Experimental and theoretical studies of reaction pathways of direct propylene epoxidation on model catalyst surfaces

IF 8.2 1区 化学 Q1 CHEMISTRY, PHYSICAL
William N. Porter, Zhexi Lin, Jingguang G. Chen
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引用次数: 10

Abstract

The direct epoxidation of propylene to propylene oxide (PO) using molecular oxygen is an attractive alternative to current production methods using chlorohydrin or hydroperoxide-mediated processes, which are environmentally harmful and expensive. Although direct ethylene epoxidation using Ag-based catalysts has been practiced industrially for decades, due to the presence of allylic hydrogen in propylene the selectivity toward epoxide is generally much lower for propylene than for ethylene. Mechanistic understanding on well-characterized surfaces of model catalysts can potentially provide guidance to effectively alter the electronic properties of the catalyst in order to increase PO selectivity. This review summarizes both experimental and theoretical studies on model catalysts for propylene epoxidation and their contributions to elucidating the reaction mechanism, intermediates, and active sites. We first show examples of experimental studies on Cu, Ag, and Au surfaces, and compare the reaction pathways and intermediates on these surfaces. Novel approaches including plasmon-mediated catalysis and utilization of shape-controlled crystal facets that open new opportunities for improving PO selectivity will also be discussed. We then describe how density functional theory (DFT) calculations have provided important insights into the reaction mechanism and active sites on Cu, Ag, and Au surfaces and clusters. Propylene oxidation pathways on other relevant metal surfaces will also be discussed. The combined experimental and computational studies elucidate the nature of surface oxygen species and the role of the oxametallacycle intermediate. We conclude by highlighting design principles and insights for guiding further development of active and selective propylene epoxidation catalysts.

模型催化剂表面丙烯直接环氧化反应途径的实验与理论研究
利用分子氧将丙烯直接环氧化为环氧丙烷(PO)是目前使用氯丙烷或过氧化氢介导的生产方法的一种有吸引力的替代方法,这些方法对环境有害且价格昂贵。虽然使用银基催化剂直接环氧化乙烯已经在工业上实践了几十年,但由于丙烯中烯丙基氢的存在,丙烯对环氧化物的选择性通常比乙烯低得多。对模型催化剂表征良好的表面的机理理解,可能为有效改变催化剂的电子性质以提高PO选择性提供指导。本文综述了丙烯环氧化模型催化剂的实验和理论研究,以及它们在阐明反应机理、中间体和活性位点方面的贡献。我们首先展示了Cu、Ag和Au表面的实验研究实例,并比较了这些表面上的反应途径和中间体。新的方法包括等离子体介导的催化和利用形状控制的晶体面,为提高PO选择性开辟了新的机会,也将讨论。然后,我们描述了密度泛函理论(DFT)计算如何为Cu, Ag和Au表面和簇上的反应机理和活性位点提供了重要的见解。丙烯在其他相关金属表面的氧化途径也将讨论。实验和计算相结合的研究阐明了表面氧的性质和氧金属环中间体的作用。最后,我们强调了设计原则和见解,以指导进一步开发活性和选择性丙烯环氧化催化剂。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Surface Science Reports
Surface Science Reports 化学-物理:凝聚态物理
CiteScore
15.90
自引率
2.00%
发文量
9
审稿时长
178 days
期刊介绍: Surface Science Reports is a journal that specializes in invited review papers on experimental and theoretical studies in the physics, chemistry, and pioneering applications of surfaces, interfaces, and nanostructures. The topics covered in the journal aim to contribute to a better understanding of the fundamental phenomena that occur on surfaces and interfaces, as well as the application of this knowledge to the development of materials, processes, and devices. In this journal, the term "surfaces" encompasses all interfaces between solids, liquids, polymers, biomaterials, nanostructures, soft matter, gases, and vacuum. Additionally, the journal includes reviews of experimental techniques and methods used to characterize surfaces and surface processes, such as those based on the interactions of photons, electrons, and ions with surfaces.
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