Non-Metal-Mediated Homogeneous Hydrogenation of CO2 to CH3OH
Non-Metal-Mediated Homogeneous Hydrogenation of CO2 to CH3OH
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DOI：
10.1002/anie.200905466
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发表时间：
2009-01-01
影响因子：
16.6
通讯作者：
O'Hare, Dermot
中科院分区：
文献类型：
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作者：
Ashley, Andrew E.;Thompson, Amber L.;O'Hare, Dermot
二氧化碳作为一种温室气体的作用及其对全球变暖的贡献得到了科学家和政府机构的广泛认可。[1]现在迫切需要发现新的反应和过程，以环境友好的方式有效地储存或利用丰富的可再生二氧化碳资源。然而，我们面临着一个根本性的挑战，因为二氧化碳在动力学和热力学上都非常稳定。非极性二氧化碳分子在固体中的储存已被证明是困难的，但通过使用一系列高比表面积的大孔和微孔材料，如无机材料(如氧化铝、二氧化硅和沸石)、有机材料(如活性碳材料)和复杂的金属-有机骨架(MOF)，正在取得进展。[2]可以说，更理想的结果是将二氧化碳低温转化为有用的化学品，既可用于能源，也可用作化学原料。以这种方式转化二氧化碳将有减少我们对化石燃料的需求的额外好处。利用二氧化碳生产一氧化碳以及甲酸及其衍生物的均相和非均相工艺已经被开发出来。然而，这些反应还很不理想，因此需要进一步的突破性技术。特别令人感兴趣的是氢还原二氧化碳以获得可再生资源，如甲醇。甲醇被认为是一种有价值的产品，因为它可以安全地储存和运输。目前世界对CH3OH的需求正在大幅增加，因为它是许多有用的有机化学品(如甲醛、醋酸)的前体，作为燃料的替代品，并在燃料电池中发电。CO2加氢生成CH3OH在热力学上是有利的，但它不是CO2与H2最有利的转化(方案1)。CO2加氢在固体氧化物催化剂上得到了广泛的发展；Sasaki等人首次报道了在均相溶液中，他们使用了[Ru3(CO)12]/KI混合物.
The role of carbon dioxide as a greenhouse gas and its contribution to global warming are widely recognized by both scientists and governmental agencies.[1] It is now imperative that new reactions and processes are discovered for the efficient storage or utilization of the abundant and renewable CO2 resource in an environmentally friendly manner. However, we face a fundamental challenge in that carbon dioxide is very kinetically and thermodynamically stable. Storage of the nonpolar CO2 molecule in a solid has proven difficult, yet progress is being made through the use of a range of high-surface-area macro-and microporous materials, such as inorganic materials (eg alumina, silicas, and zeolites), organic materials (eg activated carbon materials), and complex metal–organic frameworks (MOFs).[2] Arguably a more desirable outcome would be the low-temperature conversion of CO2 into useful chemicals for both energy and as chemical feedstocks. The transformation of CO2 in this manner would have the additional benefit of reducing our fossil-fuel requirements. Homogeneous and heterogeneous processes have been developed that utilize CO2 to produce CO as well as formic acid and its derivatives.[3] However, these reactions are far from ideal, and so further breakthrough technologies are required.Of particular interest is the reduction of CO2 by H2 to give renewable sources, such as methanol. CH3OH is considered to be a valuable product because it can be stored and transported safely. World demand for CH3OH is currently increasing enormously because of its role as a precursor to many useful organic chemicals (eg formaldehyde, acetic acid), as a substitute for fuels, and in the generation of electricity in fuel cells. The hydrogenation of CO2 to CH3OH is thermodynamically favorable, but it is not the most favorable transformation of CO2 with H2 (Scheme 1). CO2 hydrogenation has been developed extensively with solid oxide catalysts; it was first reported in homogeneous solution by Sasaki and co-workers, who used [Ru3 (CO) 12]/KI mix-