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用于金属催化乙炔氢氯化反应的碳载体设计

Design of carbon supports for metal-catalyzed acetylene hydrochlorination.

作者信息

Kaiser Selina K, Surin Ivan, Amorós-Pérez Ana, Büchele Simon, Krumeich Frank, Clark Adam H, Román-Martínez Maria C, Lillo-Ródenas Maria A, Pérez-Ramírez Javier

机构信息

Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich, Switzerland.

Department of Inorganic Chemistry and Materials Institute (IUMA), University of Alicante, Alicante, Spain.

出版信息

Nat Commun. 2021 Jun 29;12(1):4016. doi: 10.1038/s41467-021-24330-2.

Abstract

For decades, carbons have been the support of choice in acetylene hydrochlorination, a key industrial process for polyvinyl chloride manufacture. However, no unequivocal design criteria could be established to date, due to the complex interplay between the carbon host and the metal nanostructure. Herein, we disentangle the roles of carbon in determining activity and stability of platinum-, ruthenium-, and gold-based hydrochlorination catalysts and derive descriptors for optimal host design, by systematically varying the porous properties and surface functionalization of carbon, while preserving the active metal sites. The acetylene adsorption capacity is identified as central activity descriptor, while the density of acidic oxygen sites determines the coking tendency and thus catalyst stability. With this understanding, a platinum single-atom catalyst is developed with stable catalytic performance under two-fold accelerated deactivation conditions compared to the state-of-the-art system, marking a step ahead towards sustainable PVC production.

摘要

几十年来,碳一直是乙炔氢氯化反应中首选的载体,该反应是制造聚氯乙烯的关键工业过程。然而,由于碳载体与金属纳米结构之间复杂的相互作用,迄今为止尚未能确立明确的设计标准。在此,我们通过系统地改变碳的多孔性质和表面功能化,同时保留活性金属位点,厘清了碳在决定铂基、钌基和金基氢氯化催化剂的活性和稳定性方面的作用,并得出了优化载体设计的描述符。乙炔吸附容量被确定为核心活性描述符,而酸性氧位点的密度决定了结焦倾向,进而决定了催化剂的稳定性。基于这一认识,我们开发了一种铂单原子催化剂,与现有技术体系相比,在两倍加速失活条件下具有稳定的催化性能,这标志着朝着可持续聚氯乙烯生产迈出了一步。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e209/8242080/5721cd6127d2/41467_2021_24330_Fig1_HTML.jpg

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