Citation: Xu Yue, Weixing Zhao, Shuangyin Wang, Yuqin Zou. Selective Electrocatalytic Hydrogenation of 5-Hydroxymethylfurfural to 2, 5-Dihydroxymethylfuran on Bimetallic PdCu Alloy[J]. Chinese Journal of Structural Chemistry, ;2022, 41(5): 220506. doi: 10.14102/j.cnki.0254-5861.2022-0074 shu

Selective Electrocatalytic Hydrogenation of 5-Hydroxymethylfurfural to 2, 5-Dihydroxymethylfuran on Bimetallic PdCu Alloy

Xu Yue ¹ ,
Weixing Zhao ¹ ,
Shuangyin Wang ¹ ,
Yuqin Zou ^{1, 2,,}

1.
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha 410082, China
2.
Shenzhen Institute of Hunan University, Shenzhen 518057, China

Corresponding author: Yuqin Zou, yuqin_zou@hnu.edu.cn
Received Date: 3 April 2022
Accepted Date: 18 April 2022

Figures(4)

2, 5-dihydroxymethylfuran (DHMF), obtained from 5-hydroxymethylfurfural (HMF) by electrochemical method, is a promising building block for polymers. However, one challenge of this process is to reduce initial potential and improve catalytic selectivity. In this work, the PdCu bimetallic catalyst is prepared with an onset potential of-0.05 V_RHE and a selectivity of 99%. Compared with the single Cu electrocatalyst, the adsorption of HMF and proton is improved by introducing of Pd, which is demonstrated by the electrochemical results and hydrogen production rate. This work provides an effective strategy to improve the selectivity of Cu-based electrocatalyst and builds a relationship between the adsorption capacity and the electrocatalytic performance.
- biomass,
- 2, 5-dihydroxymethylfuran,
- electrocatalyst,
- bimetallic alloy,
- hydrogenation
1. [1]
  Yang, M.; Yuan, Z.; Peng, R.; Wang, S.; Zou, Y. Recent progress on electrocatalytic valorization of biomass-derived organics. Energ. Environ. Mater. 2022, Doi:10.1002/eem2.12295. doi: 10.1002/eem2.12295
2. [2]
  Dai, Y. M.; Niu, L. L.; Liu, H.; Zou, J. Q.; Yu, L. P.; Feng, Q. J. Cu-Ni alloy catalyzed electrochemical carboxylation of benzyl bromide with carbon dioxide in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate. Int. J. Electrochem. Sci. 2018, 13, 1084-1095.
3. [3]
  Feng, Q.; Lv, H.; Zhang, Y.; Dai, F.; Yan, W. New method for electrochemical activation of N-benzyl ideneaniline to dibutyl phthalate in the present of carbon dioxide. Int. J. Electrochem. Sci. 2016, 11, 692-699.
4. [4]
  Demirbas, A. Biomass resource facilities and biomass conversion processing for fuels and chemicals. Energy Convers. Manage. 2001, 42, 1357-1378. doi: 10.1016/S0196-8904(00)00137-0
5. [5]
  Kwon, Y.; Schouten, K. J. P.; van der Waal, J. C.; de Jong, E.; Koper, M. T. M. Electrocatalytic conversion of furanic compounds. ACS Catal. 2016, 6, 6704-6717. doi: 10.1021/acscatal.6b01861
6. [6]
  Mamman, A. S.; Lee, J. M.; Kim, Y. C.; Hwang, I. T.; Park, N. J.; Hwang, Y. K.; Chang, J. S.; Hwang, J. S. Furfural: hemicellulose/xylose-derived biochemical. Biofuel Bioprod. Bior. 2008, 2, 438-454. doi: 10.1002/bbb.95
7. [7]
  Roman-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A. Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature 2007, 447, 982-985. doi: 10.1038/nature05923
8. [8]
  Li, S.; Sun, X.; Yao, Z.; Zhong, X.; Coo, Y.; Liang, Y.; Wei, Z.; Deng, S.; Zhuang, G.; Li, X.; Wang, J. Biomass valorization via paired electrosynthesis over vanadium nitride-based electrocatalysts. Adv. Funct. Mater. 2019, 29, 1904780. doi: 10.1002/adfm.201904780
9. [9]
  de Luna, G. S.; Ho, P. H.; Lolli, A.; Ospitali, F.; Albonetti, S.; Fornasari, G.; Benito, P. Ag electrodeposited on Cu open-cell foams for the selective electroreduction of 5-hydroxymethylfurfural. Chemelectrochem 2020, 7, 1238-1247. doi: 10.1002/celc.201902161
10. [10]
  Nilges, P.; dos Santos, T. R.; Harnisch, F.; Schroeder, U. Electrochemistry for biofuel generation: electrochemical conversion of levulinic acid to octane. Energy & Environ. Sci. 2012, 5, 5231-5235.
11. [11]
  Govind Rajan, A.; Carter, E. A. Discovering competing electrocatalytic mechanisms and their overpotentials: automated enumeration of oxygen evolution pathways. J. Phys. Chem. C 2020, 124, 24883-24898. doi: 10.1021/acs.jpcc.0c08120
12. [12]
  Kwon, Y.; Birdja, Y. Y.; Raoufmoghaddam, S.; Koper, M. T. M. Electrocatalytic hydrogenation of 5-hydroxymethylfurfural in acidic solution. ChemSusChem 2015, 8, 1745-1751. doi: 10.1002/cssc.201500176
13. [13]
  Kwon, Y.; de Jong, E.; Raoufmoghaddam, S.; Koper, M. T. M. Electrocatalytic hydrogenation of 5-hydroxymethylfurfural in the absence and presence of glucose. ChemSusChem 2013, 6, 1659-1667. doi: 10.1002/cssc.201300443
14. [14]
  Chadderdon, X. H.; Chadderdon, D. J.; Matthiesen, J. E.; Qiu, Y.; Carraher, J. M.; Tessonnier, J. P.; Li, W. Mechanisms of furfural reduction on metal electrodes: distinguishing pathways for selective hydrogenation of bioderived oxygenates. J. Am. Chem. Soc. 2017, 139, 14120-14128. doi: 10.1021/jacs.7b06331
15. [15]
  Zhang, L.; Zhang, F.; Michel, F. C. Jr.; Co, A. C. Efficient electrochemical hydrogenation of 5-hydroxymethylfurfural to 2, 5-bis(hydroxymethyl)-furan on Ag-displaced nanotextured Cu catalysts. Chemelectrochem 2019, 6, 4739-4749. doi: 10.1002/celc.201900640
16. [16]
  Zhang, Y. R.; Wang, B. X.; Qin, L.; Li, Q.; Fan, Y. M. A non-noble bimetallic alloy in the highly selective electrochemical synthesis of the biofuel 2, 5-dimethylfuran from 5-hydroxymethylfurfural. Green Chem. 2019, 21, 1108-1113. doi: 10.1039/C8GC03689F
17. [17]
  Alonso, D. M.; Wettstein, S. G.; Dumesic, J. A. Bimetallic catalysts for upgrading of biomass to fuels and chemicals. Chem. Soc. Rev. 2012, 41, 8075-8098. doi: 10.1039/c2cs35188a
18. [18]
  Roylance, J. J.; Kim, T. W.; Choi, K. S. Efficient and selective electrochemical and photoelectrochemical reduction of 5-hydroxymethylfurfural to 2, 5-bis(hydroxymethyl)furan using water as the hydrogen source. ACS Catal. 2016, 6, 1840-1847. doi: 10.1021/acscatal.5b02586
19. [19]
  Ma, S.; Sadakiyo, M.; Heima, M.; Luo, R.; Haasch, R. T.; Gold, J. I.; Yamauchi, M.; Kenis, P. J. A. Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu-Pd catalysts with different mixing patterns. J. Am. Chem. Soc. 2017, 139, 47-50. doi: 10.1021/jacs.6b10740
20. [20]
  Li, J.; Li, F.; Guo, S. X.; Zhang, J.; Ma, J. PdCu@Pd nanocube with Pt-like activity for hydrogen evolution reaction. ACS Appl. Mater. Interfaces 2017, 9, 8151-8160. doi: 10.1021/acsami.7b01241
21. [21]
  Huang, W.; Kang, X.; Xu, C.; Zhou, J.; Deng, J.; Li, Y.; Cheng, S. 2D PdAg alloy nanodendrites for enhanced ethanol electroxidation. Adv. Mater. 2018, 30, 1706962. doi: 10.1002/adma.201706962
22. [22]
  He, J.; Chen, D.; Li, N.; Xu, Q.; Li, H.; He, J.; Lu, J. Controlled fabrication of mesoporous ZSM-5 zeolite-supported PdCu alloy nanoparticles for complete oxidation of toluene. Appl. Catal. B 2020, 265, 118560. doi: 10.1016/j.apcatb.2019.118560
23. [23]
  Shan, S.; Petkov, V.; Prasai, B.; Wu, J.; Joseph, P.; Skeete, Z.; Kim, E.; Mott, D.; Malis, O.; Luo, J.; Zhong, C. J. Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale. Nanoscale 2015, 7, 18936-18948. doi: 10.1039/C5NR04535E
24. [24]
  Wang, C.; Chen, D. P.; Sang, X.; Unocic, R. R.; Skrabalak, S. E. Size-dependent disorder-order transformation in the synthesis of monodisperse intermetallic PdCu nanocatalysts. ACS Nano 2016, 10, 6345-6353. doi: 10.1021/acsnano.6b02669
25. [25]
  Yan, Y.; Du, J. S.; Gilroy, K. D.; Yang, D.; Xia, Y.; Zhang, H. Intermetallic nanocrystals: syntheses and catalytic applications. Adv. Mater. 2017, 29, DOI: 10.1002/adma.201605997. doi: 10.1002/adma.201605997
26. [26]
  Cheng, Y.; Xue, J.; Yang, M.; Li, H.; Guo, P. Bimetallic PdCu nanoparticles for electrocatalysis: multiphase or homogeneous alloy? Inorg. Chem. 2020, 59, 10611-10619. doi: 10.1021/acs.inorgchem.0c01056
27. [27]
  He, C.; Ma, Z.; Wu, Q.; Cai, Y.; Huang, Y.; Liu, K.; Wu, X. Promoting the ORR catalysis of Pt-Fe intermetallic catalysts by increasing atomic utilization and electronic regulation. Electrochim. Acta 2020, 330, 135119. doi: 10.1016/j.electacta.2019.135119
28. [28]
  Hammer, B.; Norskov, J. K. Theoretical surface science and catalysis-calculations and concepts. Adv. Catal. 2000, 45, 71-129.
29. [29]
  Li, F.; Li, J.; Feng, Q.; Yan, J.; Tang, Y.; Wang, H. Significantly enhanced oxygen reduction activity of Cu/CuN_xC_y co-decorated ketjenblack catalyst for Al-air batteries. J. Energy Chem. 2018, 27, 419-425. doi: 10.1016/j.jechem.2017.12.002
30. [30]
  Kim, D.; Resasco, J.; Yu, Y.; Asiri, A. M.; Yang, P. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles. Nat. Commun. 2014, 5, 4948. doi: 10.1038/ncomms5948
31. [31]
  Li, J.; Liu, G.; Liu, B.; Min, Z.; Qian, D.; Jiang, J.; Li, J. Fe-doped CoSe₂ nanoparticles encapsulated in N-doped bamboo-like carbon nanotubes as an efficient electrocatalyst for oxygen evolution reaction. Electrochim. Acta 2018, 265, 577-585. doi: 10.1016/j.electacta.2018.01.211
32. [32]
  Ma, M.; Hansen, H. A.; Valenti, M.; Wang, Z.; Cao, A.; Dong, M.; Smith, W. A. Electrochemical reduction of CO₂ on compositionally variant Au-Pt bimetallic thin films. Nano Energy 2017, 42, 51-57. doi: 10.1016/j.nanoen.2017.09.043
33. [33]
  Ruban, A.; Hammer, B.; Stoltze, P.; Skriver, H. L.; Nørskov, J. K. Surface electronic structure and reactivity of transition and noble metals. J. Mol. Catal. A 1997, 115, 421-429. doi: 10.1016/S1381-1169(96)00348-2
34. [34]
  Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.; Chen, J. G. Role of strain and ligand effects in the modification of the electronic and chemical properties of bimetallic surfaces. Phys. Rev. Lett. 2004, 93, 156801. doi: 10.1103/PhysRevLett.93.156801
35. [35]
  Solanki, B. S.; Rode, C. V. Selective hydrogenation of 5-HMF to 2, 5-DMF over a magnetically recoverable non-noble metal catalyst. Green Chem. 2019, 21, 6390-6406. doi: 10.1039/C9GC03091C
36. [36]
  Dutta, S.; De, S.; Patra, A. K.; Sasidharan, M.; Bhaumik, A.; Saha, B. Microwave assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by mesoporous TiO₂ nanoparticles. Appl. Catal. A 2011, 409, 133-139.
37. [37]
  Alam, M. I.; De, S.; Singh, B.; Saha, B.; Abu-Omar, M. M. Titanium hydrogenphosphate: an efficient dual acidic catalyst for 5-hydroxy-methylfurfural (HMF) production. Appl. Catal. A 2014, 486, 42-48. doi: 10.1016/j.apcata.2014.08.019
38. [38]
  Lyons, M. E. G.; Brandon, M. P. The significance of electrochemical impedance spectra recorded during active oxygen evolution for oxide covered Ni, Co and Fe electrodes in alkaline solution. J. Electroanal. Chem. 2009, 631, 62-70. doi: 10.1016/j.jelechem.2009.03.019
39. [39]
  Wang, H. Y.; Hung, S. F.; Chen, H. Y.; Chan, T. S.; Chen, H. M.; Liu, B. In operando identification of geometrical-site-dependent water oxidation activity of spinel Co₃O₄. J. Am. Chem. Soc. 2016, 138, 36-39. doi: 10.1021/jacs.5b10525
40. [40]
  Zhao, T.; Wang, G.; Gong, M.; Xiao, D.; Chen, Y.; Shen, T.; Lu, Y.; Zhang, J.; Xin, H.; Li, Q.; Wang, D. Self-optimized ligand effect in L1₂-PtPdFe intermetallic for efficient and stable alkaline hydrogen oxidation reaction. ACS Catal. 2020, 10, 15207-15216. doi: 10.1021/acscatal.0c03938
41. [41]
  Zhou, L.; Zhu, X.; Su, H.; Lin, H.; Lyu, Y.; Zhao, X.; Chen, C.; Zhang, N.; Xie, C.; Li, Y.; Lu, Y.; Zheng, J.; Johannessen, B.; Jiang, S. P.; Liu, Q.; Li, Y.; Zou, Y.; Wang, S. Identification of the hydrogen utilization pathway for the electrocatalytic hydrogenation of phenol. Sci China-Chem. 2021, 64, 1586-1595. doi: 10.1007/s11426-021-1100-y
42. [42]
  Heidary, N.; Kornienko, N. Operando vibrational spectroscopy for electrochemical biomass valorization. Chem. Commun. 2020, 56, 8726-8734. DOI: 10.14102/j.cnki.0254-5861.2022-0074 doi: 10.14102/j.cnki.0254-5861.2022-0074
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