Efficient Catalytic Decomposition of Formic Acid for the Selective Generation of H2 and H/D Exchange with a Water-Soluble Rhodium Complex in Aqueous Solution
Efficient Catalytic Decomposition of Formic Acid for the Selective Generation of H2 and H/D Exchange with a Water-Soluble Rhodium Complex in Aqueous Solution
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DOI：
10.1002/cssc.200800147
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发表时间：
2008-01-01
期刊：
影响因子：
8.4
通讯作者：
Suenobu, Tomoyoshi
中科院分区：
文献类型：
--
作者：
Fukuzumi, Shunichi;Kobayashi, Takeshi;Suenobu, Tomoyoshi
甲酸（HCOOH）在298 K的水溶液中，在催化量的水铑络合物[Rh-III(Cp*)(bpy)(H2O)](2+)（Cp*=五甲基环戊二烯，bpy=2,2′-联吡啶）存在下，有效地分解产生H-2和选择性CO2。催化分解HCOOH不产生CO。分解速率在pH 3.8时达到最大值。在催化分解HCOOH过程中，催化剂未发生劣化，对HCOOH的重复加成反应，催化剂的催化活性保持不变。氢化铑配合物是一种催化活性物质，能与水进行高效的HID交换。在D2O中催化分解HCOOH时，选择性地生成D-2。这种高效的HID交换和DCOOH在水中催化分解过程中氘动力学同位素效应的观察为这种高效和选择性分解过程提供了有价值的机理见解。
Formic acid (HCOOH) decomposes efficiently to afford H-2 and CO2 selectively in the presence of a catalytic amount of a water-soluble rhodium aqua complex, [Rh-III(Cp*)(bpy)(H2O)](2+)(Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the some for the repeated addition of HCOOH. The rhodium-hydride complex was detected as the catalytic active species that undergoes efficient HID exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D-2 was produced selectively. Such an efficient HID exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.