Selective Hydrogenation over Supported Metal Catalysts: From Nanoparticles to Single Atoms.
Selective Hydrogenation over Supported Metal Catalysts: From Nanoparticles to Single Atoms.
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DOI：
10.1021/acs.chemrev.9b00230
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发表时间：
2019-09
期刊：
影响因子：
62.1
通讯作者：
Leilei Zhang;M. Zhou;Aiqin Wang;Tao Zhang
中科院分区：
文献类型：
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作者：
Leilei Zhang;M. Zhou;Aiqin Wang;Tao Zhang
选择性催化加氢在石油化工和精细化工领域有着广泛的应用，但当底物中同时存在两种或多种官能团时，选择性催化加氢仍具有挑战性。为了应对这一挑战，“主动场地隔离”策略已被证明是有效的，并且已经开发了各种场地隔离方法。本文综述了近年来在金属表面吸附/接枝含N/S的有机分子、通过掺杂或金属与载体的强相互作用使金属氧化物部分覆盖活性金属表面、将活性金属纳米颗粒限制在载体的微孔或介孔中、- 与相对惰性的金属（IB和II B）或非金属元素（B、C、S等）形成双金属合金或金属间化合物或核@壳结构，以及在可还原氧化物或惰性金属上构建单原子催化剂。讨论了三种不同的化学选择性氢化反应的位置分离方法的优缺点，包括从炔/二烯到单烯，从α，β-不饱和醛/酮到不饱和醇，从取代硝基芳烃到相应的苯胺的位置分离。影响催化活性/选择性的关键因素，特别是，活性位点的几何和电子结构，进行了讨论，旨在提取的基本原则，为开发高效和选择性的催化剂在加氢以及其他转换。
Selective catalytic hydrogenation has wide applications in both petrochemical and fine chemical industries, however, it remains challenging when two or multiple functional groups coexist in the substrate. To tackle this challenge, the "active site isolation" strategy has been proved effective, and various approaches to the site isolation have been developed. In this review, we have summarized these approaches, including adsorption/grafting of N/S-containing organic molecules on the metal surface, partial covering of active metal surface by metal oxides either via doping or through strong metal-support interaction, confinement of active metal nanoparticles in micro- or mesopores of the supports, formation of bimetallic alloys or intermetallics or core@shell structures with a relatively inert metal (IB and IIB) or nonmetal element (B, C, S, etc.), and construction of single-atom catalysts on reducible oxides or inert metals. Both advantages and disadvantages of each approach toward the site isolation have been discussed for three types of chemoselective hydrogenation reactions, including alkynes/dienes to monoenes, α,β-unsaturated aldehydes/ketones to the unsaturated alcohols, and substituted nitroarenes to the corresponding anilines. The key factors affecting the catalytic activity/selectivity, in particular, the geometric and electronic structure of the active sites, are discussed with the aim to extract fundamental principles for the development of efficient and selective catalysts in hydrogenation as well as other transformations.