Skip to main content
SpringerLink
Log in

The Regulation of Surface Copper Species Coupled with Ammonia-Evaporation and Hydrothermal Aging Process to Enhance Catalytic Hydrogenation Properties of Cu–SiO2 Catalysts

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

The ammonia-evaporation method is one of the most commonly methods for preparing Cu–SiO2 catalysts, and the improvement of this method is desirable. This work showed that it could improve the catalytic performance of the Cu–SiO2 catalyst in the hydrogenation of dimethyl oxalates (DMO) to ethylene glycol by introducing hydrothermal aging process and adjusting the aging time after evaporated ammonia. There was no obvious effect on copper phyllosilicate formation with the hydrothermal aging time increasing, but it affected the dispersion of Cu0 species among the copper phyllosilicate layers. As the number of Cu0 species is enough on the catalyst surface, the density of surface Cu0 species would affect the synergistic effect between Cu0 and Cu0 active sites. It is possible that the DMO absorbed on the Cu+ species would be inhibited while the density of surface Cu0 species is highly. Thus, the modified Cu–SiO2 catalyst by hydrothermal aging process with relatively low Cu0 dispersion exhibited enhanced catalytic performance in DMO catalytic hydrogenation.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Scheme 1

Similar content being viewed by others

References

  1. Zhou Z, Li Z, Pan P, Lin L, Qin Y, Yao Y (2010) Progress in technologies of coal-based ethylene glycol synthesis. Chem Ind Eng Prog 29:2003–2009

    CAS  Google Scholar 

  2. Cui G, Meng X, Zhang X, Wang W, Xu S, Ye Y, Tang K, Wang W, Zhu J, Wei M, Evans DG, Duan X (2019) Low-temperature hydrogenation of dimethyl oxalate to ethylene glycol via ternary synergistic catalysis of Cu and acid−base sites. Appl Catal B 248:394–404

    Article  CAS  Google Scholar 

  3. Ye R-P, Lin L, Li Q, Zhou Z, Wang T, Russell CK, Adidharma H, Xu Z, Yao Y-G, Fan M (2018) Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds. Catal Sci Technol 8:3428–3449

    Article  CAS  Google Scholar 

  4. Van Der Grift CJ, Elberse PA, Mulder A, Geus JW (1989) Preparation of silica-supported copper catalysts by means of deposition-precipitation. Appl Catal 59:275

    Article  Google Scholar 

  5. Ding J, Popa T, Tang J, Gasem KAM, Fan M, Zhong Q (2017) Highly selective and stable Cu/SiO2 catalysts prepared with a green method for hydrogenation of diethyl oxalate into ethylene glycol. Appl Catal B 209:530–542

    Article  CAS  Google Scholar 

  6. Sui N, Luo M, Xiao W (2016) Effect of hydrothermal treatment on performance of Cu/SiO2 catalysts for hydrogenation of dimethyl oxalate to ethylene glycol. Nat Gas Chem Ind 41:34

    CAS  Google Scholar 

  7. Chang S, Xu C, Wu T, Shen S (2020) Effect of aging time on catalytic performance of Cu/SiO2 for hydrogenation of acetic acid to ethanol. Nat Gas Chem Ind 45:25

    CAS  Google Scholar 

  8. Chen C-C, Lin L, Ye R-P, Huang L, Zhu L-B, Huang Y-Y, Qin Y-Y, Yao Y-G (2021) Construction of Cu-Ce composite oxides by simultaneous ammonia evaporation method to enhance catalytic performance of Ce-Cu/SiO2 catalysts for dimethyl oxalate hydrogenation. Fuel 290:120083

    Article  CAS  Google Scholar 

  9. Zheng X, Lin H, Zheng J, Duan X, Yuan Y (2013) Lanthanum oxide-modified Cu/SiO2 as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol. ACS Catal 3:2738–2749

    Article  CAS  Google Scholar 

  10. Li Z, Hu Z, Zeng Z, Guo S, Lv J, Huang S, Wang Y, Ma X (2022) Lamellar-structured silicate derived highly dispersed CoCu catalyst for higher alcohol synthesis from syngas. Ind Eng Chem Res 61:6859–6871

    Article  CAS  Google Scholar 

  11. Ye R-P, Lin L, Wang L-C, Ding D, Zhou Z, Pan P, Xu Z, Liu J, Adidharma H, Radosz M, Fan M, Yao Y-G (2020) Perspectives on the active sites and catalyst design for the hydrogenation of dimethyl oxalate. ACS Catal 10:4465–4490

    Article  CAS  Google Scholar 

  12. Zhang X, Wangbao W, Guoyuan Y, Xugen H (2011) Deactivation behavior of SiO2 supported copper catalyst in hydrogenation of diethyl oxalate. Fuel Chem Technol 39:702–705

    CAS  Google Scholar 

  13. Chen LF, Guo PJ, Qiao MH, Yan SR, Li HX, Shen W, Xu HL, Fan KN (2008) Cu/SiO2 catalysts prepared by the ammonia-evaporation method: texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol. J Catal 257:172–180

    Article  CAS  Google Scholar 

  14. Dong X, Ma X, Xu H, Ge Q (2016) Comparative study of silica-supported copper catalysts prepared by different methods: formation and transition of copper phyllosilicate. Catal Sci Technol 6:4151–4158

    Article  CAS  Google Scholar 

  15. Vandergrift CJG, Wielers AFH, Mulder A, Geus JW (1990) The reduction behavior of silica-supported copper-catalysts prepared by deposition precipitation. Thermochim Acta 171:95–113

    Article  CAS  Google Scholar 

  16. He Z, Lin HQ, He P, Yuan YZ (2011) Effect of boric oxide doping on the stability and activity of a Cu-SiO2 catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol. J Catal 277:54–63

    Article  CAS  Google Scholar 

  17. Yang W, Zhao Y, Wang S, Ma X (2016) Formation of copper phyllosilicate in silica supported copper catalyst. Chem Ind Eng 33:1–5

    Google Scholar 

  18. Ligui X, Zengxiao L, Yunhong F, Li Q, Lihong W, Bian J (2018) Preparation of Cu-HMS catalysts by hydrothermal method and study on catalytic hydrogenation performance of dimethyl oxalate. J Mol Catal (China) 32:1–7

    ADS  Google Scholar 

  19. Li T, Lin L, Chen C, Ye R, Huang L, Yang J, Zhang P, Qin Y, Cheng J, Yao Y (2022) Insights into a new formation mechanism of robust Cu/SiO2 catalysts for low-temperature dimethyl oxalate hydrogenation induced by a Chelating Ligand of EDTA. Catalysts 12:320

    Article  Google Scholar 

  20. Ye R-P, Lin L, Chen C-C, Yang J-X, Li F, Zhang X, Li D-J, Qin Y-Y, Zhou Z, Yao Y-G (2018) Synthesis of robust MOF-derived Cu/SiO2 catalyst with low copper loading via sol-gel method for the dimethyl oxalate hydrogenation reaction. ACS Catal 8:3382–3394

    Article  CAS  Google Scholar 

  21. Zhang R-B, Tu Z-A, Meng S, Feng G, Lu Z-H, Yu Y-Z, Reina TR, Hu F-Y, Chen X-H, Ye R-P (2022) Engineering morphologies of yttrium oxide supported nickel catalysts for hydrogen production. Rare Met 42:176–188

    Article  CAS  Google Scholar 

  22. San X, Gong X, Lu Y, Xu J, He L, Meng D, Wang G, Qi J, Jin Q (2022) Anchoring Cu species over SiO2 for hydrogenation of dimethyl oxalate to ethylene glycol. Catalysts 12:1326

    Article  CAS  Google Scholar 

  23. Huang L, Lin L, Chen C-C, Ye R, Zhu L-B, Yang J-X, Qin Y-Y, Cheng J-K, Yao Y-G (2022) β-Cyclodextrin promoted the formation of copper phyllosilicate on Cu-SiO2 microspheres catalysts to enhance the low-temperature hydrogenation of dimethyl oxalate. J Catal 413:943–955

    Article  CAS  Google Scholar 

  24. Toupance T, Kermarec M, Lambert JF, Louis C (2002) Conditions of formation of copper phyllosilicates in silica-supported copper catalysts prepared by selective adsorption. J Phys Chem B 106:2277–2286

    Article  CAS  Google Scholar 

  25. Wang Z-Q, Xu Z-N, Peng S-Y, Zhang M-J, Lu G, Chen Q-S, Chen Y, Guo G-C (2015) High-performance and long-lived Cu/SiO2 nanocatalyst for CO2 hydrogenation. ACS Catal 5:4255–4259

    Article  CAS  Google Scholar 

  26. Ma X, Yang Z, Liu X, Tan X, Ge Q (2015) Dynamic redox cycle of Cu0 and Cu+ over Cu/SiO2 catalyst in ester hydrogenation. RSC Adv 5:37581–37584

    Article  ADS  CAS  Google Scholar 

  27. Sun J, Yu J, Ma Q, Meng F, Wei X, Sun Y, Tsubaki N (2018) Freezing copper as a noble metal-like catalyst for preliminary hydrogenation. Sci Adv 4:eaau3275

    Article  ADS  CAS  PubMed  PubMed Central  Google Scholar 

  28. Huang Y, Ariga H, Zheng X, Duan X, Takakusagi S, Asakura K, Yuan Y (2013) Silver-modulated SiO2-supported copper catalysts for selective hydrogenation of dimethyl oxalate to ethylene glycol. J Catal 307:74–83

    Article  CAS  Google Scholar 

  29. Qi W, Ling Q, Ding D, Yazhong C, Chengwu S, Peng C, Ye W, Qinghong Z, Rong L, Hao S (2018) Performance enhancement of Cu/SiO2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol through zinc incorporation. Catal Commun 108:68–72

    Article  CAS  Google Scholar 

  30. Wang Y, Shen Y, Zhao Y, Lv J, Wang S, Ma X (2015) Insight into the balancing effect of active Cu species for hydrogenation of carbon-oxygen bonds. ACS Catal 5:6200–6208

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported financially by National Key R&D Program of China (2018YFA0704500), and the National Natural Science Foundation of China (No. 22102186).

Author information

Authors and Affiliations

  1. College of Chemistry, Fuzhou University, Fuzhou, 350108, Fujian, People’s Republic of China

    Peng Zhang & Yuan-Gen Yao

  2. Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research On the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, People’s Republic of China

    Peng Zhang, Long Huang, Jin-Xia Yang, Ming-Ling Sun, Fei Li, Ling Lin & Yuan-Gen Yao

  3. University of Chinese Academy of Sciences, Beijing, 100049, People’s Republic of China

    Long Huang & Yi-Hua Wang

  4. Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, College of Chemistry, Nanchang University, Nanchang, 330031, Jiangxi, People’s Republic of China

    Runping Ye

Authors
  1. Peng Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Long Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jin-Xia Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Runping Ye
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ming-Ling Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Fei Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yi-Hua Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ling Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yuan-Gen Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

PZ: Conceptualization, Data curation, Investigation, Writing—original draft, Writing—review and editing. LH: Conceptualization, Methodology, Writing—review and editing. J-XY: Data curation, Methodology. RY: Writing—review and editing. M-LS: Writing—review and editing. FL: Writing—review and editing. Y-HW: Data curation. LL: Conceptualization, Resources, Supervision, Project administration, Writing—review and editing. Y-GY: Supervision, Writing—review and editing, Funding acquisition.

Corresponding authors

Correspondence to Ling Lin or Yuan-Gen Yao.

Ethics declarations

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 1046 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, P., Huang, L., Yang, JX. et al. The Regulation of Surface Copper Species Coupled with Ammonia-Evaporation and Hydrothermal Aging Process to Enhance Catalytic Hydrogenation Properties of Cu–SiO2 Catalysts. Catal Lett 154, 1007–1017 (2024). https://doi.org/10.1007/s10562-023-04365-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10562-023-04365-4

Keywords

Search

Navigation