Skip to main content
SpringerLink
Log in

Synergetic effect of phosphorus-dopant and graphene-covering layer on hydrogen evolution activity and durability of NiCo2S4 electrocatalysts

磷掺杂剂和石墨烯包覆层对NiCo2S4电催化剂析氢活 性和耐久性的协同影响

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

The investigation of highly conductive and stable non-noble metal electrocatalysts is imperative for promoting the hydrogen economy. Herein, we employed het-eroatom-doping and graphene-covering techniques to enhance the electronic properties of NiCo2S4 (NCS) yolk-shell microspheres, boosting their resistance to H2O and O2 corrosion in acidic environments. Based on the results of density functional theory (DFT) simulations and comprehensive characterizations, P heteroatom introduction into NCS was found to expedite electron transfer from bulk to surface, reducing the barrier for the hydrogen evolution reaction (HER) on neighboring active S sites. DFT-calculated energy barriers and X-ray photoelectron spectrometer analysis substantiated that the reduced graphene oxide (rGO)-covering layer played a vital role by facilitating proton permeability in HER while hindering H2O and O2 molecule penetration. By leveraging charge transfer and mass transfer, a balanced catalyst with high activity and corrosion resistance was achieved. The optimized P-NCS/rGO catalyst exhibited a current density of 10 mA cm−2 at a low overpotential of 70 mV, demonstrating excellent durability over 80 h. This study exemplified the rational design of graphene-covered sulfide catalysts, enhancing electrocatalyst performance through the regulation of electronic structures and proton/molecule penetration.

摘要

探索具有优异导电性和稳定性的非贵金属电催化剂对氢经济至关重要. 本研究将杂原子掺杂和石墨烯包覆相结合, 以控制NiCo2S4(NCS)蛋黄壳微球的电子性能, 并抵抗酸性介质中H2O和O2的腐蚀. 密度泛函理论(DFT)模拟结合综合表征和实验首次揭示了在NCS中引入P杂原子不仅加速了电子从体相向表面的转移动力学, 而且降低了掺杂P原子附近活性S位上的析氢反应势垒. 利用DFT计算的穿透能垒预测了rGO覆盖层在P掺杂NCS (P-NCS)表面对质子的渗透性和对H2O和O2分子的抵抗性等重要功能, 并用X射线光电子能谱对新催化剂和回收催化剂进行了验证. 利用P掺杂剂和rGO覆盖层分别辅助电荷传递和质子传递, 通过二者的协同作用获得了催化活性和耐久性之间的平衡. 因此, 优化后的P-NCS/rGO在70 mV的低过电位下实现了10 mA cm−2的电流密度, 并具有令人满意的80小时耐用性. 本工作阐明了石墨烯覆盖硫化物催化剂可通过调控电子结构和质子/分子穿透提高电催化性能.

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

Similar content being viewed by others

References

  1. Cai X, Zeng Z, Liu Y, et al. Visible-light-driven water splitting by yolk-shelled ZnIn2S4-based heterostructure without noble-metal co-catalyst and sacrificial agent. Appl Catal B-Environ, 2021, 297: 120391

    CAS  Google Scholar 

  2. Gao X, Zhou Y, Cheng Z, et al. Distance synergy of single Ag atoms doped MoS2 for hydrogen evolution electrocatalysis. Appl Surf Sci, 2021, 547: 149113

    CAS  Google Scholar 

  3. Li M, Wang J, Guo X, et al. Structural engineering of Fe-doped Ni2P nanosheets arrays for enhancing bifunctional electrocatalysis towards overall water splitting. Appl Surf Sci, 2021, 536: 147909

    CAS  Google Scholar 

  4. Li P, Li W, Zhao S, et al. Advanced hydrogen evolution electrocatalysis enabled by ruthenium phosphide with tailored hydrogen binding strength via interfacial electronic interaction. Chem Eng J, 2022, 429: 132557

    CAS  Google Scholar 

  5. Li X, Wang C, Zheng S, et al. Electrochemical activation-induced surface-reconstruction of NiOx microbelt superstructure of core-shell nanoparticles for superior durability electrocatalysis. J Colloid Interface Sci, 2022, 624: 443–449

    CAS  Google Scholar 

  6. Zheng H, Huang X, Gao H, et al. Cobalt-tuned nickel phosphide na-noparticles for highly efficient electrocatalysis. Appl Surf Sci, 2019, 479: 1254–1261

    CAS  Google Scholar 

  7. Gu H, Fan W, Liu T. Phosphorus-doped NiCo2S4 nanocrystals grown on electrospun carbon nanofibers as ultra-efficient electrocatalysts for the hydrogen evolution reaction. Nanoscale Horiz, 2017, 2: 277–283

    CAS  Google Scholar 

  8. Lin F, Lv B, Gao H, et al. Graphite nanoflake-modified Mo2C with ameliorated interfacial interaction as an electrocatalyst for hydrogen evolution reaction. ACS Appl Mater Interfaces, 2022, 14: 56407–56415

    CAS  Google Scholar 

  9. Wang C, Zhang M, Song J, et al. Two-dimensional conductive n-con-jugated metal-organic frameworks as promising electrocatalysts for highly efficient hydrogen evolution reaction. Appl Surf Sci, 2022, 601: 154241

    CAS  Google Scholar 

  10. Zhang H, Liu S, Tian P, et al. Mesoporous RhTe nanowires towards all-pH-value hydrogen evolution electrocatalysis. Chem Eng J, 2022, 435: 134798

    CAS  Google Scholar 

  11. Lu C, You D, Li J, et al. Full-spectrum nonmetallic plasmonic carriers for efficient isopropanol dehydration. Nat Commun, 2022, 13: 6984

    CAS  Google Scholar 

  12. Xu W, Tang H, Gu H, et al. Research progress of asymmetrically coordinated single-atom catalysts for electrocatalytic reactions. J Mater Chem A, 2022, 10: 14732–14746

    CAS  Google Scholar 

  13. Dai W, Pan Y, Ren K, et al. Heteroatom Ni alloyed pyrite-phase FeS2 as a pre-catalyst for enhanced oxygen evolution reaction. Electrochim Acta, 2020, 355: 136821

    CAS  Google Scholar 

  14. Ji X, Zhang R, Shi X, et al. Fabrication of hierarchical CoP na-nosheet@microwire arrays via space-confined phosphidation toward high-efficiency water oxidation electrocatalysis under alkaline conditions. Nanoscale, 2018, 10: 7941–7945

    CAS  Google Scholar 

  15. Lan M, Xie C, Li B, et al. Two-dimensional cobalt sulfide/iron-nitro-gen-carbon holey sheets with improved durability for oxygen electro-catalysis. ACS Appl Mater Interfaces, 2022, 14: 11538–11546

    CAS  Google Scholar 

  16. Lin J, Wang H, Cao J, et al. Engineering Se vacancies to promote the intrinsic activities of P doped NiSe2 nanosheets for overall water splitting. J Colloid Interface Sci, 2020, 571: 260–266

    CAS  Google Scholar 

  17. Men Y, Jia S, Li P, et al. Boosting alkaline hydrogen evolution elec-trocatalysis through electronic communicating vessels on Co2P/Co4N heterostructure catalyst. Chem Eng J, 2022, 433: 133831

    CAS  Google Scholar 

  18. Meng X, Yu L, Ma C, et al. Three-dimensionally hierarchical MoS2/graphene architecture for high-performance hydrogen evolution reaction. Nano Energy, 2019, 61: 611–616

    CAS  Google Scholar 

  19. Pak S, Lim J, Hong J, et al. Enhanced hydrogen evolution reaction in surface functionalized MoS2 monolayers. Catalysts, 2021, 11: 70

    CAS  Google Scholar 

  20. Sekar K, Raji G, Chen S, et al. Ultrathin VS2 nanosheets vertically aligned on NiCo2S4@C3N4 hybrid for asymmetric supercapacitor and alkaline hydrogen evolution reaction. Appl Surf Sci, 2020, 527: 146856

    CAS  Google Scholar 

  21. Wang Z, Tian Y, Wen M, et al. Integrating CoNiSe2 nanorod-arrays onto N-doped sea-sponge-C spheres for highly efficient electrocatalysis of hydrogen evolution reaction. Chem Eng J, 2022, 446: 137335

    CAS  Google Scholar 

  22. Chen Y, Liu T, Zhang L, et al. NiCo2S4 nanotubes anchored 3D nitrogen-doped graphene framework as electrode material with enhanced performance for asymmetric supercapacitors. ACS Sustain Chem Eng, 2019, 7: 11157–11165

    CAS  Google Scholar 

  23. Su H, Song S, Gao Y, et al. In situ electronic redistribution tuning of NiCo2S4 nanosheets for enhanced electrocatalysis. Adv Funct Mater, 2021, 32: 2109731

    Google Scholar 

  24. Feng X, Jiao Q, Cui H, et al. One-pot synthesis of NiCo2S4 hollow spheres via sequential ion-exchange as an enhanced oxygen bifunctional electrocatalyst in alkaline solution. ACS Appl Mater Interfaces, 2018, 10: 29521–29531

    CAS  Google Scholar 

  25. Zhang J, Guan H, Liu Y, et al. Hierarchical polypyrrole nanotu-bes@NiCo2S4 nanosheets core-shell composites with improved electrochemical performance as supercapacitors. Electrochim Acta, 2017, 258: 182–191

    CAS  Google Scholar 

  26. Han X, Zhang W, Ma X, et al. Identifying the activation of bimetallic sites in NiCo2S4@g-C3N4-CNT hybrid electrocatalysts for synergistic oxygen reduction and evolution. Adv Mater, 2019, 31: 1808281

    Google Scholar 

  27. Liu J, Wang J, Fo Y, et al. Engineering of unique Ni-Ru nano-twins for highly active and robust bifunctional hydrogen oxidation and hydrogen evolution electrocatalysis. Chem Eng J, 2023, 454: 139959

    CAS  Google Scholar 

  28. Wang M, Fu W, Du L, et al. Surface engineering by doping manganese into cobalt phosphide towards highly efficient bifunctional HER and OER electrocatalysis. Appl Surf Sci, 2020, 515: 146059

    CAS  Google Scholar 

  29. Zhao Y, Liu X, Liu Y, et al. Favorable pore size distribution of biomass-derived N, S dual-doped carbon materials for advanced oxygen reduction reaction. Int J Hydrogen Energy, 2022, 47: 12964–12974

    CAS  Google Scholar 

  30. Wu Y, Liu X, Han D, et al. Electron density modulation of NiCo2S4 nanowires by nitrogen incorporation for highly efficient hydrogen evolution catalysis. Nat Commun, 2018, 9: 1425

    Google Scholar 

  31. Lu XF, Zhang SL, Sim WL, et al. Phosphorized CoNi2S4 yolk-shell spheres for highly efficient hydrogen production via water and urea electrolysis. Angew Chem Int Ed, 2021, 60: 22885–22891

    CAS  Google Scholar 

  32. Le TT, Liu X, Xin P, et al. Phosphorus-doped Fe7S8@C nanowires for efficient electrochemical hydrogen and oxygen evolutions: Controlled synthesis and electronic modulation on active sites. J Mater Sci Tech, 2021, 74: 168–175

    CAS  Google Scholar 

  33. Huang L, Li W, Shen X, et al. Phosphorus-bridged ternary metal alloy encapsulated in few-layered nitrogen-doped graphene for highly efficient electrocatalytic hydrogen evolution. J Mater Chem A, 2022, 10: 7111–7121

    CAS  Google Scholar 

  34. Liu Q, Jin J, Zhang J. NiCo2S4@graphene as a bifunctional electro-catalyst for oxygen reduction and evolution reactions. ACS Appl Mater Interfaces, 2013, 5: 5002–5008

    CAS  Google Scholar 

  35. Shi X, Dai C, Wang X, et al. Protruding Pt single-sites on hexagonal ZnIn2S4 to accelerate photocatalytic hydrogen evolution. Nat Commun, 2022, 13: 1287

    CAS  Google Scholar 

  36. Li H, Chen L, Jin P, et al. NiCo2S4 microspheres grown on N, S co-doped reduced graphene oxide as an efficient bifunctional electro-catalyst for overall water splitting in alkaline and neutral pH. Nano Res, 2021, 15: 950–958

    Google Scholar 

  37. Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B, 1999, 59: 1758–1775

    CAS  Google Scholar 

  38. Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54: 11169–11186

    CAS  Google Scholar 

  39. Huo J, Wu J, Zheng M, et al. Flower-like nickel cobalt sulfide micro-spheres modified with nickel sulfide as Pt-free counter electrode for dye-sensitized solar cells. J Power Sources, 2016, 304: 266–272

    CAS  Google Scholar 

  40. Min K, Yoo R, Kim S, et al. Facile synthesis of P-doped NiCo2S4 na-noneedles supported on Ni foam as highly efficient electrocatalysts for alkaline oxygen evolution reaction. Electrochim Acta, 2021, 396: 139236

    CAS  Google Scholar 

  41. Hu S, Lozada-Hidalgo M, Wang FC, et al. Proton transport through one-atom-thick crystals. Nature, 2014, 516: 227–230

    CAS  Google Scholar 

  42. Shi L, Ying Z, Xu A, et al. Unraveling the water-mediated proton conduction mechanism along the surface of graphene oxide. Chem Mater, 2020, 32: 6062–6069

    CAS  Google Scholar 

  43. Hu K, Ohto T, Nagata Y, et al. Catalytic activity of graphene-covered non-noble metals governed by proton penetration in electrochemical hydrogen evolution reaction. Nat Commun, 2021, 12: 203

    CAS  Google Scholar 

  44. Leenaerts O, Partoens B, Peeters FM, et al. The work function of few-layer graphene. J Phys-Condens Matter, 2017, 29: 035003

    CAS  Google Scholar 

  45. Zhang L, Zhang H, Chu X, et al. Synthesis of size-controllable NiCo2S4 hollow nanospheres toward enhanced electrochemical performance. Energy Environ Mater, 2020, 3: 421–428

    CAS  Google Scholar 

  46. Jiang Y, Qian X, Zhu C, et al. Nickel cobalt sulfide double-shelled hollow nanospheres as superior bifunctional electrocatalysts for pho-tovoltaics and alkaline hydrogen evolution. ACS Appl Mater Interfaces, 2018, 10: 9379–9389

    CAS  Google Scholar 

  47. Song W, Xu M, Teng X, et al. Construction of self-supporting, hierarchically structured caterpillar-like NiCo2S4 arrays as an efficient tri-functional electrocatalyst for water and urea electrolysis. Nanoscale, 2021, 13: 1680–1688

    CAS  Google Scholar 

  48. Wu X, Yang Y, Zhang T, et al. CeOx-decorated hierarchical NiCo2S4 hollow nanotubes arrays for enhanced oxygen evolution reaction electrocatalysis. ACS Appl Mater Interfaces, 2019, 11: 39841–39847

    CAS  Google Scholar 

  49. Li M, Zhu Y, Song N, et al. Fabrication of Pt nanoparticles on nitrogen-doped carbon/Ni nanofibers for improved hydrogen evolution activity. J Colloid Interface Sci, 2018, 514: 199–207

    CAS  Google Scholar 

  50. Santhosh Kumar R, Ramakrishnan S, Prabhakaran S, et al. Structural, electronic, and electrocatalytic evaluation of spinel transition metal sulfide supported reduced graphene oxide. J Mater Chem A, 2022, 10: 1999–2011

    CAS  Google Scholar 

  51. Jia Y, Zhang L, Du A, et al. Defect graphene as a trifunctional catalyst for electrochemical reactions. Adv Mater, 2016, 28: 9532–9538

    CAS  Google Scholar 

  52. Jiao Y, Zheng Y, Davey K, et al. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nat Energy, 2016, 1: 16130

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Key R&D Program of China (2021YFA1501900), the National Natural Science Foundation of China-Yunnan Joint Fund (U2102215), the National Natural Science Foundation of China (22209203), China Postdoctoral Science Foundation (2021M693419), Jiangsu Key Laboratory of Coal-based Greenhouse Gas Control and Utilization (PCSX202202), the Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology (CUMTMS202202 and CUMTMS202207), and the Open Sharing Fund for the Large-scale Instruments and Equipment of China University of Mining and Technology.

Author information

Authors and Affiliations

  1. School of Materials Science and Physics, China University of Mining and Technology, Xuzhou, 221116, China

    Jie Chen  (陈杰), Liang Mao  (毛梁), Jiachen Xu  (徐家琛), Xiuquan Gu  (顾修全), Yulong Zhao  (赵宇龙), Yihan Ling  (凌意瀚), Yanwei Sui  (隋艳伟), Pengzhan Ying  (应鹏展) & Xiaoyan Cai  (蔡晓燕)

  2. Emanuel Institute of Biochemical Physics RAS, 119334, 4 Kosigin st., Moscow, Russian Federation

    Zakhar I. Popov

  3. School of Physics, Beihang University, Beijing, 100191, China

    Junying Zhang  (张俊英)

Authors
  1. Jie Chen  (陈杰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Liang Mao  (毛梁)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiachen Xu  (徐家琛)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiuquan Gu  (顾修全)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zakhar I. Popov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yulong Zhao  (赵宇龙)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yihan Ling  (凌意瀚)
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yanwei Sui  (隋艳伟)
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Pengzhan Ying  (应鹏展)
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Xiaoyan Cai  (蔡晓燕)
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Junying Zhang  (张俊英)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Author contributions Cai X conceived the idea and supervised the current work; Mao L co-supervised the current work and performed the theoretical calculations; Chen J and Xu J performed the experiments and data analysis and wrote the manuscript; Zhao Y, Ling Y, Sui Y and Ying P provided resources; Gu X, Popov ZI and Zhang J were involved in data analysis and revised the manuscript. All the authors participated in the general discussion.

Corresponding authors

Correspondence to Liang Mao  (毛梁) or Xiaoyan Cai  (蔡晓燕).

Ethics declarations

Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Jie Chen received his BS degree from Changshu Institute of Technology. He is currently studying for an MS degree under the supervision of Prof. Pengzhan Ying at China University of Mining and Technology. His research interest focuses on electrocatalytic hydrogen production.

Liang Mao received his PhD degree from Beihang University (2018) and is now a faculty member of the School of Materials Science and Physics, China University of Mining and Technology. His research interest focuses on the first principle calculation of catalytic materials and their energy and environmental applications.

Xiaoyan Cai received her PhD degree from Beihang University (2018) and is now a faculty member of the School of Materials Science and Physics, China University of Mining and Technology. Her research interests are photocatalytic and electrocatalytic materials for energy conversion and environmental remediation.

Supplementary information Supporting data are available in the online version of the paper.

Supplementary Information

40843_2023_2546_MOESM1_ESM.pdf

Synergetic effect of phosphorus-dopant and graphene-covering layer on hydrogen evolution activity and durability of NiCo2S4 electrocatalysts

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, J., Mao, L., Xu, J. et al. Synergetic effect of phosphorus-dopant and graphene-covering layer on hydrogen evolution activity and durability of NiCo2S4 electrocatalysts. Sci. China Mater. 66, 3875–3886 (2023). https://doi.org/10.1007/s40843-023-2546-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-023-2546-3

Keywords

Search

Navigation