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用于高效脱氢芳构化的超低负载量Pt/Zn杂化簇负载于沸石HZSM-5中

Ultralow-Loading Pt/Zn Hybrid Cluster in Zeolite HZSM-5 for Efficient Dehydroaromatization.

作者信息

Chen Genwei, Fang Lingzhe, Li Tao, Xiang Yizhi

机构信息

Dave C. Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, Mississippi 39762, United States.

Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, United States.

出版信息

J Am Chem Soc. 2022 Jul 6;144(26):11831-11839. doi: 10.1021/jacs.2c04278. Epub 2022 Jun 24.

Abstract

Minimizing Pt loading without sacrificing catalytic performance is critical, particularly for designing cost-efficient hydrocarbon transformation catalysts. Here, we show that ultralow-loading (0.001-0.05 wt %) Pt- and Zn-functionalized HZSM-5 catalysts, prepared through simple ion exchange and impregnation, are highly active and stable for light alkane dehydroaromatization (DHA). The specific activity of benzene, toluene, and xylene is up to 8.2 mol/g/min (or 1592 min) over the 0.001 wt % Pt-Zn/HZSM-5 catalyst during ethane DHA at 550 °C under atmospheric pressure. Additionally, such bimetallic Pt-Zn/HZSM-5 catalysts are highly stable in contrast to the monometallic Pt/HZSM-5 catalysts. The rate constant of deactivation (), according to the first-order generalized power law equation model, for the bimetallic catalysts is up to 120 times lower than that of the monometallic counterparts, depending on the Pt loading. This breakthrough is achieved through the formation of the [Pt-Zn] hybrid cluster, instead of Pt cluster-proton adducts, in the micropores of the ZSM-5 zeolite.

摘要

在不牺牲催化性能的前提下尽量减少铂负载量至关重要,这对于设计具有成本效益的烃类转化催化剂尤为关键。在此,我们表明,通过简单的离子交换和浸渍制备的超低负载量(0.001 - 0.05 wt%)的铂和锌功能化HZSM - 5催化剂,对于轻质烷烃脱氢芳构化(DHA)具有高活性和稳定性。在550℃、常压下乙烷脱氢芳构化过程中,0.001 wt%的Pt - Zn/HZSM - 5催化剂上苯、甲苯和二甲苯的比活性高达8.2 mol/g/min(或1592 min)。此外,与单金属Pt/HZSM - 5催化剂相比,这种双金属Pt - Zn/HZSM - 5催化剂具有高度稳定性。根据一级广义幂律方程模型,双金属催化剂的失活速率常数()比单金属催化剂低达120倍,这取决于铂负载量。这一突破是通过在ZSM - 5沸石的微孔中形成[Pt - Zn]杂化簇而非铂簇 - 质子加合物实现的。

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