Efficient production of hydrogen from formic acid using a Covalent Triazine Framework supported molecular catalyst
Efficient production of hydrogen from formic acid using a Covalent Triazine Framework supported molecular catalyst
复制标题
DOI：
10.1002/cssc.201403173
复制
发表时间：
2015-03-01
期刊：
影响因子：
8.4
通讯作者：
Gascon, J.
中科院分区：
文献类型：
--
作者：
Bavykina, A. V.;Goesten, M. G.;Gascon, J.
报道了一种以(IrCp)-Cp-III* （Cp*=五甲基环戊二烯基）为共价三嗪骨架（CTF）的异相分子催化剂。它催化甲酸制氢，初始周转频率（TOFs）高达27000h(-1)，周转数（吨）超过100万。CTF支架的表面积为1800m(2)g(-1)，由联苯和吡啶碳腈的最佳比例为2:1构建而成。联苯结构块诱导介孔，从而促进反应物和产物的扩散，而游离吡啶位点激活甲酸在金属中消除-氢化物，从而实现前所未有的产氢速率。催化剂在空气中稳定，产生无co的氢，并且完全可回收。在16wt% Ir的高催化剂负载下，产氢率超过60molL(-1)h(-1)，使其对工艺强化具有吸引力。
A heterogeneous molecular catalyst based on (IrCp)-Cp-III* (Cp*=pentamethylcyclopentadienyl) attached to a covalent triazine framework (CTF) is reported. It catalyses the production of hydrogen from formic acid with initial turnover frequencies (TOFs) up to 27000h(-1) and turnover numbers (TONs) of more than one million in continuous operation. The CTF support, with a Brunauer-Emmett-Teller (BET) surface area of 1800m(2)g(-1), was constructed from an optimal 2:1 ratio of biphenyl and pyridine carbonitrile building blocks. Biphenyl building blocks induce mesoporosity and, therefore, facilitate diffusion of reactants and products whereas free pyridinic sites activate formic acid towards -hydride elimination at the metal, rendering unprecedented rates in hydrogen production. The catalyst is air stable, produces CO-free hydrogen, and is fully recyclable. Hydrogen production rates of more than 60molL(-1)h(-1) were obtained at high catalyst loadings of 16wt% Ir, making it attractive towards process intensification.