Mechanism of Formic Acid Disproportionation Catalyzed by an Iridium Complex Immobilized on Bipyridine‐Periodic Mesoporous Organosilica: A Case Study based on Kinetics Analysis,Asian Journal of Organic Chemistry

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Mechanism of Formic Acid Disproportionation Catalyzed by an Iridium Complex Immobilized on Bipyridine‐Periodic Mesoporous Organosilica: A Case Study based on Kinetics Analysis
Asian Journal of Organic Chemistry ( IF 2.8 ) Pub Date : 2019-12-23 , DOI: 10.1002/ajoc.201900692
Sho Yamaguchi ₁ , Shunsuke Hashimoto ₁

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This work investigated the kinetics of formic acid (FA) disproportionation using an Ir complex immobilized on bipyridine‐periodic mesoporous organosilica (BPy‐PMO). The selectivity for methanol (MeOH) is increased using this catalyst compared to conventional homogeneous Ir complexes. This enhanced selectivity is attributed to the retention of H₂ and CO₂ generated by the competing FA dehydrogenation in PMO mesochannels having a high aspect ratio. However, no direct evidence for this process was previously obtained. The present work clarified the unique catalysis mechanism associated with a PMO catalyst exhibiting higher MeOH selectivity based on a hypothesis that the generation of MeOH via FA hydrogenation is promoted by the confinement of H₂ in the PMO pores. The results obtained from the present kinetics study and data regarding H₂ diffusion in the PMO pores strongly support this hypothesis.

中文翻译：

固定在联吡啶-周期介孔有机硅上的铱配合物催化甲酸歧化的机理：基于动力学分析的案例研究

这项工作使用固定在联吡啶-周期介孔有机二氧化硅（BPy-PMO）上的Ir配合物研究了甲酸（FA）歧化的动力学。与传统的均相Ir配合物相比，使用该催化剂提高了对甲醇（MeOH）的选择性。这种提高的选择性归因于在高长宽比的PMO介孔中保留了由竞争性FA脱氢产生的H ₂和CO ₂保留。但是，以前没有获得此过程的直接证据。本工作与澄清表现出基于一个假设更高的MeOH选择性经由FA氢化MeOH中的生成是由H的约束促进的PMO催化剂相关联的唯一的催化机制₂在PMO的毛孔中。从目前的动力学研究获得的结果以及有关PMO孔中H ₂扩散的数据强烈支持了这一假设。

更新日期：2019-12-23

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