Design of highly selective ethanol dehydration nanocatalysts for ethylene production
Design of highly selective ethanol dehydration nanocatalysts for ethylene production
复制标题
用于乙烯生产的高选择性乙醇脱水纳米催化剂的设计
DOI：
10.1039/c7nr08678d
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发表时间：
2018
期刊：
影响因子：
6.7
通讯作者：
Mpourmpakis, Giannis
中科院分区：
文献类型：
--
作者：
Austin, Natalie;Kostetskyy, Pavlo;Mpourmpakis, Giannis
合理设计用于将醇选择性转化为烯烃的催化剂是关键，因为由于竞争的醚化反应，产物选择性仍然是一个问题。使用第一性原理计算和化学规则，我们设计了新型的金属氧化物保护的金属纳米团簇（M13X4O12，与M = Cu，Ag，和Au和X = Al，Ga，和In）在其表面上表现出强的刘易斯酸位点，从醇选择性地形成烯烃的活性。这些对称的纳米催化剂，由于其曲率，显示出不利的醚化化学，而有利于烯烃生产。此外，我们确定，水的去除和再生的纳米催化剂是更可行的相比，用于醇脱水的固体酸上的等价强酸位点。我们的研究结果表明，这些新的纳米结构具有优异的稳定性，其中最有利的是基于Cu的。因此，高选择性和稳定性，这些在硅片预测的新型纳米团簇（如Cu13Al4O12）使他们有吸引力的催化剂，用于选择性脱水醇烯烃。
Rational design of catalysts for selective conversion of alcohols to olefins is key since product selectivity remains an issue due to competing etherification reactions. Using first principles calculations and chemical rules, we designed novel metal–oxide-protected metal nanoclusters (M13X4O12, with M = Cu, Ag, and Au and X = Al, Ga, and In) exhibiting strong Lewis acid sites on their surface, active for the selective formation of olefins from alcohols. These symmetrical nanocatalysts, due to their curvature, show unfavorable etherification chemistries, while favoring the olefin production. Furthermore, we determined that water removal and regeneration of the nanocatalysts is more feasible compared to the equivalent strong acid sites on solid acids used for alcohol dehydration. Our results demonstrate an exceptional stability of these new nanostructures with the most energetically favorable being Cu-based. Thus, the high selectivity and stability of these in-silico-predicted novel nanoclusters (e.g. Cu13Al4O12) make them attractive catalysts for the selective dehydration of alcohols to olefins.