Skip to main content
SpringerLink
Log in

Amorphous MoO2 with a porous nanostructure as a highly efficient electrocatalyst for overall water splitting

  • Published:
Applied Physics A Aims and scope Submit manuscript

Abstract

Designing an economical, superior activity, excellent stability, and earth-rich catalysts is of crucial significance in the progress of electrochemical water splitting and still remains huge challenge to overcome. In this work, amorphous MoO2 with a porous nanostructure as a novel bifunctional electrocatalyst has been prepared by the hydrothermal method. This nanostructure has excellent HER/OER properties, in which the amorphous and porous states have a large number of vacancies and active sites exposed to the electrolyte. The as-prepared sample has been researched in detail via X-ray diffraction (XRD) and transmission electron microscopy (TEM). Electrochemical experiments show that when the current density reaches − 10 mA cm−2, the as-prepared samples need an overpotential of only about − 0.930 V (vs. RHE) in 1 M H2SO4 and − 0.777 V (vs. RHE) in 1 M KOH for HER, respectively. Furthermore, MoO2 exhibits an extremely overpotential of 2.414 V (vs. RHE) at 10 mA cm−2 in 1 M KOH for OER. It is believed that the amorphous and porous nanostructure remains a promising and efficient hydrolytic electrocatalyst.

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

Similar content being viewed by others

Data availability statement

All data generated or analysed during this study are included in this published article (and its supplementary information files).

References

  1. C. Iffelsberger, S. Ng, M. Pumera, Catalyst coating of 3D printed structures via electrochemical deposition: case of the transition metal chalcogenide MoSx for hydrogen evolution reaction. Appl. Mater. Today 20, 100654 (2020)

    Google Scholar 

  2. A. Muthurasu, V. Maruthapandian, H.Y. Kim, Metal-organic framework derived Co3O4/MoS2 heterostructure for efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction. Appl. Catal. B 248, 202–210 (2019)

    Google Scholar 

  3. Z. Wu, D. Nie, M. Song, T. Jiao, G. Fu, X. Liu, Facile synthesis of Co–Fe–B–P nanochains as an efficient bifunctional electrocatalyst for overall water-splitting. Nanoscale 11, 7506–7512 (2019)

    Google Scholar 

  4. B. Liu, C. Wu, G. Chen, W. Chen, L. Peng, Y. Yao, Z. Wei, H. Zhu, T. Han, D. Tang, All-in-one surface engineering strategy on nickel phosphide arrays towards a robust electrocatalyst for hydrogen evolution reaction. J. Power Sources 429, 46–54 (2019)

    ADS  Google Scholar 

  5. T.A. Le, N.Q. Tran, Y. Hong, M. Kim, H. Lee, Porosity-engineering of MXene as a support material for a highly efficient electrocatalyst toward overall water splitting. Chemsuschem 13(5), 945–955 (2020)

    Article  Google Scholar 

  6. H. Qiao, H. Liu, Z. Huang, Q. Ma, S. Luo, J. Li, Y. Liu, J. Zhong, X. Qi, Black phosphorus nanosheets modified with Au nanoparticles as high conductivity and high activity electrocatalyst for oxygen evolution reaction. Adv. Energy Mater. 10, 2002424 (2020)

    Google Scholar 

  7. B. Wang, Y. Hu, B. Yu, X. Zhang, D. Yang, Y. Chen, Heterogeneous CoFe–Co8FeS8 nanoparticles embedded in CNT networks as highly efficient and stable electrocatalysts for oxygen evolution reaction. J. Power Sources 433, 126688 (2019)

    Google Scholar 

  8. C.C. Chang, S.R. Li, H.L. Chou, Y.C. Lee, S. Patil, Y.S. Lin, C.C. Chang, Y.J. Chang, D.Y. Wang, Photoactive earth-abundant iron pyrite catalysts for electrocatalytic nitrogen reduction reaction. Small 15, 1904723 (2019)

    Google Scholar 

  9. Z.P. Wu, X.F. Lu, S.Q. Zang, X.W. Lou, Non-noble-metal-based electrocatalysts toward the oxygen evolution reaction. Adv. Funct. Mater. 30, 1910274 (2020)

    Google Scholar 

  10. D. Chen, C. Chen, Z.M. Baiyee, Z. Shao, F. Ciucci, Nonstoichiometric oxides as low-cost and highly-efficient oxygen reduction/evolution catalysts for low-temperature electrochemical devices. Chem. Rev. 115, 9869–9921 (2015)

    Google Scholar 

  11. C.G. Morales-Guio, L.A. Stern, X. Hu, Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 43, 6555–6569 (2014)

    Google Scholar 

  12. Y. Zhong, B. Chang, Y. Shao, C. Xu, Y. Wu, X. Hao, Regulating phase conversion from Ni3Se2 into NiSe in a bifunctional electrocatalyst for overall water-splitting enhancement. Chemsuschem 12, 2008–2014 (2019)

    Google Scholar 

  13. X. Sun, J. Dai, Y. Guo, C. Wu, F. Hu, J. Zhao, X. Zeng, Y. Xie, Semimetallic molybdenum disulfide ultrathin nanosheets as an efficient electrocatalyst for hydrogen evolution. Nanoscale 6, 8359–8367 (2014)

    ADS  Google Scholar 

  14. X. Ren, J. Zhou, X. Qi, Y. Liu, Z. Huang, Z. Li, Y. Ge, S.C. Dhanabalan, J.S. Ponraj, S. Wang, Few-layer black phosphorus nanosheets as electrocatalysts for highly efficient oxygen evolution reaction. Adv. Energy Mater. 7, 1700396 (2017)

    Google Scholar 

  15. H. Du, K. Wang, S. He, K. Yang, W. Ai, W. Huang, Defect-rich crystalline WSe2 nanosheets as efficient electrocatalysts for hydrogen evolution reaction. Mater. Rep. 34(1), 1195–1200 (2020)

    Google Scholar 

  16. L. Chen, T. Liu, S. Liu et al., S vacant CuIn5S8 confined in a few-layer MoSe2 with interlayer-expanded hollow heterostructures boost photocatalytic CO2 reduction. Rare Met. 41(1), 144–154 (2022)

    Google Scholar 

  17. C. An, W. Kang, Q. Deng, N. Hu, Pt and Te codoped ultrathin MoS2 nanosheets for enhanced hydrogen evolution reaction with wide pH range. Rare Met. 41(2), 378–384 (2021)

    Article  Google Scholar 

  18. H. Wang, H.W. Lee, Y. Deng, Z. Lu, P.C. Hsu, Y. Liu, D. Lin, Y. Cui, Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting. Nature Commun. 6, 7261 (2015)

    ADS  Google Scholar 

  19. J. Zhou, Y. Liu, Z. Zhang, Z. Huang, X. Chen, X. Ren, L. Ren, X. Qi, J. Zhong, Hierarchical NiSe2 sheet-like nano-architectures as an efficient and stable bifunctional electrocatalyst for overall water splitting: phase and morphology engineering. Electrochim. Acta 279, 195–203 (2018)

    Article  Google Scholar 

  20. J. Zhao, H. Hu, M. Wu, N-Doped-carbon/cobalt-nanoparticle/N-doped-carbon multi-layer sandwich nanohybrids derived from cobalt MOFs having 3D molecular structures as bifunctional electrocatalysts for on-chip solid-state Zn–air batteries. Nanoscale 12, 3750–3762 (2020)

    Google Scholar 

  21. H. Huang, S. Zhou, C. Yu, H. Huang, J. Zhao, L. Dai, J. Qiu, Rapid and energy-efficient microwave pyrolysis for high-yield production of highly-active bifunctional electrocatalysts for water splitting. Energy Environ. Sci. 13, 545–553 (2020)

    Google Scholar 

  22. Y. Jin, P.K. Shen, Nanoflower-like metallic conductive MoO2 as a high-performance non-precious metal electrocatalyst for hydrogen evolution reaction. J. Mater. Chem. A 3, 20080–20085 (2015)

    Google Scholar 

  23. G. Hu, Q. Ou, G. Si, Y. Wu, J. Wu, Z. Dai, A. Krasnok, Y. Mazor, Q. Zhang, Q. Bao, Topological polaritons and photonic magic angles in twisted α-MoO3 bilayers. Nature 582, 209–213 (2020)

    ADS  Google Scholar 

  24. B.A. Yusuf, M. Xie, N. Ullah, C.J. Oluigbo, W. Yaseen, J. Xie, Y. Xu, Facile synthesis of N, S co-doped MoO2@C nanorods as an outstanding electrocatalyst for hydrogen evolution reaction. Appl. Surf. Sci. 537, 147971 (2021)

    Google Scholar 

  25. Y. Shi, B. Guo, S.A. Corr, Q. Shi, Y.S. Hu, K.R. Heier, L. Chen, R. Seshadri, G.D. Stucky, Ordered mesoporous metallic MoO2 materials with highly reversible lithium storage capacity. Nano Lett. 9, 4215 (2009)

    ADS  Google Scholar 

  26. B. Guo, X. Fang, B. Li, Y. Shi, C. Ouyang, Y.S. Hu, Z. Wang, G.D. Stucky, L. Chen, Synthesis and lithium storage mechanism of ultrafine MoO2 nanorods. Chem. Mater. 24, 457–463 (2012)

    Google Scholar 

  27. B. Zhang, Y. Xue, A. Jiang, Z. Xue, Z. Li, J. Hao, An ionic liquid as reaction medium for synthesis of hierarchically structured one-dimensional MoO2 for efficient hydrogen evolution. ACS Appl. Mater. Interfaces 9, 7217–7223 (2017)

    Google Scholar 

  28. B.B. Li, Y.Q. Liang, X.J. Yang, Z.D. Cui, S.Z. Qiao, S.L. Zhu, Z.Y. Li, K. Yin, MoO2-CoO coupled with a macroporous carbon hybrid electrocatalyst for highly efficient oxygen evolution. Nanoscale 7, 16704–16714 (2015)

    ADS  Google Scholar 

  29. B.A. Yusuf, Y. Xu, N. Ullah, M. Xie, C.J. Oluigbo, W. Yaseen, J.K. Alagarasan, K. Rajalakshmi, J. Xie, B-doped carbon enclosed Ni nanoparticles: a robust, stable and efficient electrocatalyst for hydrogen evolution reaction. J. Electroanal. Chem. 869, 114085 (2020)

    Google Scholar 

  30. F. Sun, G. Wang, Y. Ding, C. Wang, B. Yuan, Y. Lin, NiFe-based metal-organic framework nanosheets directly supported on nickel foam acting as robust electrodes for electrochemical oxygen evolution reaction. Adv. Energy Mater. 8, 1800584 (2018)

    Google Scholar 

  31. L. Jing, D. Wang, Y. Xu, M. Xie, J. Yan, M. He, Z. Song, H. Xu, H. Li, Porous defective carbon nitride obtained by a universal method for photocatalytic hydrogen production from water splitting. J. Colloid Interface Sci. 566, 171–182 (2020)

    ADS  Google Scholar 

  32. D. Kong, H. Wang, Z. Lu, Y. Cui, CoSe2 nanoparticles grown on carbon fiber paper: an efficient and stable electrocatalyst for hydrogen evolution reaction. J. Am. Chem. Soc. 136, 4897–4900 (2014)

    Google Scholar 

  33. Y. Jin, H. Wang, J. Li, X. Yue, Y. Han, P.K. Shen, Y. Cui, Porous MoO2 nanosheets as non-noble bifunctional electrocatalysts for overall water splitting. Adv. Mater. 28, 3785–3790 (2016)

    Google Scholar 

  34. S. Wu, X. Lv, D. Ping, G. Zhang, S. Wang, H. Wang, X. Yang, D. Guo, S. Fang, Highly exposed atomic Fe–N active sites within carbon nanorods towards electrocatalytic reduction of CO2 to CO. Electrochim. Acta 340, 135930 (2020)

    Google Scholar 

  35. G. Chen, P. Liu, Z. Liao, F. Sun, Y. He, H. Zhong, T. Zhang, E. Zschech, M. Chen, G. Wu, Zinc-mediated template synthesis of Fe–N–C electrocatalysts with densely accessible Fe–Nx active sites for efficient oxygen reduction. Adv. Mater. 32, 1907399 (2020)

    Google Scholar 

  36. R. Liu, Y. Wang, D. Liu, Y. Zou, S. Wang, Water-plasma-enabled exfoliation of ultrathin layered double hydroxide nanosheets with multivacancies for water oxidation. Adv. Mater. 29, 1701546 (2017)

    Google Scholar 

  37. L. Pei, X. Zhang, Z. Yuan, Catalytic performance of amorphous alloy in wastewater treatment. Mater. Rep. 36(2), 20080033–20080039 (2022)

    Google Scholar 

  38. E. Tsuji, A. Imanishi, K.I. Fukui, Y. Nakato, Electrocatalytic activity of amorphous RuO electrode for oxygen evolution in an aqueous solution. Electrochim. Acta 56, 2009–2016 (2011)

    Google Scholar 

  39. D. Zhang, Y. Guo, Z. Zhao, Porous defect-modified graphitic carbon nitride via a facile one-step approach with significantly enhanced photocatalytic hydrogen evolution under visible light irradiation. Appl. Catal. B 226, 1–9 (2018)

    Google Scholar 

  40. J.-J. Li, S.-C. Cai, Z. Xu, X. Chen, J. Chen, H.-P. Jia, J. Chen, Solvothermal syntheses of Bi and Zn co-doped TiO2 with enhanced electron-hole separation and efficient photodegradation of gaseous toluene under visible-light. J. Hazard. Mater. 325, 261–270 (2017)

    Google Scholar 

  41. H. Li, S. Chen, X. Jia, B. Xu, H. Lin, H. Yang, L. Song, X. Wang, Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting. Nat. Commun. 8, 15377 (2017)

    ADS  Google Scholar 

  42. Y. Yang, Y. Yang, S. Chen, Q. Lu, L. Song, Y. Wei, X. Wang, Atomic-level molybdenum oxide nanorings with full-spectrum absorption and photoresponsive properties. Nat. Commun. 8, 1559 (2017)

    ADS  Google Scholar 

  43. D. Zhou, Z. Cai, X. Lei, W. Tian, Y. Bi, Y. Jia, N. Han, T. Gao, Q. Zhang, Y. Kuang, NiCoFe-layered double hydroxides/N-doped graphene oxide array colloid composite as an efficient bifunctional catalyst for oxygen electrocatalytic reactions. Adv. Energy Mater. 8(9), 1701905 (2017)

    Article  Google Scholar 

  44. M. Xu, L. Han, Y. Han, Y. Yu, J. Zhai, S. Dong, Porous CoP concave polyhedron electrocatalysts synthesized from metal–organic frameworks with enhanced electrochemical properties for hydrogen evolution. J. Mater. Chem. A 3, 21471–21477 (2015)

    Google Scholar 

  45. X. Duan, J. Xu, Z. Wei, J. Ma, S. Guo, H. Liu, S. Dou, Atomically thin transition-metal dichalcogenides for electrocatalysis and energy storage. Small Methods 1, 1700156 (2017)

    Google Scholar 

  46. N.H. Attanayake, A.C. Thenuwara, A. Patra, Y.V. Aulin, T. Tran, H. Chakraborty, E. Borguet, M.L. Klein, J.P. Perdew, D.R. Strongin, Effect of intercalated metals on the electrocatalytic activity of 1T-MoS2 for the hydrogen evolution reaction. ACS Energy Lett. 3, 7–13 (2017)

    Google Scholar 

  47. I. Liberman, R. Shimoni, R. Ifraemov, I. Rozenberg, C. Singh, I. Hod, Active-site modulation in an Fe-Porphyrin-based metal-organic framework through ligand axial coordination: accelerating electrocatalysis and charge-transport kinetics. J Am Chem Soc 142, 1933–1940 (2020)

    Google Scholar 

  48. M.R. Gao, M.K.Y. Chan, Y. Sun, Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production. Nat. Commun. 6, 7493 (2015)

    ADS  Google Scholar 

  49. C. Xie, Y. Wang, D. Yan, L. Tao, S. Wang, In situ growth of cobalt@cobalt–borate core–shell nanosheets as highly-efficient electrocatalysts for oxygen evolution reaction in alkaline/neutral medium. Nanoscale 9, 16059 (2017)

    Google Scholar 

  50. D. Voiry, H. Yamaguchi, J. Li, R. Silva, D.C. Alves, T. Fujita, M. Chen, T. Asefa, V.B. Shenoy, G. Eda, Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 12, 850–855 (2013)

    ADS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Grants from National Natural Science Foundation of China (No. 11504312), Excellent Youth Foundation of Hubei Province (Grant No. 2019CFA083), Provincial Natural Science Foundation of Hunan (No. 2016JJ2132, 2021JJ30298), the Science and Technology Program of Hunan Province, China (Grant No. 2019TP1014), as well as the Program for Changjiang Scholars and Innovative Research Team in University (IRT_17R91).

Author information

Authors and Affiliations

  1. Key Laboratory of Hunan Province on Information Photonics and Freespace Optical Communications, School of Physics and Electrical Sciences, Hunan Institute of Science and Technology, Yueyang, 414006, People’s Republic of China

    Jiayou Tao, Yanmo Liao, Gaohua Liao, Zhijun Zou, Lin Lang & Chang Li

  2. School of Physics and Optoelectronics, Xiangtan University, Xiangtan, 411105, People’s Republic of China

    Shuhua Liu, Yanmo Liao, Hui Qiao & Xiang Qi

  3. The Institute of Technological Sciences, Wuhan University, Wuhan, 430072, People’s Republic of China

    Ziyu Wang

Authors
  1. Jiayou Tao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shuhua Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yanmo Liao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hui Qiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Gaohua Liao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zhijun Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Lin Lang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Chang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Ziyu Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Xiang Qi
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

JT contributed to the experiment, processed the data and wrote the paper. The data analysis was performed and the grammar was modified by SL, YL and HQ, GL, ZZ and LL conducted the experiment and discussed the results. CL and XQ proposed the study conception and design. ZW is responsible for part of the experimental data, data discussion and grammar revision.

Corresponding authors

Correspondence to Chang Li or Xiang Qi.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

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 4994 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tao, J., Liu, S., Liao, Y. et al. Amorphous MoO2 with a porous nanostructure as a highly efficient electrocatalyst for overall water splitting. Appl. Phys. A 128, 618 (2022). https://doi.org/10.1007/s00339-022-05734-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00339-022-05734-3

Keywords

Search

Navigation