Synergistic effects between electrocatalyst and electrolyte in the electrocatalytic reduction of lignin model compounds in a stirred slurry reactor

Abstract

Valorization of biomass-derived substrates via electrocatalytic hydrogenation-hydrogenolysis (ECH) is an attractive approach for selective production of organic chemicals. The electrocatalytic activity is strongly dependent on the surface coverage of adsorbed hydrogen radicals, which is a complex function of the catalytically active surface sites, electrolyte (pH and composition) and electrode potential. The performance of carbon-supported catalysts (Pt/C, Ru/C, Pd/C) was explored in the ECH of phenol and guaiacol in a stirred slurry electrochemical reactor where the cathode and anode compartments were separated by a Nafion® 117 membrane. Acid (H2SO4) and neutral (NaCl) catholytes were used. Pt/C showed superior activity in the acid-acid electrolyte pair, while the activity of Ru/C and Pd/C were significantly improved in the neutral-acid catholyte-anolyte pairs. By pairing neutral catholyte and acid anolyte, the anodic protons transported through the membrane can be effectively utilized for ECH reactions. In terms of reaction pathways for guaiacol ECH, ring saturation leading to 2-methoxycyclohexanol was generally the dominant pathway. However, for Pt/C in either 0.2 or 0.5 M NaCl catholyte paired with 0.5 M H2SO4 anolyte the demethoxylation–ring saturation pathway producing cyclohexanol and cyclohexanone was equally competitive at a constant superficial current density of -109 mA cm−2 and 50 0C. Efficient reductive upgrading of lignin model compounds can be achieved under mild conditions via electrocatalysis in the slurry reactor by exploiting synergistic effects between the catalyst and electrolyte.

Graphic abstract

This is a preview of subscription content, access via your institution.

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

References

  1. 1.

    Li K, Sun Y (2018) Electrocatalytic upgrading of biomass-derived intermediate compounds to value-added products. Chem A Eur J 24(69):18258–18270

    CAS  Article  Google Scholar 

  2. 2.

    Cardoso DSP, Šljukić B, Santos DMF, Sequeira CAC (2017) Organic electrosynthesis: from laboratorial practice to industrial applications. Org Process Res Dev 21(9):1213–1226

    CAS  Article  Google Scholar 

  3. 3.

    Zhao B, Chen M, Guo Q, Fu Y (2014) Electrocatalytic hydrogenation of furfural to furfuryl alcohol using platinum supported on activated carbon fibers. Electrochim Acta 135:139–146

    CAS  Article  Google Scholar 

  4. 4.

    Ho Lam C, Das SC, Erickson N, Hyzer CD, Garedew M, Anderson JE, Wallington TJ, Tamor MA, Jackson JE, Saffron CM (2017) Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading. Sustain Energy Fuels 1(2):219–398

    Article  Google Scholar 

  5. 5.

    Turner J, Sverdrup G, Mann MK, Manness PC, Kroposki B, Ghirardi M, Evans RJ, Blake D (2008) Renewable hydrigen production. Int J Engergy Res 32:379–407

    CAS  Article  Google Scholar 

  6. 6.

    Green SK, Lee J, Kim HJ, Tompsett GA, Kim WB, Huber GW (2013) The electrocatalytic hydrogenation of furanic compounds in a continuous electrocatalytic membrane reactor. Green Chem 15(7):1869

    CAS  Article  Google Scholar 

  7. 7.

    Jung S, Biddinger EJ (2016) Electrocatalytic hydrogenation and hydrogenolysis of furfural and the impact of homogeneous side reactions of furanic compounds in acidic electrolytes. ACS Sustain Chem Eng 4(12):6500–6508

    CAS  Article  Google Scholar 

  8. 8.

    Xin L, Zhang Z, Qi J, Chadderdon DJ, Qiu Y, Warsko KM, Li W (2013) Electricity storage in biofuels: selective electrocatalytic reduction of levulinic acid to valeric acid or γ-valerolactone. Chemsuschem 6(4):674–686

    CAS  Article  Google Scholar 

  9. 9.

    Li Z, Garedew M, Lam CH, Jackson JE, Miller DJ, Saffron CM (2012) Mild electrocatalytic hydrogenation and hydrodeoxygenation of bio-oil derived phenolic compounds using ruthenium supported on activated carbon cloth. Green Chem 14(9):2540

    CAS  Article  Google Scholar 

  10. 10.

    Garedew M, Young-Farhat D, Jackson JE, Saffron CM (2019) Electrocatalytic upgrading of phenolic compounds observed after lignin pyrolysis. ACS Sustain Chem Eng 7:8375–8386

    CAS  Article  Google Scholar 

  11. 11.

    Song Y, Sanyal U, Pangotra D, Holladay JD, Camaioni DM, Gutiérrez OY, Lercher JA (2018) Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals. J Catal 359:68–75

    CAS  Article  Google Scholar 

  12. 12.

    Dubé P, Kerdouss F, Laplante F, Proulx P, Brossard L, Mé Nard H (2003) Electrocatalytic hydrogenation of cyclohexanone: simple dynamic cell design. J Appl Electrochem 33(6):541–547

    Article  Google Scholar 

  13. 13.

    Ftouni J, Genuino HC, Muñoz-Murillo A, Bruijnincx PCA, Weckhuysen BM (2017) Influence of sulfuric acid on the performance of ruthenium-based catalysts in the liquid-phase hydrogenation of levulinic acid to γ-valerolactone. Chemsuschem 10(14):2891–2896

    CAS  Article  Google Scholar 

  14. 14.

    Lu B, Guo L, Wu F, Peng Y, Lu JE, Smart TJ, Wang N, Finfrock YZ, Morris D, Zhang P, Li N, Gao P, Ping Y, Chen S (2019) Ruthenium atomically dispersed in carbon outperforms platinum toward hydrogen evolution in alkaline media. Nat Commun 10(1):1–11

    Article  Google Scholar 

  15. 15.

    Zheng Y, Jiao Y, Zhu Y, Li LH, Han Y, Chen Y, Jaroniec M, Qiao SZ (2016) High electrocatalytic hydrogen evolution activity of an anomalous ruthenium catalyst. J Am Chem Soc 138(49):16174–16181

    CAS  Article  Google Scholar 

  16. 16.

    Wijaya YP, Grossmann-Neuhaeusler T, Putra RDD, Smith KJ, Kim CS, Gyenge EL (2019) Electrocatalytic hydrogenation of guaiacol in diverse electrolytes using a stirred slurry reactor. Chemsuschem 13(3):629–639

    Article  Google Scholar 

  17. 17.

    Mahmood N, Yao Y, Zhang J-W, Pan L, Zhang X, Zou J-J (2018) Electrocatalysts for hydrogen evolution in alkaline electrolytes: mechanisms, challenges, and prospective solutions. Adv Sci 5(2):1700464

    Article  Google Scholar 

  18. 18.

    Saffron CM, Li Z, Miller DJ, Jackson JE (2015) Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds. US Patent, US 2015/0008139 A1, 1(19)

  19. 19.

    Zadick A, Dubau L, Sergent N, Grégory G, Berthomé B, Chatenet M (2015) Huge instability of Pt/C catalysts in alkaline medium. ACS Catal 5:4819–4824

    CAS  Article  Google Scholar 

  20. 20.

    Zadick A, Dubau L, Demirci UB, Chatenet M (2016) Effects of Pd nanoparticle size and solution reducer strength on Pd/C electrocatalyst stability in alkaline electrolyte. J Electrochem Soc 163(8):F781–F787

    CAS  Article  Google Scholar 

  21. 21.

    Michel C, Gallezot P (2015) Why is ruthenium an efficient catalyst for the aqueous-phase hydrogenation of biosourced carbonyl compounds? ACS Catal 5(7):4130–4132

    CAS  Article  Google Scholar 

  22. 22.

    Lu M, Du H, Wei B, Zhu J, Li M, Shan Y, Song C (2017) Catalytic hydrodeoxygenation of guaiacol over palladium catalyst on different titania supports. Energy Fuels 31(10):10858–10865

    CAS  Article  Google Scholar 

  23. 23.

    Song Y, Gutiérrez OY, Herranz J, Lercher JA (2016) Aqueous phase electrocatalysis and thermal catalysis for the hydrogenation of phenol at mild conditions. Appl Catal B Environ 182:236–246

    CAS  Article  Google Scholar 

  24. 24.

    Hodnik N, Jovanovič P, Pavlišič A, Jozinović B, Zorko M, Bele M, Šelih VS, Šala M, Hočevar S, Gaberšček M (2015) New insights into corrosion of ruthenium and ruthenium oxide nanoparticles in acidic media. J Phys Chem C 119(18):10140–10147

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work is supported by a collaborative project between the University of British Columbia and Korea Institute of Science and Technology (KIST) on-site laboratory. The support of NSERC through the Discovery Grant (for EG) is gratefully acknowledged. The authors thank Priyanthika Adinamozhi, Daichi Hirata, and Robertus D. D. Putra for the technical supports.

Author information

Affiliations

Authors

Corresponding authors

Correspondence to Kevin J. Smith or Chang Soo Kim or Elöd L. Gyenge.

Additional information

Publisher's Note

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

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 566 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Wijaya, Y.P., Smith, K.J., Kim, C.S. et al. Synergistic effects between electrocatalyst and electrolyte in the electrocatalytic reduction of lignin model compounds in a stirred slurry reactor. J Appl Electrochem 51, 51–63 (2021). https://doi.org/10.1007/s10800-020-01429-w

Download citation

Keywords

  • Biomass conversion
  • Electrocatalytic hydrogenation
  • Lignin
  • Guaiacol
  • Phenol