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用于丁烷厌氧氧化脱氢的碱金属卤化物包覆的钙钛矿氧化还原催化剂。

Alkali metal halide-coated perovskite redox catalysts for anaerobic oxidative dehydrogenation of -butane.

作者信息

Gao Yunfei, Wang Xijun, Corolla Noel, Eldred Tim, Bose Arnab, Gao Wenpei, Li Fanxing

机构信息

North Carolina State University, Campus Box 7905, Raleigh, NC 27695-7905, USA.

Institute of Clean Coal Technology, East China University of Science and Technology, Shanghai 200237, China.

出版信息

Sci Adv. 2022 Jul 29;8(30):eabo7343. doi: 10.1126/sciadv.abo7343. Epub 2022 Jul 27.

Abstract

Oxidative dehydrogenation (ODH) of -butane has the potential to efficiently produce butadiene without equilibrium limitation or coke formation. Despite extensive research efforts, single-pass butadiene yields are limited to <23% in conventional catalytic ODH with gaseous O. This article reports molten LiBr as an effective promoter to modify a redox-active perovskite oxide, i.e., LaSrFeO (LSF), for chemical looping-oxidative dehydrogenation of -butane (CL-ODHB). Under the working state, the redox catalyst is composed of a molten LiBr layer covering the solid LSF substrate. Characterizations and ab initio molecular dynamics (AIMD) simulations indicate that peroxide species formed on LSF react with molten LiBr to form active atomic Br, which act as reaction intermediates for C─H bond activation. Meanwhile, molten LiBr layer inhibits unselective CO formation, leading to 42.5% butadiene yield. The redox catalyst design strategy can be extended to CL-ODH of other light alkanes such as -butane conversion to -butylene, providing a generalized approach for olefin production.

摘要

正丁烷的氧化脱氢(ODH)具有在无平衡限制或积炭的情况下高效生产丁二烯的潜力。尽管进行了广泛的研究,但在传统的以气态氧气进行催化ODH过程中,单程丁二烯产率限制在<23%。本文报道了熔融溴化锂作为一种有效的促进剂,用于改性氧化还原活性钙钛矿氧化物,即LaSrFeO(LSF),用于正丁烷的化学链氧化脱氢(CL-ODHB)。在工作状态下,氧化还原催化剂由覆盖在固体LSF基底上的熔融溴化锂层组成。表征和从头算分子动力学(AIMD)模拟表明,在LSF上形成的过氧化物物种与熔融溴化锂反应形成活性原子溴,其作为C─H键活化的反应中间体。同时,熔融溴化锂层抑制了非选择性CO的形成,丁二烯产率达到42.5%。这种氧化还原催化剂设计策略可扩展到其他轻质烷烃的CL-ODH,如正丁烷转化为丁烯,为烯烃生产提供了一种通用方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5504/9328686/ae9d217deda6/sciadv.abo7343-f1.jpg

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