High-Density Formation of Ir/MoOx Interface through Hybrid Clustering for Chemoselective Nitrostyrene Hydrogenation

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY ACS Organic & Inorganic Au Pub Date : 2023-07-13 DOI:10.1021/acsorginorgau.3c00017
Shun Hayashi*,  and , Tetsuya Shishido, 
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Abstract

To form high-density metal/oxide interfacial active sites, we developed a catalyst preparation method based on hybrid clustering. An iridium–molybdenum (Ir–Mo) hybrid clustering catalyst was prepared by using the hybrid cluster [(IrCp*)4Mo4O16] (Cp* = η5-C5Me5) as the precursor. The Ir–Mo hybrid clustering catalyst selectively reduced the nitro group in the hydrogenation of 4-nitrostyrene, whereas the coimpregnated Ir–Mo catalyst reduced both the nitro and vinyl groups nonselectively. The hybrid clustering catalyst also exhibited high selectivity, even at a high Ir loading (5 wt %), in contrast to Ir/MoO3, which exhibited high selectivity only at low Ir loadings (<0.3 wt %). In situ X-ray absorption spectroscopy analysis revealed that oxygen vacancies were formed at the Ir/MoOx interface in the presence of H2. We concluded that a high-density Ir/MoOx interface contributes to the preferential adsorption of nitro groups on vacant sites, promoting the selective hydrogenation of nitro groups.

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化学选择性硝基苯乙烯加氢反应中Ir/MoOx界面的高密度形成
为了形成高密度的金属/氧化物界面活性位点,我们开发了一种基于混合聚类的催化剂制备方法。以杂化簇合物[(IrCp*)4Mo4O16](Cp*=η5-C5Me5)为前驱体,制备了铱钼(Ir–Mo)杂化簇合催化剂。Ir–Mo杂化簇催化剂选择性地还原了4-硝基苯乙烯加氢过程中的硝基,而共聚的Ir–Mo催化剂非选择性地同时还原了硝基和乙烯基。与仅在低Ir负载量(<0.3wt%)下表现出高选择性的Ir/MoO3相比,即使在高Ir负载(5wt%)下,混合簇催化剂也表现出高的选择性。原位X射线吸收光谱分析表明,在H2存在的情况下,在Ir/MoOx界面形成了氧空位。我们得出结论,高密度Ir/MoOx界面有助于硝基在空位上的优先吸附,促进硝基的选择性氢化。
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来源期刊
ACS Organic & Inorganic Au
ACS Organic & Inorganic Au 有机化学、无机化学-
CiteScore
4.10
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0.00%
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期刊介绍: ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.
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