling of encapsulated metallophthalocyanine catalysts with precious metal,which could catalyze the in situ generation of H_2O_2, realized the activation of methane by molecular oxygen at room temperature. The results showed that the synergism between palladium and copper(Ⅱ) phthalocyanine led to the improved catalytic activity in selective oxidation of methane at room temperature.
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