Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions,Journal of the American Chemical Society

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Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-11-15 00:00:00 , DOI: 10.1021/jacs.7b08252
Tian-Nan Ye _{1,

2} , Yangfan Lu _{1,

2} , Jiang Li _{1,

2} , Takuya Nakao ₃ , Hongsheng Yang _{1,

2} , Tomofumi Tada ₁ , Masaaki Kitano ₁ , Hideo Hosono _{1,

2,

3}

Affiliation

The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a new copper-based intermetallic electride catalyst, LaCu_0.67Si_1.33, in which Cu sites activated by anionic electrons with low work function are atomically dispersed in the lattice framework and affords selective hydrogenation of nitroarenes with above 40-times higher turnover frequencies (TOFs up to 5084 h^–1) than well-studied metal-loaded catalysts. Kinetic analysis utilizing isotope effect reveals that the cleavage of the H–H bond is the rate-determining step. Surprisingly, the high carrier density and low work function (LWF) properties of LaCu_0.67Si_1.33 enable the activation of hydrogen molecules with extreme low activation energy (E_a = 14.8 kJ·mol^–1). Furthermore, preferential adsorption of nitroarenes via a nitro group is achieved by high oxygen affinity of LaCu_0.67Si_1.33 surface, resulting in high chemoselectivity. The present efficient catalyst can further trigger the hydrogenation of other oxygen-containing functional groups such as aldehydes and ketones with high activities. These findings demonstrate that the transition metals incorporated in the specific lattice site function as catalytically active centers and surpass the conventional metal-loaded catalysts in activity and stability.

中文翻译：

用于化学选择加氢反应的铜基金属间化合物催化剂

过渡金属间化合物的开发，其中活性位点并入晶格骨架中，具有很大的潜力来调节活性位点的局部结构和电子性质，并增强催化活性和稳定性。在这里，我们报道了一种新型的铜基金属间电催化剂LaCu _0.67 Si _1.33，其中具有低功函的阴离子电子激活的Cu位原子原子地分散在晶格骨架中，并提供硝基芳烃的选择性加氢，其营业额高40倍以上频率（TOF高达5084 h ^–1），而不是经过深入研究的金属负载催化剂。利用同位素效应的动力学分析表明，氢键的裂解是决定速率的步骤。出乎意料的是，LaCu _0.67 Si _1.33的高载流子密度和低逸出功（LWF）特性使得能够以极低的活化能（E _a = 14.8 kJ·mol ^–1）活化氢分子。此外，LaCu _0.67 Si _1.33的高氧亲合力可实现通过硝基优先吸附硝基芳烃表面，导致高化学选择性。本发明的有效催化剂可以进一步引发具有高活性的其他含氧官能团例如醛和酮的氢化。这些发现表明，结合在特定晶格位点中的过渡金属具有催化活性中心的作用，其活性和稳定性均超过了传统的金属负载催化剂。

更新日期：2017-11-16

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