Abstract
Chemical looping partial oxidation of methane (CL-POM) offers a promising approach to produce syngas with high selectivity and reduced explosion risk. However, the design of metal oxide oxygen carriers with excellent performance and continuous oxygen release capacity remains a challenge. In this study, we developed a composite oxygen carrier (LaFeO3−δ/Ca1−ηSrηMnO3) with the aim of modulating the oxygen transport capacity of Ca1−ηSrηMnO3 to maintain active structures on the LaFeO3−δ (121) defected surface, thereby enhancing the activity and selectivity of CL-POM. The Fe-O4(OV) and Fe-O3(OV)2 local structures were found to serve as active sites for methane oxidation on the LaFeO3−δ (121) defected surface, with comparable free energy barriers of reaction (ΔGa = 1.44 and 1.40 eV, respectively). Based on the oxygen migration energy barriers and reaction energy barriers calculated by DFT, we determined oxygen transport coefficients and surface reaction rate constants to further assess the degree of rate matching between bulk oxygen transport and surface oxygen consumption. Finally, LaFeO3−δ/Ca0.75Sr0.25-MnO3 was proposed as a potential candidate for CL-POM. This composite material achieves commendable rate matching between surface reactivity and bulk oxygen transport, and notably exhibits the highest phase transition energy barrier, effectively inhibiting adverse phase transitions.
摘要
甲烷化学链部分氧化(CL-POM)是一种有前景的合成气生产技术, 具有高选择性和低爆炸风险的优势. 然而, 开发性能优异、可持续释氧的金属载氧体仍然面临挑战. 为此, 本研究设计了一种复合载氧体(LaFeO3−δ/Ca1−ηSrηMnO3), 通过调控Ca1−ηSrηMnO3的氧扩散来维持LaFeO3−δ(121)缺陷表面的活性结构, 从而提升了CL-POM的活性和选择性. 理论计算结果表明, 甲烷在LaFeO3−δ(121)缺陷表面上的反应活性位点主要是Fe-O4(OV)和Fe-O3(OV)2, 它们表现出相近的反应能垒(ΔGa = 1.44 和1.40 eV). 氧扩散系数和表面反应速率常数分别由体相氧迁移能垒和表面反应能垒确定, 进而计算得到体相氧扩散和表面反应的速率, 用以评估两者的匹配程度. 最后, 本研究证实了LaFeO3−δ/Ca0.75-Sr0.25MnO3是一种有潜力的CL-POM载氧体, 其能够实现体相氧扩散速率与表面氧消耗速率的合理匹配, 并有效地抑制不利的相变过程.
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Acknowledgements
We thank Prof. Lyudmila Moskaleva for the discussion on the manuscript. This work was supported by the National Key R&D Program of China (2022YFE0102000), the National Natural Science Foundation of China (22121004 and U22A20409), Haihe Laboratory of Sustainable Chemical Transformations, the Program of Introducing Talents of Discipline to Universities (BP0618007) and the XPLORER PRIZE for financial support. We also acknowledge generous computing resources at High Performance Computing Center of Tianjin University.
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Author contributions Yang T performed the calculations and drafted the manuscript. Luo R, Shi X, and Wu S assisted in the analysis of the calculated results. Zhang X and Pei C contributed to useful discussion. Zhao ZJ and Gong J designed and supervised the project. All authors participated in general discussion and the manuscript revision.
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Tingting Yang received her BSc degree in chemical engineering and technology from the South China University of Technology. She is currently an MSc candidate at the School of Chemical Engineering and Technology, Tianjin University. Her current interest focuses on theoretical studies of thermocatalytic reactions.
Zhi-Jian Zhao received his BSc and MSc degrees in chemistry from Zhejiang University and his PhD degree from Technische Universität München. He then worked as a postdoctoral fellow with Prof. Greeley in Purdue University, and with Dr. Studt and Prof. Nørskov at Stanford University. Currently, he holds a professorship at Tianjin University. His current research focuses on mechanistic studies on heterogeneous catalysts using multi-scaling simulation methods.
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Achieving Surface and Bulk Rate Matching for Chemical Looping Partial Oxidation of Methane by Modulating Oxygen Transport
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Yang, T., Luo, R., Shi, X. et al. Achieving surface and bulk rate matching for chemical looping partial oxidation of methane by modulating oxygen transport. Sci. China Mater. 67, 1217–1224 (2024). https://doi.org/10.1007/s40843-023-2853-0
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DOI: https://doi.org/10.1007/s40843-023-2853-0