Isolated Pt Atoms Stabilized by Ga2O3 Clusters Confined in ZSM-5 for Nonoxidative Activation of Ethane

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY JACS Au Pub Date : 2024-08-26 DOI:10.1021/jacsau.4c0048010.1021/jacsau.4c00480
Xiaomeng Dou, Kailang Li, Kun Zhang, Chaofeng Zhu, Debora M. Meira, Yang Song, Peng He*, Liang Zhang* and Lichen Liu*, 
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Abstract

Selective activation of light alkanes is an essential reaction in the petrochemical industry for producing commodity chemicals, such as light olefins and aromatics. Because of the much higher intrinsic activities of noble metals in comparison to non-noble metals, it is desirable to employ solid catalysts with low noble metal loadings to reduce the cost of catalysts. Herein, we report the introduction of a tiny amount of Pt (at levels of hundreds of ppm) as a promoter of the Ga2O3 clusters encapsulated in ZSM-5 zeolite, which leads to ∼20-fold improvement in the activity for ethane dehydrogenation reaction. A combination of experimental and theoretical studies shows that the isolated Pt atoms stabilized by small Ga2O3 clusters are the active sites for activating the inert C–H bonds in ethane. The synergy of atomically dispersed Pt and Ga2O3 clusters confined in the 10MR channels of ZSM-5 can serve as a bifunctional catalyst for the direct ethane–benzene coupling reaction for the production of ethylbenzene, surpassing the performances of the counterpart catalysts made with PtGa nanoclusters and nanoparticles.

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隔离的铂原子通过密闭在 ZSM-5 中的 Ga2O3 簇稳定,用于乙烷的非氧化活化
轻质烷烃的选择性活化是石化工业生产轻质烯烃和芳烃等商品化学品的一个基本反应。与非贵金属相比,贵金属的内在活性要高得多,因此最好采用贵金属负载量低的固体催化剂,以降低催化剂的成本。在此,我们报告了引入微量铂(含量为数百 ppm)作为 ZSM-5 沸石中封装的 Ga2O3 簇的促进剂,从而使乙烷脱氢反应的活性提高了 20 倍。实验和理论研究的综合结果表明,由 Ga2O3 小簇稳定的孤立铂原子是激活乙烷中惰性 C-H 键的活性位点。封闭在 ZSM-5 10MR 沟道中的原子分散铂和 Ga2O3 团簇的协同作用可作为乙烷-苯直接偶联反应的双功能催化剂,用于生产乙苯,其性能超过了用 PtGa 纳米团簇和纳米颗粒制成的对应催化剂。
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