Issue

Vol. 15 (2023)

Optimized Electronic Modification of S-Doped CuO Induced by Oxidative Reconstruction for Coupling Glycerol Electrooxidation with Hydrogen Evolution

https://doi.org/10.1007/s40820-023-01159-6
Ruo‑Yao Fan
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Xue‑Jun Zhai
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Wei‑Zhen Qiao
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Yu‑Sheng Zhang
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Ning Yu
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Na Xu
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Qian‑Xi Lv
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Yong‑Ming Chai
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Bin Dong
China State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China

Corresponding Author: Bin Dong

dongbin@upc.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 190

Abstract

Glycerol (electrochemical) oxidation reaction (GOR) producing organic small molecule acid and coupling with hydrogen evolution reaction is a critical aspect of ensuring balanced glycerol capacity and promoting hydrogen generation on a large scale. However, the development of highly efficient and selective non-noble metal-based GOR electrocatalysts is still a key problem. Here, an S-doped CuO nanorod array catalyst (S-CuO/CF) constructed by sulfur leaching and oxidative remodeling is used to drive GOR at low potentials: It requires potentials of only 1.23 and 1.33 V versus RHE to provide currents of 100 and 500 mA cm−2, respectively. Moreover, it shows satisfactory comprehensive performance (at 100 mA cm−2, Vcell = 1.37 V) when assembled as the anode in asymmetric coupled electrolytic cell. Furthermore, we propose a detailed cycle reaction pathway (in alkaline environment) of S-doped CuO surface promoting GOR to produce formic acid and glycolic acid. Among them, the C–C bond breaking and lattice oxygen deintercalation steps frequently involved in the reaction pathway are the key factors to determine the catalytic performance and product selectivity. This research provides valuable guidance for the development of transition metal-based electrocatalysts for GOR and valuable insights into the glycerol oxidation cycle reaction pathway.


Highlights:
1 S-doped CuO nanorod arrays (S-CuO/CF) constructed by sulfur leaching and oxidative remodeling strategy require only 1.23 and 1.33 V versus hydrogen evolution reaction (HER) to provide glycerol oxidation currents of 100 and 500 mA cm−2.
2 S-CuO/CF shows satisfactory performance (at 100 mA cm−2, Vcell = 1.37 V) assembled as the anode in asymmetric coupled electrolytic cell of glycerol oxidation reaction and HER.
3 The study identifies the key factors involved in the GOR reaction pathway, which include the C–C bond breaking and lattice oxygen deintercalation steps.

Keywords

Glycerol oxidation reaction (GOR) Hydrogen evolution reaction (HER) CuO Oxidative reconstruction Electronic modification
Fan, Ruo‑Yao, Xue‑Jun Zhai, Wei‑Zhen Qiao, Yu‑Sheng Zhang, Ning Yu, Na Xu, Qian‑Xi Lv, Yong‑Ming Chai, and Bin Dong. 2023. “Optimized Electronic Modification of S-Doped CuO Induced by Oxidative Reconstruction for Coupling Glycerol Electrooxidation With Hydrogen Evolution”. Nano-Micro Letters 15 (July):190. https://doi.org/10.1007/s40820-023-01159-6.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. M.L. Yue, H. Lambert, E. Pahon, R. Roche, S. Jemei et al., Hydrogen energy systems: A critical review of technologies, applications, trends and challenges. Renew. Sust. Energy Rev. 146, 111180 (2021). https://doi.org/10.1016/j.rser.2021.111180
  2. N. Heinemann, J. Alcalde, J.M. Miocic, S.J.T. Hangx et al., Enabling large-scale hydrogen storage in porous media the scientific challenges. Energy Environ. Sci. 14(2), 853–864 (2021). https://doi.org/10.1039/D0EE03536J
  3. K.W. Wang, K.F. Yu, S.N. Xu, S.S. Yuan, L.J. Xiang et al., Synergizing lattice strain and electron transfer in TMSs@1T-MoS2 in-plane heterostructures for efficient hydrogen evolution reaction. Appl. Catal. B Environ. 328(5), 122445 (2023). https://doi.org/10.1016/j.apcatb.2023.122445
  4. M.L. Yu, K. Wang, H. Vredenburg, Insights into low-carbon hydrogen production methods: green, blue and aqua hydrogen. Int. J. Hydrogen Energy 46(41), 21261–21273 (2021). https://doi.org/10.1016/j.ijhydene.2021.04.016
  5. S.Y. Tee, K.Y. Win, W.S. Teo, L.D. Koh, S.H. Liu, C.P. Teng, M.Y. Han, Recent progress in energy-driven water splitting. Adv. Sci. 4(5), 1600337 (2017). https://doi.org/10.1002/advs.201600337
  6. S.L. Jiao, X.W. Fu, S.Y. Wang, Y. Zhao, Perfecting electrocatalysts via imperfections: towards the large-scale deployment of water electrolysis technology. Energy Environ. Sci. 14(4), 1722–1770 (2021). https://doi.org/10.1039/D0EE03635H
  7. S. Wang, A. Lu, C.J. Zhong, Hydrogen production from water electrolysis: role of catalysts. Nano Converg. 8(1), 4 (2021). https://doi.org/10.1186/s40580-021-00254-x
  8. J. Wang, S.J. Kim, J.P. Liu, Y. Gao, S. Choi et al., Redirecting dynamic surface restructuring of a layered transition metal oxide catalyst for superior water oxidation. Nat. Catal. 4(3), 212–222 (2021). https://doi.org/10.1038/s41929-021-00578-1
  9. J.J. Song, C. Wei, Z.F. Huang, C.T. Liu, L. Zeng et al., A review on fundamentals for designing oxygen evolution electrocatalysts. Chem. Soc. Rev. 49(7), 2196–2214 (2020). https://doi.org/10.1039/C9CS00607A
  10. R.Y. Fan, J.Y. Xie, H.J. Liu, H.Y. Wang, M.X. Li et al., Directional regulating dynamic equilibrium to continuously update electrocatalytic interface for oxygen evolution reaction. Chem. Eng. J. 431(2), 134040 (2022). https://doi.org/10.1016/j.cej.2021.134040
  11. H.A. Miller, K. Bouzek, J. Hnat, S. Loos, C.I. Bernacker et al., Green hydrogen from anion exchange membrane water electrolysis: a review of recent developments in critical materials and operating conditions. Sustain. Energy Fuels 4(5), 2114–2133 (2020). https://doi.org/10.1039/C9SE01240K
  12. B. You, X. Liu, N. Jiang, Y. Sun, A general strategy for decoupled hydrogenproduction from water splitting by integrating oxidative biomass valorization. J. Am. Chem. Soc. 138(41), 13639–13646 (2016). https://doi.org/10.1021/jacs.6b07127
  13. B. Rausch, M.D. Symes, G. Chisholm, L. Cronin, Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting. Science 345(6202), 1326–1330 (2014). https://doi.org/10.1126/science.1257443
  14. R.J. Quimet, J.R. Glenn, D.D. Porcellinis, A.R. Motz, M. Carmo et al., The role of electrocatalysts in the development of gigawatt-scale PEM electrolyzers. ACS Catal. 12(10), 6159–6171 (2022). https://doi.org/10.1021/acscatal.2c00570
  15. H.Y. Jin, X.S. Wang, C. Tang, A. Vasileff, L.Q. Li et al., Stable and highly efficient hydrogen evolution from seawater enabled by an unsaturated nickel surface nitride. Adv. Mater. 33(13), 2007508 (2021). https://doi.org/10.1002/adma.202007508
  16. W. Chen, L.T. Xu, X.R. Zhu, Y.C. Huang, W. Zhou et al., Unveiling the electrooxidation of urea: intramolecular coupling of the N–N bond. Angew. Chem. Int. Ed. 60(13), 7297–7307 (2021). https://doi.org/10.1002/anie.202015773
  17. X. Liu, Y. Han, Y. Guo, X.T. Zhao, D. Pan et al., Electrochemical hydrogen generation by oxygen evolution reaction-alternative anodic oxidation reactions. Adv. Energy Sustain. Res. 3(7), 2200005 (2022). https://doi.org/10.1002/aesr.202200005
  18. S.K. Geng, Y. Zheng, S.Q. Li, H. Su, X. Zhao et al., Nickel ferrocyanide as a high-performance urea oxidation electrocatalyst. Nat. Energy 6(9), 904–912 (2021). https://doi.org/10.1038/s41560-021-00899-2
  19. B.J. Zhu, Z.B. Liang, R.Q. Zou, Designing advanced catalysts for energy conversion based on urea oxidation reaction. Small 16(7), 1906133 (2020). https://doi.org/10.1002/smll.201906133
  20. P. Zhou, X.S. Lv, S.S. Tao, J.C. Wu, H.F. Wang et al., Heterogeneous-interface-enhanced adsorption of organic and hydroxyl for biomass electrooxidation. Adv. Mater. 34(42), 2204089 (2022). https://doi.org/10.1002/adma.202204089
  21. T.H. Wang, Z.F. Huang, T.Y. Liu, L. Tao, J. Tian et al., Transforming electrocatalytic biomass upgrading and hydrogen production from electricity input to electricity output. Angew. Chem. Int. Ed. 61(12), 2115636 (2022). https://doi.org/10.1002/anie.202115636
  22. X.D. Li, P. Jia, T.F. Wang, Furfural: a promising platform compound for sustainable production of C4 and C5 Chemicals. ACS Catal. 6, 7621–7640 (2016). https://doi.org/10.1021/acscatal.6b01838
  23. C.A.G. Quispe, C.J.R. Coronado, J.A. Carvalho, Glycerol: production, consumption, prices, characterization and new trends in combustion. Renew. Sust. Energ. Rev. 27(11), 475–493 (2013). https://doi.org/10.1021/acscatal.6b01838
  24. J.J. Bozell, G.R. Petersen, Technology development for the production of biobased products from biorefinery carbohydrates-the US Department of Energy’s “Top 10” revisited. Green Chem. 12(4), 539–554 (2010). https://doi.org/10.1039/B922014C
  25. S. Bagheri, N.M. Julkapli, W.A. Yehye, Catalytic conversion of biodiesel derived raw glycerol to value added products. Renew. Sust. Energ. Rev. 41, 113–127 (2015). https://doi.org/10.1016/j.rser.2014.08.031
  26. G. Dodekatos, S. Schunemann, H. Tuysuz, Recent advances in thermo-, photo-, and electrocatalytic glycerol oxidation. ACS Catal. 8(7), 6301–6333 (2018). https://doi.org/10.1021/acscatal.8b01317
  27. L. Luo, W.S. Chen, S.M. Xu, J.R. Yang, M. Li et al., Selective photoelectrocatalytic glycerol oxidation to dihydroxyacetone via enhanced middle hydroxyl adsorption over a Bi2O3-incorporated catalyst. J. Am. Chem. Soc. 144(17), 7720–7730 (2022). https://doi.org/10.1021/jacs.2c00465
  28. Z.Y. He, J. Hwang, Z.H. Gong, M.Z. Zhou, N. Zhang et al., Promoting biomass electrooxidation via modulating proton and oxygen anion deintercalation in hydroxide. Nat. Commun. 13(1), 3777 (2022). https://doi.org/10.1038/s41467-022-31484-0
  29. X.T. Han, H.Y. Sheng, C. Yu, T.W. Walker, G.W. Huber et al., Electrocatalytic oxidation of glycerol to formic acid by CuCo2O4 spinel oxide nanostructure catalysts. ACS Catal. 10(12), 6741–6752 (2020). https://doi.org/10.1021/acscatal.0c01498
  30. Y. Li, X.F. Wei, L.S. Chen, J.L. Shi, M.Y. He, Nickel-molybdenum nitride nanoplate electrocatalysts for concurrent electrolytic hydrogen and formate productions. Nat. Commun. 10, 5335 (2019). https://doi.org/10.1038/s41467-019-13375-z
  31. E. Kociolek-Balawejder, E. Stanislawska, I. Jacukowicz-Sobala, P. Mazur, Cuprite-doped macroreticular anion exchanger obtained by reduction of the Cu(OH)2 deposit. J. Environ. Chem. Eng. 7(3), 103198 (2019). https://doi.org/10.1016/j.jece.2019.103198
  32. B. Peng, T.T. Song, T. Wang, L.Y. Chai, W.C. Yang et al., Facile synthesis of Fe3O4@Cu(OH)2 composites and their arsenic adsorption application. Chem. Eng. J. 299(1), 15–22 (2016). https://doi.org/10.1016/j.cej.2016.03.135
  33. Y.L. Deng, A.D. Handoko, Y.H. Du, S.B. Xi, B.S. Yeo, In situ raman spectroscopy of copper and copper oxide surfaces during electrochemical oxygen evolution reaction: Identification of CuIII oxides as catalytically active species. ACS Catal. 6(4), 2473–2481 (2016). https://doi.org/10.1021/acscatal.6b00205
  34. J.Y. Sun, H.B. Zhou, P. Song, Y.J. Liu, X.Y. Wang et al., Cuprous sulfide derived CuO nanowires as effective electrocatalyst for oxygen evolution. Appl. Surf. Sci. 547, 149235 (2021). https://doi.org/10.1016/j.apsusc.2021.149235
  35. L. Meda, G.F. Cerofolini, A decomposition procedure for the determination of copper oxidation states in Cu-zeolites by XPS. Surf. Interface Anal. 36(8), 756–759 (2004). https://doi.org/10.1002/sia.1757
  36. M.C. Biesinger, L.W.M. Lau, A.R. Gerson, R.S.C. Smart, Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn. Appl. Surf. Sci. 257(3), 887–898 (2010). https://doi.org/10.1016/j.apsusc.2010.07.086
  37. J.Y. Kim, D. Hong, J.C. Lee, H.G. Kim, S. Lee et al., Quasi-graphitic carbon shell-induced Cu confinement promotes electrocatalytic CO2 reduction toward C2+ products. Nat. Commun. 12(1), 3765 (2021). https://doi.org/10.1016/10.1038/s41467-021-24105-9
  38. M. Chauhan, K.P. Reddy, C.S. Gopinath, S. Deka, Copper cobalt sulfide nanosheets Realizing a promising electrocatalytic oxygen evolution reaction. ACS Catal. 7(9), 5871–5879 (2017). https://doi.org/10.1021/acscatal.7b01831
  39. D.T. Chen, L.H. Zhang, J. Du, H.H. Wang, J.Y. Guo et al., A tandem strategy for enhancing electrochemical CO2 reduction activity of single-atom Cu–S1N3 catalysts via integration with Cu nanoclusters. Angew. Chem. Int. Ed. 60(45), 24022–24027 (2021). https://doi.org/10.1002/anie.202109579
  40. Y. Xu, T.T. Liu, K.K. Shi, H.J. Yu, K. Deng et al., Ru-doping induced lattice strain in hetero-phase Ni2P-Ni12P5 arrays enables simultaneous efficient energy-saving hydrogen generation and formate electrosynthesis. J. Mater. Chem. A 10(38), 20365–20374 (2022). https://doi.org/10.1039/D2TA05151F
  41. M.R. Rizk, M.G.A. El-Moghny, H.H. Abdelhady, W.M. Ragheb, A.H. Mohamed et al., Tailor-designed bimetallic Co/Ni macroporous electrocatalyst for efficient glycerol oxidation and water electrolysis. Int. J. Hydrogen Energy 47(75), 32145–32157 (2022). https://doi.org/10.1016/j.ijhydene.2022.07.129
  42. G. Ma, N. Yang, G.F. Zhou, X. Wang, The electrochemical reforming of glycerol at Pd nanocrystals modified ultrathin NiO nanoplates hybrids: An efficient system for glyceraldehyde and hydrogen coproduction. Nano Res. 15(3), 1934–1941 (2022). https://doi.org/10.1007/s12274-021-3829-6
  43. Z.J. Ke, N. Williams, X.X. Yan, S. Younan, D. He et al., Solar-assisted co-electrolysis of glycerol and water for concurrent production of formic acid and hydrogen. J. Mater. Chem. A 9(35), 19975–19983 (2021). https://doi.org/10.1039/D1TA02654B
  44. L.S. Oh, M. Park, Y.S. Park, Y. Kim, W. Yoon et al., How to change the reaction chemistry on nonprecious metal oxide nanostructure materials for electrocatalytic oxidation of biomass-derived glycerol to renewable chemicals. Adv. Mater. 35(4), 2203285 (2023). https://doi.org/10.1002/adma.202203285
  45. Y. Zhu, Q.Z. Qian, Y.X. Chen, X.Y. He, X.W. Shi et al., Biphasic transition metal nitride electrode promotes nucleophile oxidation reaction for practicable hybrid water electrocatalysis. Adv. Funct. Mater. (2023). https://doi.org/10.1002/adfm.202300547
  46. B.W. Liu, G.X. Wang, X. Feng, L. Dai, Z.H. Wen et al., Energy-saving H2 production from a hybrid acid/alkali electrolyzer assisted by anodic glycerol oxidation. Nanoscale 14, 12841–12848 (2022). https://doi.org/10.1039/D2NR02689A
  47. J.W. Du, Y. Qin, T. Dou, J.M. Ge, Y.P. Wang et al., Copper nanops dotted on copper sulfide nanosheets for selective electrocatalytic oxidation of glycerol to formate. ACS Appl. Nano Mater. 5(8), 10174–10182 (2022). https://doi.org/10.1021/acsanm.2c00323
  48. W. Chen, C. Xie, Y.Y. Wang, Y.Q. Zou, C.L. Dong et al., Activity origins and design principles of nickel-based catalysts for nucleophile electrooxidation. Chem 6(11), 2974–2993 (2020). https://doi.org/10.1016/j.chempr.2020.07.022
  49. X. Liu, Z.Y. Fang, X. Teng, Y.L. Niu, S.Q. Gong et al., Paired formate and H2 productions via efficient bifunctional Ni–Mo nitride nanowire electrocatalysts. J. Energy Chem. 72, 432–441 (2022). https://doi.org/10.1016/j.jechem.2022.04.040
  50. J.X. Wu, J.L. Li, Y.F. Li, X.Y. Ma, W.Y. Zhang et al., Steering the glycerol electro-reforming selectivity via cation–intermediate interactions. Angew. Chem. Int. Ed. 61(11), 202113362 (2022). https://doi.org/10.1002/anie.202113362
  51. F. Yang, J.Y. Ye, Q. Yuan, X.T. Yang, Z.X. Xie et al., Ultrasmall Pd–Cu–Pt trimetallic twin Iicosahedrons boost the electrocatalytic performance of glycerol oxidation at the operating temperature of fuel cells. Adv. Funct. Mater. 30(11), 1908235 (2020). https://doi.org/10.1002/adfm.201908235
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 3510 Download : 2626

Most read articles by the same author(s)