Intermetallic Nanocatalyst for Highly Active Heterogeneous Hydroformylation
Intermetallic Nanocatalyst for Highly Active Heterogeneous Hydroformylation
复制标题
DOI：
10.1021/jacs.1c09665
复制
发表时间：
2021-12-15
影响因子：
15
通讯作者：
Huang, Wenyu
中科院分区：
文献类型：
--
作者：
Chen, Minda;Gupta, Geet;Huang, Wenyu
加氢甲酰化是传统上由均相催化剂催化的重要化学过程。设计一种在加氢甲酰化中具有高活性和选择性的多相催化剂具有挑战性，但对于方便分离和回收贵重催化剂至关重要。在此，我们报告了一种用于高效非均相加氢甲酰化的出色催化剂的开发，即 RhZn 金属间纳米颗粒。在苯乙烯的加氢甲酰化反应中，与基准均相威尔金森催化剂（966 h(-1)）相比，它的周转频率（3090 h(-1)）高出三倍，并且对醛类产物具有高化学选择性。 RhZn 对多种烯烃底物都具有活性，并且可以回收利用而不会显着丧失活性。密度泛函理论计算表明，与纯Rh(111)相比，RhZn表面降低了反应中间体的结合强度，并且具有更低的加氢甲酰化活化能垒，从而导致RhZn上的反应能量更加有利。计算还预测了实现高区域选择性的潜在催化剂设计策略。
Hydroformylation is an imperative chemical process traditionally catalyzed by homogeneous catalysts. Designing a heterogeneous catalyst with high activity and selectivity in hydroformylation is challenging but essential to allow the convenient separation and recycling of precious catalysts. Here, we report the development of an outstanding catalyst for efficient heterogeneous hydroformylation, RhZn intermetallic nanoparticles. In the hydroformylation of styrene, it shows three times higher turnover frequency (3090 h(-1)) compared to the benchmark homogeneous Wilkinson's catalyst (966 h(-1)), as well as a high chemoselectivity toward aldehyde products. RhZn is active for a variety of olefin substrates and can be recycled without a significant loss of activity. Density functional theory calculations show that the RhZn surfaces reduce the binding strength of reaction intermediates and have lower hydroformylation activation energy barriers compared to pure Rh(111), leading to more favorable reaction energetics on RhZn. The calculations also predict potential catalyst design strategies to achieve high regioselectivity.