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用于活性和稳定丙烷脱氢催化剂的铂多金属合金的动态行为

Dynamic Behavior of Pt Multimetallic Alloys for Active and Stable Propane Dehydrogenation Catalysts.

作者信息

Werghi Baraa, Saini Shikha, Chung Pin-Hung, Kumar Abinash, Ebrahim Amani M, Abels Kristen, Chi Miaofang, Abild-Pedersen Frank, Bare Simon R, Cargnello Matteo

机构信息

Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.

SSRL, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.

出版信息

J Am Chem Soc. 2024 Nov 13;146(45):30966-30975. doi: 10.1021/jacs.4c09424. Epub 2024 Oct 30.

Abstract

Improving the use of platinum in propane dehydrogenation catalysts is a crucial aspect to increasing the efficiency and sustainability of propylene production. A known and practiced strategy involves incorporating more abundant metals in supported platinum catalysts, increasing its activity and stability while decreasing the overall loading. Here, using colloidal techniques to control the size and composition of the active phase, we show that Pt/Cu alloy nanoparticles supported on alumina (Pt/Cu/AlO) displayed elevated rates for propane dehydrogenation at low temperature compared to a monometallic Pt/AlO catalyst. We demonstrate that the enhanced catalytic activity is correlated with a higher surface Cu content and formation of a Pt-rich core and Cu-rich shell that isolates Pt sites and increases their intrinsic activity. However, rates declined on stream because of dynamic metal diffusion processes that led to a more uniform alloy structure. This transformation was only partially inhibited by adding excess hydrogen to the feed stream. Instead, cobalt was introduced to provide trimetallic Pt/Cu/Co catalysts with stabilized surface structure and stable activity and higher rates than the original Pt/Cu system. The structure-activity relationship insights in this work offer improved knowledge of propane dehydrogenation catalyst development featuring reduced Pt loadings and notable thermal stability for propylene production.

摘要

提高铂在丙烷脱氢催化剂中的利用率是提高丙烯生产效率和可持续性的关键因素。一种已知且常用的策略是在负载型铂催化剂中加入更丰富的金属,提高其活性和稳定性,同时降低总体负载量。在此,我们利用胶体技术控制活性相的尺寸和组成,结果表明,与单金属Pt/AlO催化剂相比,负载在氧化铝上的Pt/Cu合金纳米颗粒(Pt/Cu/AlO)在低温下丙烷脱氢速率更高。我们证明,增强的催化活性与更高的表面铜含量以及形成富铂核心和富铜壳层有关,该壳层隔离了铂位点并提高了其固有活性。然而,由于动态金属扩散过程导致合金结构更加均匀,反应过程中的速率下降。通过向进料流中添加过量氢气,这种转变仅得到部分抑制。相反,引入钴以提供具有稳定表面结构、稳定活性且比原始Pt/Cu体系具有更高速率的三金属Pt/Cu/Co催化剂。这项工作中关于结构-活性关系的见解为丙烷脱氢催化剂的开发提供了更深入的认识,该催化剂具有降低的铂负载量和用于丙烯生产的显著热稳定性。

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