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Oxygen Vacancy in CeO2 Facilitate the Catalytic Activity of Pd/CeO2 for CO Direct Esterification to Dimethyl Oxalate

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Abstract

CO direct esterification to dimethyl oxalate (DMO) has important industrial application value. Pd-based heterogeneous catalysts have been often utilized for this reaction. However, the effects of defect structures causing by the different morphologies of the support on the catalytic performance has not been investigated sufficiently. In this work, three different morphologies of CeO2 support (denoted as rod, cube, and octahedron) loading Pd were synthesized, and further investigated their catalytic activities for CO direct esterification to DMO. The Pd/CeO2-rod catalyst exhibited the best CO conversion compared with Pd/CeO2-cube and Pd/CeO2-octa. The results of Raman and XPS show that CeO2-rod has the highest oxygen vacancy concentration than those of CeO2-cube and CeO2-octa. In addition, it was found that partial interfacial electrons transfer from Pd to CeO2 support at the interface from the result of XPS. More intriguingly, the result of in situ DRIRS of CO exhibits that the partial interfacial electrons transfer from CeO2 to Pd, resulting from oxygen vacancies serve as a charge compensator to promote partial electrons transfer. The enriched electron of Pd would promote the adsorption and activation of CO, thus enhancing the catalytic activity. This work will provide a general understanding of the support effect to catalytic performance, which induced by the oxygen vacancies.

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References

  1. Zhao T, Chen D, Dai Y, Yuan W, Holmen A (2004) Synthesis of dimethyl oxalate from CO and CH3ONO on carbon nanofiber supported palladium catalysts. Ind Eng Chem Res 43:4595–4601

    Article  CAS  Google Scholar 

  2. Fenton DM, Steinwand PJ (1974) Preparation of dialkyl oxalates by oxidative Car= bonylation. J Org Chem 39:701–704

    Article  CAS  Google Scholar 

  3. Xu Z-N, Sun J, Lin C-S, Jiang X-M, Chen Q-S, Peng S-Y, Wang M-S, Guo G-C (2013) High-performance and long-lived Pd nanocatalyst directed by shape effect for CO oxidative coupling to dimethyl oxalate. ACS Catal 3:118–122

    Article  CAS  Google Scholar 

  4. Peng S-Y, Xu Z-N, Chen Q-S, Chen Y-M, Sun J, Wang Z-Q, Wang M-S, Guo G-C (2013) An ultra-low Pd loading nanocatalyst with high activity and stability for CO oxidative coupling to dimethyl oxalate. Chem Commun 49:5718–5720

    Article  CAS  Google Scholar 

  5. Peng S-Y, Xu Z-N, Chen Q-S, Wang Z-Q, Chen Y-M, Lv D-M, Lu G, Guo G-C (2014) MgO: an excellent catalyst support for CO oxidative coupling to dimethyl oxalate. Catal Sci Technol 4:1925–1930

    Article  CAS  Google Scholar 

  6. Peng S-Y, Xu Z-N, Chen Q-S, Wang Z-Q, Lv D-M, Sun J, Chen Y-M, Guo G-C (2015) Enhanced stability of Pd/ZnO catalyst for CO oxidative coupling to dimethyl oxalate: effect of Mg2+ doping. ACS Catal 5:4410–4417

    Article  CAS  Google Scholar 

  7. Zhao X, Lin Q, Xiao W (2005) Characterization of Pd-CeO2/α-alumina catalyst for synthesis of dimethyl oxalate. Appl Catal A 284:253–257

    Article  CAS  Google Scholar 

  8. Ji Y, Liu G, Li W, Xiao W (2009) The mechanism of CO coupling reaction to form dimethyl oxalate over Pd/α-Al2O3. J Mol Catal A: Chem 314:63–70

    Article  CAS  Google Scholar 

  9. Jin E, He L, Zhang Y, Richard AR, Fan M (2014) A nanostructured CeO2 promoted Pd/α-alumina diethyl oxalate catalyst with high activity and stability. RSC Adv 4:48901–48904

    Article  CAS  Google Scholar 

  10. Jing K-Q, Fu Y-Q, Wang Z-Q, Chen Z-N, Tan H-Z, Sun J, Xu Z-N, Guo G-C (2020) Zn2+ stabilized Pd clusters with enhanced covalent metal-support interaction via forming Pd-Zn bond to promote catalytic thermal stability. Nanoscale 12:14825–14830

    Article  CAS  Google Scholar 

  11. Hu Z, Liu X, Meng D, Guo GY, Lu G (2016) Effect of ceria crystal plane on the physicochemical and catalytic properties of Pd/ceria for CO and propane oxidation. ACS Catal 6:2265–2279

    Article  CAS  Google Scholar 

  12. Tan H, Wang J, Yu S, Zhou K (2015) Support morphology-dependent catalytic activity of Pd/CeO2 for formaldehyde oxidation. Environ Sci Technol 49(14):8675–8682

    Article  CAS  Google Scholar 

  13. Wang Z, Sun J, Xu Z, Guo G (2020) CO direct esteri fi cation to dimethyl oxalate and dimethyl carbonate: the key functional motifs for catalytic selectivity. Nanoscale 12:20131–20140

    Article  CAS  Google Scholar 

  14. Xu Y-P, Wang Z-Q, Tan H-Z, Jing K-Q, Xu Z-N, Guo G-C (2020) Lewis acid sites in MOFs supports promoting the catalytic activity and selectivity for CO esterification to dimethyl carbonate. Catal Sci Technol 10:1699–1707

    Article  CAS  Google Scholar 

  15. Jiang F, Wang S, Liu B, Liu J, Wang L, Xiao Y, Xu Y, Liu X (2020) Insights into the influence of CeO2 crystal facet on CO2 hydrogenation to methanol over Pd/CeO2 catalysts. ACS Catal 10:11493–11509

    Article  CAS  Google Scholar 

  16. Li K, Ji J, Huang H, He M (2020) Efficient activation of Pd/CeO2 catalyst by non-thermal plasma for complete oxidation of indoor formaldehyde at room temperature. Chemosphere 246:125762

    Article  CAS  Google Scholar 

  17. Yan Y, Li H, Lu Z, Wang X, Zhang R, Feng G (2019) Effects of reduction temperature and content of Pd loading on the performance Pd/CeO2 catalyst for CO oxidation. Chin Chem Lett 30:1153–1156

    Article  CAS  Google Scholar 

  18. Xie Q, Zhang H, Kang J, Cheng J, Zhang Q, Wang Y (2018) Oxidative dehydrogenation of propane to propylene in the presence of HCl catalyzed by CeO2 and NiO-modified CeO2 nanocrystals. ACS Catal 8:4902–4916

    Article  CAS  Google Scholar 

  19. Spezzati G, Benavidez AD, DeLaRiva AT, Su Y, Hofmann JP, Asahina S, Olivier EJ, Neethling JH, Miller JT, Datye AK, Hensen EJM (2019) CO oxidation by Pd supported on CeO2(100) and CeO2(111) facets. Appl Catal B 243:36–46

    Article  CAS  Google Scholar 

  20. Chang L, Sasirekha N, Chen Y, Wang W (2006) Preferential oxidation of CO in H2 stream over Au/MnO2-CeO2 catalysts. Ind Eng Chem Res 45:4927–4935

    Article  CAS  Google Scholar 

  21. Romeo M, Bak K, Fallah JEI, Normand FL, Hilaire L (1993) XPS study of the reduction of cerium dioxide. Surf Interface Anal 20:508–512

    Article  CAS  Google Scholar 

  22. Gao Y, Li R, Chen S, Luo L, Cao T, Huang W (2015) Morphology-dependent interplay of reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO2 nanocrystals. Phys Chem Chem Phys 17:31862

    Article  CAS  Google Scholar 

  23. Guo Y, Mei S, Yuan K, Wang D, Liu H, Yan C, Zhang Y (2018) Low-temperature CO2 methanation over CeO2-supported Ru single atoms, nanoclusters, and nanoparticles competitively tuned by strong metal-support interactions and H-spillover effect. ACS Catal 8:6203–6215

    Article  CAS  Google Scholar 

  24. Lu Z, Yang Z (2010) Interfacial properties of NM/CeO2(111) (NM = noble metal atoms or clusters of Pd, Pt and Rh): a first principles study. J Phys: Condens Matter 22:475003

    Google Scholar 

  25. Guo Y, Zhang Y (2018) Metal clusters dispersed on oxide supports: preparation methods and metal-support interactions. Top Catal 61:855–874

    Article  CAS  Google Scholar 

  26. Nakamura I, Negishi N, Kutsuna S, Ihara T, Sugihara S, Takeuchi K (2000) Role of oxygen vacancy in the plasma-treated TiO2 photocatalyst with visible light activity for NO removal. J Mol Catal A: Chem 161(1/2):205–212

    Article  CAS  Google Scholar 

  27. Pan X, Yang M, Fu X, Zhang N, Xu Y (2013) Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications. Nanoscale 5(9):3601–3614

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Key Research and Development Program of China (2017YFA0206802, 2017YFA0700103, 2018YFA0704500), the Programs of the Chinese Academy of Sciences (QYZDJ-SSW-SLH028).

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Correspondence to Zhong-Ning Xu or Guo-Cong Guo.

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Hu, C., Jing, KQ., Lin, XQ. et al. Oxygen Vacancy in CeO2 Facilitate the Catalytic Activity of Pd/CeO2 for CO Direct Esterification to Dimethyl Oxalate. Catal Lett 152, 503–512 (2022). https://doi.org/10.1007/s10562-021-03650-4

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