Selectivity for ethanol partial oxidation: the unique chemistry of single-atom alloy catalysts on Au, Ag, and Cu(111)
Selectivity for ethanol partial oxidation: the unique chemistry of single-atom alloy catalysts on Au, Ag, and Cu(111)
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DOI：
10.1039/c9ta04572d
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发表时间：
2019-11-07
影响因子：
11.9
通讯作者：
Henkelman, Graeme
中科院分区：
文献类型：
--
作者：
Li, Hao;Chai, Wenrui;Henkelman, Graeme
最近，我们发现，原子系综效应是影响强结合元素和弱结合元素合金化表面催化的主导效应，决定了合金表面上许多反应的活性和选择性。在这项研究中，我们设计的单原子合金，具有独特的脱氢选择性对乙醇（EtOH）的部分氧化，使用密度泛函理论计算的合金化效应的知识。我们发现，掺杂强结合的单原子元素（例如，Ir、Pd、Pt和Rh）结合到弱结合惰性密堆积基底（例如，Au、Ag和Cu）导致在吸附的EtOH的α-C-H位点处的高度活性和选择性的初始脱氢。我们发现，许多这些稳定的单原子合金表面不仅具有可调的氢键，这使得容易的氢解吸，但也耐碳焦化。更重要的是，我们表明，一个合理的设计的系综几何结构可以调整催化反应的选择性。
Recently, we found that the atomic ensemble effect is the dominant effect influencing catalysis on surfaces alloyed with strong- and weak-binding elements, determining the activity and selectivity of many reactions on the alloy surface. In this study we design single-atom alloys that possess unique dehydrogenation selectivity towards ethanol (EtOH) partial oxidation, using knowledge of the alloying effects from density functional theory calculations. We found that doping of a strong-binding single-atom element (e.g., Ir, Pd, Pt, and Rh) into weak-binding inert close-packed substrates (e.g., Au, Ag, and Cu) leads to a highly active and selective initial dehydrogenation at the alpha-C-H site of adsorbed EtOH. We show that many of these stable single-atom alloy surfaces not only have tunable hydrogen binding, which allows for facile hydrogen desorption, but are also resistant to carbon coking. More importantly, we show that a rational design of the ensemble geometry can tune the selectivity of a catalytic reaction.