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控制二氧化铈负载金属纳米颗粒催化的聚酰胺氢解反应的选择性。

Controlling the selectivity of the hydrogenolysis of polyamides catalysed by ceria-supported metal nanoparticles.

作者信息

Wu XinBang, Lee Wei-Tse, Turnell-Ritson Roland C, Delannoi Pauline C L, Lin Kun-Han, Dyson Paul J

机构信息

Institute of Chemical Sciences and Engineering, Swiss Federal Institute of Technology Lausanne (EPFL), Lausanne, Switzerland.

Department of Chemical Engineering, National Tsing Hua University (NTHU), Hsinchu, Taiwan.

出版信息

Nat Commun. 2023 Oct 16;14(1):6524. doi: 10.1038/s41467-023-42246-x.

Abstract

Catalytic hydrogenolysis is a promising approach to transform waste plastic into valuable chemicals. However, the transformation of N-containing polymers, such as polyamides (i.e. nylon), remains under-investigated, particularly by heterogeneous catalysis. Here, we demonstrate the hydrogenolysis of various polyamides catalysed by platinum-group metal nanoparticles supported on CeO. Ru/CeO and Pt/CeO are both highly active but display different selectivity; Ru/CeO is selective for the conversion of all polyamides into water, ammonia, and methane, whereas Pt/CeO yields hydrocarbons retaining the carbon backbone of the parent polyamide. Density functional theory computations illustrate that Pt nanoparticles require higher activation energy for carbon-carbon bond cleavage than Ru nanoparticles, rationalising the observed selectivity. The high activity and product selectivity of both catalysts was maintained when converting real-world polyamide products, such as fishing net. This study provides a mechanistic basis for heterogeneously catalysed polyamide hydrogenolysis, and a new approach to the valorisation of polyamide containing waste.

摘要

催化氢解是一种将废塑料转化为有价值化学品的有前景的方法。然而,含氮聚合物(如聚酰胺,即尼龙)的转化仍未得到充分研究,特别是在非均相催化方面。在此,我们展示了负载在CeO上的铂族金属纳米颗粒催化各种聚酰胺的氢解。Ru/CeO和Pt/CeO都具有高活性,但表现出不同的选择性;Ru/CeO能将所有聚酰胺选择性地转化为水、氨和甲烷,而Pt/CeO则生成保留母体聚酰胺碳骨架的碳氢化合物。密度泛函理论计算表明,Pt纳米颗粒比Ru纳米颗粒需要更高的活化能来裂解碳 - 碳键,这解释了观察到的选择性。在转化实际的聚酰胺产品(如渔网)时,两种催化剂都保持了高活性和产物选择性。这项研究为非均相催化聚酰胺氢解提供了机理基础,并为含聚酰胺废物的增值利用提供了新方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f616/10579319/4601f6a0c722/41467_2023_42246_Fig1_HTML.jpg

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