Synthesis and Application of Nanoporous Photocatalysts

光催化剂通过分解水和分解甲醇将能量转化为清洁的氢能，因此受到广泛关注。在过去的十年里，在紫外线方面取得的显著进展仅限于紫外线，而不是更有用的可见光区域。可见光光催化剂的开发已成为当今光催化研究的重要课题之一。微孔有机-无机杂化配位聚合物由于具有分子吸附、离子交换和催化活性而受到人们的广泛关注。在所有这些有效的多孔材料中，我们研究了过渡金属羧酸盐配位聚合物的合成，例如，铜、钼和钌的二羧酸盐，其能够吸留大量的各种气体。“最近，我们还成功地合成了含金属卟啉的微孔过渡金属羧酸配合物，它们显示出高的气体封闭性能和高的氧化和氢化反应催化活性。（M=Cu^<2+>，Fe^<3+>;H_2TCPP = 4，4 ′，4 ″，4 ″′-（21 H，23 H-porphine-5，10，15，20-tetrayl）tetrakis benzoate）配合物在可见光照射下对甲醇的光催化分解.气态甲醇的光分解是在传统的封闭气体循环系统中进行的。采用气相色谱法（TCD，不锈钢柱，Porapak Q和Molecular sieve 5A，FID毛细管柱，DB-WAX）对产物进行分析，结果表明，Fe[FeTCPP]在可见光区有5个吸附带。它们显示出5.6和6.2 μ m的微孔。它们在155小时后显示出约25个周转次数，这远高于Fe[CuTCPP]和Fe[PdTCPP]。

Photocatalysts have attracted much attention because they convert energy into clean hydrogen energy by water splitting and decomposition of methanol. The remarkable progress of the past decade in photocatalysis has been limited to ultraviolet light instead of the more useful visible-light region. The development of visible-light photocatalysts, therefore, has become one of the most important topics in photocatalysis research today. Microporous organic-inorganic hybrid coordination polymers have attracted much attention because of their molecular adsorption, ion-exchange, and catalytic activities. Of all these efficient porous materials, we have studied the synthesis of transition-metal carboxylate coordination polymers, e.g., dicarboxylates of copper, molybdenum, and ruthenium, which are capable of occluding large amounts of various gases. 'Very recently, we have also succeeded to synthesize microporous transition-metal carboxylate complexes containing metalloporphyrins, which showed high gas occlusion properties and high catalytic activities for oxidation and hydrogenation reaction.In this study, we demonstrated the catalytic activities of Fe[MTCPP] (M=Cu^<2+>,Fe^<3+>;H_2TCPP = 4,4′,4″,4″′-(21H,23H-porphine-5,10,15,20-tetrayl)tetrakis benzoate) complexes for photo-decomposition of methanol under visible-light irradiation. The photo-decomposition of gaseous methanol was carried in a conventional closed gas circulation system. The products were hydrogen, formaldehyde and water, which were analyzed by GC (TCD, Stainless column, Porapak Q and Molecular sieve 5A, FID Capillary column, DB-WAX).Fe[FeTCPP] showed five adsorption bands in visible-light region. They showed the micropores of 5.6 and 6.2 Å. They showed ca.25 turnover numbers after 155h, which was much higher than that of Fe[CuTCPP] and Fe[PdTCPP].