A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures
A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures
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DOI：
10.1038/nchem.1595
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发表时间：
2013-04-01
期刊：
影响因子：
21.8
通讯作者：
Gruetzmacher, Hansjoerg
中科院分区：
文献类型：
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作者：
Rodriguez-Lugo, Rafael E.;Trincado, Monica;Gruetzmacher, Hansjoerg
开发一种有效的催化过程，模拟乙醇脱氢酶的酶功能是使用生物质醇生产H-2作为化学能载体和精细化学品在无废物条件下的关键。具有螯合双（烯烃）二氮二烯配体的钌络合物可以催化醇-水混合物脱氢成其相应的酸，其中分子氢作为反应的唯一副产物。这种络合物[K（dme）（2）][Ru（H）（trop（2）dad）]在分子内储存多达两当量的氢，并在水和碱的存在下在均相条件下催化醇类生成H-2。MeOH-H2O混合物的转化在中性条件下选择性地进行到CO2/H-2气体形成，从而允许使用全部氢含量（12重量%）。从这些反应中分离和表征的钌配合物提出了一个机制的方案，其中trop（2）dad配体表现为化学上的“非无辜的”合作配体。
The development of an efficient catalytic process that mimics the enzymatic function of alcohol dehydrogenase is critical for using biomass alcohols for both the production of H-2 as a chemical energy carrier and fine chemicals under waste-free conditions. Dehydrogenation of alcohol-water mixtures into their corresponding acids with molecular hydrogen as the sole by-product from the reaction can be catalysed by a ruthenium complex with a chelating bis(olefin) diazadiene ligand. This complex, [K(dme)(2)][Ru(H)(trop(2)dad)], stores up to two equivalents of hydrogen intramolecularly, and catalyses the production of H-2 from alcohols in the presence of water and a base under homogeneous conditions. The conversion of a MeOH-H2O mixture proceeds selectively to CO2/H-2 gas formation under neutral conditions, thereby allowing the use of the entire hydrogen content (12% by weight). Isolation and characterization of the ruthenium complexes from these reactions suggested a mechanistic scenario in which the trop(2)dad ligand behaves as a chemically 'non-innocent' co-operative ligand.