Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim, Germany.
ChemSusChem. 2010 Feb 22;3(2):277-82. doi: 10.1002/cssc.200900123.
The direct low-temperature oxidation of methane to methanol is demonstrated on a highly active homogeneous molecular catalyst system and on heterogeneous molecular catalysts based on polymeric materials possessing ligand motifs within the material structure. The N-(2-methylpropyl)-4,5-diazacarbazolyl-dichloro-platinum(II) complex reaches significantly higher activity compared to the well-known Periana system and allows first conclusions on electronic and structural requirements for high catalytic activity in this reaction. Interestingly, comparable activities could be achieved utilizing a platinum modified poly(benzimidazole) material, which demonstrates for the first time a solid catalyst with superior activity compared to the Periana system. Although the material shows platinum leaching, improved activity and altered electronic properties, compared to the conventional Periana system, support the proposed conclusions on structure-activity relationships. In comparison, platinum modified triazine-based catalysts show lower catalytic activity, but rather stable platinum coordination even after several catalytic cycles. Based on these systems, further development of improved solid catalysts for the direct low-temperature oxidation of methane to methanol is feasible.
甲烷的直接低温氧化在高效均相分子催化剂体系和基于聚合材料的多相分子催化剂上得到了证明，这些聚合材料在材料结构内具有配体基序。N-(2-甲基丙基)-4,5-二氮杂咔唑基-二氯-铂(II)配合物与著名的佩里纳体系相比具有显著更高的活性，允许对该反应中高催化活性的电子和结构要求进行初步推断。有趣的是，利用一种经过铂修饰的聚（苯并咪唑）材料可以实现可比的活性，这首次证明了与佩里纳体系相比，具有优越活性的固体催化剂。尽管该材料显示出铂浸出，但与传统的佩里纳体系相比，改进的活性和改变的电子性质支持了关于结构-活性关系的提出的结论。相比之下，经过铂修饰的三嗪基催化剂显示出较低的催化活性，但即使经过几个催化循环，其铂配位也相当稳定。基于这些体系，进一步开发用于甲烷直接低温氧化为甲醇的改进的固体催化剂是可行的。
