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Preparation, characterization and catalytic performance of high stability of LaCoO3@CuO composite with core-shell structure for methanol steam reforming

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Abstract

The CuO modified LaCoO3@CuO-x catalysts were prepared through sol-gel method, and applied for methanol steam reforming (MSR). The catalysts were characterized by means of XPS, XRD, SEM, BET, TEM and EDS techniques. XPS and XRD analyses show that the synthesized catalysts are the combination of LaCoO3 and CuO. The results of XPS also demonstrated that the Co ion in perovskite exhibits a mixed valence state of Co3+ and Co2+, and the presence of Co2+ contributes to the reduction of Cu2+ to copper and also promotes the formation of hydrogen. The results of SEM and TEM show that LaCoO3@CuO-0.2 catalyst with core-shell type has porous structure, which contributes to expedite the contact between the reaction medium and the catalyst surface, therefore, improving the catalytic performance. The results of the pore size show that LaCoO3@CuO-0.2 exhibits remarkably large pores compared with other catalyst samples. The MSR experimental results illustrate that LaCoO3@CuO-0.2 has the optimal catalytic performance, and the methanol conversion of LaCoO3@CuO-0.2 is 100%. In addition, the stability of LaCoO3@CuO-0.2 was evaluated under the optimum operating parameters (the catalytic temperature, LHSV and W/M are 873 K, 20 h−1 and 4:1, respectively). The results show that the developed LaCoO3@CuO-0.2 has excellent stability within 50 h without deactivation.

Graphical abstract

The LaCoO3@CuO-0.2 developed in this study with core-shell structure has outstanding catalytic performance and excellent stability. The presence of Co2+ proves the existence of oxygen vacancies on the surface of the catalyst, which is helpful for the reduction of Cu2+ to copper and promotes the MSR reaction.

Highlights

  • The preparation method of core-shell LaCoO3@CuO is simple, and the catalyst does not need reduction step before MSR test.

  • Proper CuO doping could improve the activity of the catalysts.

  • The methanol conversion rate of LaCoO3@CuO-0.2 is 100%, and it has excellent catalytic activity and stability without deactivation under the stability test of 50 h.

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Acknowledgements

This work was supported by the China Postdoctoral Science Foundation (No.2019M651094), and Science and Technology Innovation Foundation of Dalian (2021JJ11CG004).

Author contributions

Writing-original draft preparation—GC; conceptualization—QS; formal analysis—SL; writing-review and editing—QS and SL; data curation—XZ and ZC; supervision—QS and GY. All authors reviewed the manuscript.

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Authors and Affiliations

  1. Marine Engineering College, Dalian Maritime University, Dalian, China

    Gaokui Chen, Qiuwan Shen, Shian Li, Xin Zhang, Zhongwen Cai & Guogang Yang

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  1. Gaokui Chen
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Chen, G., Shen, Q., Li, S. et al. Preparation, characterization and catalytic performance of high stability of LaCoO3@CuO composite with core-shell structure for methanol steam reforming. J Sol-Gel Sci Technol 108, 721–733 (2023). https://doi.org/10.1007/s10971-023-06217-4

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