Phenylacetylene hydrogenation coupled with benzyl alcohol dehydrogenation over Cu/CeO2: A consideration of Cu oxidation state
Phenylacetylene hydrogenation coupled with benzyl alcohol dehydrogenation over Cu/CeO2: A consideration of Cu oxidation state
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DOI：
10.1016/j.jcat.2020.11.002
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发表时间：
2020-11
影响因子：
7.3
通讯作者：
Chiara Pischetola;S. Francis;F. Grillo;C. Baddeley;F. Cárdenas-Lizana
中科院分区：
文献类型：
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作者：
Chiara Pischetola;S. Francis;F. Grillo;C. Baddeley;F. Cárdenas-Lizana
我们已经研究了铜的氧化态在连续气相耦合苯乙炔加氢（苯乙烯）与苯甲醇脱氢（苯甲醛）在Cu/CeO 2的效果。通过H2-TPR、XPS、XRD和STEM-EDX分析的分析表明产生了一系列Cu氧化态（Cu 0（13-77%）、Cu+（13-74%）、Cu 2+（0-55%））。在苯乙炔单独加氢反应中，苯乙烯和异戊二烯的逐步生成得到促进。Cu 0/Cu+（来自H2-TPR和XPS）的增加增强了H2化学吸附和苯乙烯TOF，但具有低的氢利用效率。在苯甲醇单独脱氢反应中，苯甲醛和甲苯的生成得到促进，苯甲醛的选择性和TOF与Cu 0.充分利用氢，独家苯甲醛/苯乙烯的形成和（3倍）更大的苯乙烯TOF（达到100%的收率）实现在耦合的过程中，其中氢化/脱氢活性与Cu+/Cu 0。这为非贵金属Cu催化剂上的可持续“无氢”加氢开辟了新的方向。
We have examined the effect of copper oxidation state in the continuous gas phase coupled phenylacetylene hydrogenation (to styrene) with benzyl alcohol dehydrogenation (to benzaldehyde) over Cu/CeO2. Analysis by H2-TPR, XPS, XRD and STEM-EDX analyses demonstrates the generation of a range of Cu oxidation states (Cu0(13–77%), Cu+(13–74%), Cu2+(0–55%)). The stepwise formation of styrene and ethylbenzene was promoted in the stand-alone phenylacetylene hydrogenation. An increase in Cu0/Cu+(from H2-TPR and XPS) enhanced H2chemisorption and styreneTOF, but with low hydrogen utilisation efficiency. The formation of benzaldehyde and toluene was promoted in the stand-alone dehydrogenation of benzyl alcohol, where benzaldehyde selectivity andTOFcorrelate with the concentration of Cu0. Full hydrogen utilisation, exclusive benzaldehyde/styrene formation and a (3-fold) greater styreneTOF(to attain 100% yield) was achieved in the coupled process, where hydrogenation/dehydrogenation activity correlates with Cu+/Cu0. This opens new directions for sustainable “hydrogen free” hydrogenations overnon-noble Cu catalysts.