Lattice oxygen modulation for efficient chemical looping redox oxidative cracking of cycloalkane to light olefins: The influence of the active sites configuration

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL Journal of Catalysis Pub Date : 2024-09-07 DOI:10.1016/j.jcat.2024.115727

Lei Chen , Jinshan Chi , Li Chen , Wei Xiong , Yunfei Gao , Fang Hao

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Abstract

The local environment of active sites is a key focus in the field of redox chemistry research. Here, the manipulation of lattice oxygen in La_0.8Sr_0.2Fe_0.8M_0.2O₃ facilitates the chemical looping redox oxidative cracking (CL-ROC) process. Among the samples, La_0.8Sr_0.2Fe_0.8Cu_0.2O₃ exhibits exceptional olefin yield (61.74 %) in the cyclohexane CL-ROC reaction. The integration of experiments and density theory calculations shows that the introduction of foreign redox-inert cations into the B-sites of the matrix can effectively alter the configuration of FeO₆, improve the activation of lattice oxygen, and enhance the activity of surface oxygen and the mobility of bulk lattice oxygen. Furthermore, the improvement in olefin selectivity is closely linked to the suppression of peroxide products formation, a result of increased oxygen vacancy and decreased bulk lattice oxygen. These findings exemplify the feasibility to manipulate the activity of lattice oxygen in perovskite oxides by adjusting the distortion of the BO₆ in ABO₃ perovskite structures.

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通过晶格氧调制实现环烷到轻质烯烃的高效化学循环氧化还原裂解：活性位点构型的影响

活性位点的局部环境是氧化还原化学研究领域的一个重点。在这里，对 La0.8Sr0.2Fe0.8M0.2O3 中晶格氧的处理促进了化学循环氧化还原裂解（CL-ROC）过程。在这些样品中，La0.8Sr0.2Fe0.8Cu0.2O3 在环己烷 CL-ROC 反应中表现出优异的烯烃产率（61.74%）。实验和密度理论计算的综合结果表明，在基质的 B 位引入外来氧化还原惰性阳离子可以有效地改变 FeO6 的构型，改善晶格氧的活化，提高表面氧的活性和体格氧的流动性。此外，烯烃选择性的提高与过氧化物产物形成的抑制密切相关，这是氧空位增加和晶格氧减少的结果。这些发现证明了通过调整 ABO3 包晶结构中 BO6 的畸变来操纵包晶氧化物中晶格氧活性的可行性。

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.