Yang Huan, Wang Xu, Xie Ya-Dong, Lu An-Hui
State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China.
ACS Appl Mater Interfaces. 2024 Sep 11;16(36):47773-47783. doi: 10.1021/acsami.4c11358. Epub 2024 Aug 28.
Alumina-supported PtSn is an industrialized catalyst for propane dehydrogenation. During the catalyst impregnation, the acidic impregnation solution with chloroplatinic acid as a precursor inevitably leads to the partial dissolution of the surface of amphoteric alumina support and finally varies catalytic performance. Herein, the structure evolution of the active phase, induced by an impregnated acidic solution, was studied with special care. According to the diffused double layer theory, we proposed a model of microgels during impregnation. The microgels formed in the solution with suitable acidity on the surface of the catalysts evolved into a structure of AlO-coated oxidized Pt by reprecipitation during drying and calcination. The covered Pt species could be exposed by Ar sputtering or migrate to the surface during reduction to serve as active sites for propane dehydrogenation. Noticeably, the surface Sn species was generated when the pH of the impregnated solution was around 0.56, which is solid proof for the unique active phase with the PtSn alloy present on SnO species existing on the surface of the Sn-AlO support. The synthesized catalyst exhibited high propylene selectivity (99.4%) and superior stability ( = 0.002 h). This study provides new insight for the precise preparation of Pt/Sn-AlO catalysts.
氧化铝负载的PtSn是一种用于丙烷脱氢的工业化催化剂。在催化剂浸渍过程中,以氯铂酸为前驱体的酸性浸渍溶液不可避免地导致两性氧化铝载体表面部分溶解,最终改变催化性能。在此,我们特别关注了浸渍酸性溶液引起的活性相结构演变。根据扩散双层理论,我们提出了浸渍过程中的微凝胶模型。在催化剂表面具有合适酸度的溶液中形成的微凝胶在干燥和煅烧过程中通过再沉淀演变成AlO包覆的氧化Pt结构。包覆的Pt物种可以通过Ar溅射暴露出来,或者在还原过程中迁移到表面,作为丙烷脱氢的活性位点。值得注意的是,当浸渍溶液的pH值约为0.56时会生成表面Sn物种,这有力地证明了在Sn-AlO载体表面存在的SnO物种上存在PtSn合金的独特活性相。合成的催化剂表现出高丙烯选择性(99.4%)和优异的稳定性(= 0.002 h)。该研究为精确制备Pt/Sn-AlO催化剂提供了新的见解。