上海科技大学刘晓培团队报道了氢溢出增强了Cu-O-Ce界面上α，β-不饱和醛的选择性加氢反应。相关研究成果发表在2024年9月18日出版的《结构化学》。

使用非均相氢化催化剂将α，β-不饱和醛选择性氢化为烯丙醇在工业上具有重要意义，但实现这一目标仍然具有挑战性。由于Cu的电子结构，负载型Cu催化剂显示出适度的选择性，但反应活性较低。

通过将原子分散的Pd原子锚定在暴露的Cu表面上形成Cu@CeO₂，在温和的反应条件下氢溢出会激活Cu@CeO₂惰性金属氧化物界面，转化为用于氢化的高效和选择性的催化位点。所制备的催化剂在丙烯醛的选择性加氢中表现出比Cu@CeO₂高得多的催化活性。

综合研究表明，原子分散的Pd物种对H₂的活化和均裂至关重要。活化的H原子很容易以Cu-H^δ-和Ce-O-H^δ+物种的形式溢出到Cu-O-Ce界面，这使得Cu-O-Ce接口成为极性C=O键氢化的活性位点。此外，烯丙醇在Pd和Cu-O-Ce界面位点上的弱吸附阻碍了深度氢化，导致几种α，β-不饱和醛的选择性氢化。

总的来说，研究人员证明了单原子合金与惰性金属氧化物界面活化为选择性催化位点。

附：英文原文

Title: Hydrogen spillover enhances the selective hydrogenation of α,β-unsaturated aldehydes on the Cu–O–Ce interface

Author: Jinyun Cui, Tingting Yang, Teng Xu, Jin Lin, Kunlong Liu, Pengxin Liu

Issue&Volume: 2024-09-18

Abstract: The industrially important selective hydrogenation of α,β-unsaturated aldehydes to allyl alcohol is still challenging to realize using heterogenous hydrogenation catalysts. Supported Cu catalysts have shown moderate selectivity, yet low activity for the reaction, due to the electronic structure of Cu. By anchoring atomically dispersed Pd atoms onto the exposed Cu surface of Cu@CeO2, we report in this work that hydrogen spillover activates the inert metal-oxide interfaces of Cu@CeO2 into highly effective and selective catalytic sites for hydrogenation under mild reaction conditions. The as-prepared catalysts exhibited much higher catalytic activity in the selective hydrogenation of acrolein than Cu@CeO2. Comprehensive studies revealed that atomically dispersed Pd species are critical for the activation and homolytic splitting of H2. The activated H atoms easily spill to the Cu-O-Ce interfaces as Cu-Hδ- and interfacial Ce-O-Hδ+ species, which makes the Cu-O-Ce interfaces as the active sites for the hydrogenation of polar C=O bonds. Moreover, the weak adsorption of allyl alcohol on the Pd and the Cu-O-Ce interfacial sites prevents deep hydrogenation, leading to selective hydrogenation of several α,β-unsaturated aldehydes. Overall, we demonstrate here a synergic effect between single atom alloy and the support for activation of an inert metal-oxide interface into selective catalytic sites.

DOI: 10.1016/j.cjsc.2024.100438

Source: http://cjsc.ac.cn/cms/issues/701