Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation
Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation
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DOI：
10.1038/nmat3347
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发表时间：
2012-08-01
期刊：
影响因子：
41.2
通讯作者：
Grin, Yu
中科院分区：
文献类型：
--
作者：
Armbruester, M.;Kovnir, K.;Grin, Yu
100多年来，用低成本的替代品取代非均相催化剂中的贵金属一直推动着科学和工业研究。廉价且无处不在的铁尤其受欢迎，因为它不像镍那样有潜在的健康风险。为了净化乙烯原料用于生产聚乙烯，采用乙炔半加氢法（80 × 10(6)吨/年）；参考文献1 - 3)。小而分离的过渡金属原子系综的存在（所谓的位点隔离）和抑制氢化物的形成有利于催化性能（4-6）。对于不饱和C-C键的氢化，铁催化剂至少需要50巴和100摄氏度，对半氢化只有有限的选择性（7-13）。催化半氢化的最新创新是基于对替代合金的计算筛选，以利用尺度函数识别有前途的金属组合（14），以及利用结构有序且原位稳定的Ga与Pd的金属间化合物实现位点隔离概念的实验实现（参考文献15-19）。通过将观察到的催化性质分配给金属间化合物的晶体和电子结构，稳定性使得基于知识的开发成为可能（20,21）。根据这种方法，我们确定了低成本和环保的金属间化合物Al13Fe4作为活性和选择性半加氢催化剂。这种以知识为基础的发展可能被证明适用于广泛的多相催化反应。
Replacing noble metals in heterogeneous catalysts by low-cost substitutes has driven scientific and industrial research for more than 100 years. Cheap and ubiquitous iron is especially desirable, because it does not bear potential health risks like, for example, nickel. To purify the ethylene feed for the production of polyethylene, the semi-hydrogenation of acetylene is applied (80 x 10(6) tons per annum; refs 1-3). The presence of small and separated transition-metal atom ensembles (so-called site-isolation), and the suppression of hydride formation are beneficial for the catalytic performance(4-6). Iron catalysts necessitate at least 50 bar and 100 degrees C for the hydrogenation of unsaturated C-C bonds, showing only limited selectivity towards semi-hydrogenation(7-13). Recent innovation in catalytic semi-hydrogenation is based on computational screening of substitutional alloys to identify promising metal combinations using scaling functions(14) and the experimental realization of the site-isolation concept employing structurally well-ordered and in situ stable intermetallic compounds of Ga with Pd (refs 15-19). The stability enables a knowledge-based development by assigning the observed catalytic properties to the crystal and electronic structures of the intermetallic compounds(20,21). Following this approach, we identified the low-cost and environmentally benign intermetallic compound Al13Fe4 as an active and selective semi-hydrogenation catalyst. This knowledge-based development might prove applicable to a wide range of heterogeneously catalysed reactions.