Structural principles to steer the selectivity of the electrocatalytic reduction of aliphatic ketones on platinum
Structural principles to steer the selectivity of the electrocatalytic reduction of aliphatic ketones on platinum
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DOI：
10.1038/s41929-019-0229-3
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发表时间：
2019-03-01
期刊：
影响因子：
37.8
通讯作者：
Koper, Marc T. M.
中科院分区：
文献类型：
--
作者：
Bondue, Christoph J.;Calle-Vallejo, Federico;Koper, Marc T. M.
由于普遍的原料转变，化学工业的任务是寻找将可再生酮转化为增值产品的方法。这样做的可行途径是羰基官能团的电化学氢化。在这里，我们报告的研究丙酮还原铂单晶电极使用在线电化学质谱，原位傅里叶变换红外光谱和密度泛函理论计算。丙酮在铂还原显示出显着的结构敏感性：不仅活性，而且产品分布取决于表面的晶体取向。在Pt（111）处，既不发生吸附也不发生氢化。使电极失活的分解反应发生在Pt（100）处。丙酮还原在（110）步骤进行：Pt[（n-1）（111）x（110）]电极产生2-丙醇，Pt[（n + 1）（100）x（110）]电极产生丙烷。使用密度泛函理论计算，我们建立了一个选择性地图来解释复杂的丙酮还原铂。最后，我们将我们的结论推广到高级脂肪酮的还原。
Due to a general feedstock shift, the chemical industry is charged with the task of finding ways to transform renewable ketones into value-added products. A viable route to do so is the electrochemical hydrogenation of the carbonyl functional group. Here we report a study on acetone reduction at platinum single-crystal electrodes using online electrochemical mass spectroscopy, in situ Fourier transform infrared spectroscopy and density functional theory calculations. Acetone reduction at platinum displays a remarkable structural sensitivity: not only the activity, but also the product distribution depends on the surface crystallographic orientation. At Pt(111) neither adsorption nor hydrogenation occur. A decomposition reaction that deactivates the electrode happens at Pt(100). Acetone reduction proceeds at the (110) steps: Pt[(n-1)(111) x (110)] electrodes produce 2-propanol and Pt[(n + 1)(100) x (110)] electrodes produce propane. Using density functional theory calculations, we built a selectivity map to explain the intricacies of the acetone reduction on platinum. Finally, we extend our conclusions to the reduction of higher aliphatic ketones.