Noble-Metal-Free Visible Light Driven Hetero-structural Ni/ZnxCd1−xS Photocatalyst for Efficient Hydrogen Production

  • Yang Liu
  • Guorong WangEmail author
  • Youlin Ma
  • Zhiliang JinEmail author


Ni/ZnxCd1−xS composite photocatalyst was successfully synthesized by hydrothermal method and in situ photodeposition method, and certain hydrogen evolution results were obtained in acidic, neutral and alkaline sacrificial reagents. Among them, hydrogen evolution amount reached 11.993 mmol h−1 g−1 in alkaline Na2S/Na2SO3 solution. According to SEM, TEM and Mapping, two solid solutions of ZnxCd1−xS were formed under specific reaction conditions, which provided a large specific surface area and increased the contact area between metal Ni and ZnxCd1−xS, leading to more electron transfer. The UV–Vis diffuse reflectance spectra indicates that, due to the interface interaction between Ni and ZnxCd1−xS, the photodeposition of Ni leads to the reduction of the band gap of the photocatalyst, the expansion of visible light absorption range, and the generation of more photogenerated electrons. The excellent electron transport ability of Ni leads to the rapid separation of electron–hole pairs, inhibits the recombination of electron–hole pairs, and greatly improves the photocatalytic activity. This work describes the effective synergistic effect of Ni/ZnxCd1−xS photocatalysis, showing good hydrogen evolution effect, and emphasizes the excellent electronic conductivity without noble metal synergistic catalyst.

Graphical Abstract


Ni/ZnxCd1−xHydrogen production Noble-metal-free Hetero-structural 



This work was financially supported by the Chinese National Natural Science Foundation (41663012 and 21862002), The new technology and system for clean energy catalytic production, Major scientific project of North Minzu University (ZDZX201803).The Ningxia low-grade resource high value utilization and environmental chemical integration technology innovation team project, North Minzu University and the Key Laboratory for the development and application of electrochemical energy conversion technology, North Minzu University.

Author Contributions

YL conceived and designed the experiments; ZJ and GW contributed reagents/materials; YM assisted in the testing of the experiment.

Compliance with Ethical Standards

Conflicts of interest

The authors declare that they have no competing interests.


  1. 1.
    Jin Z, Hao X, Min S et al (2014) Efficient photocatalytic hydrogen evolution over platinum and boron Co-doped TiO2 photoatalysts. J Mater Sci 20(4):392–395Google Scholar
  2. 2.
    Hao X, Jin Z, Xu J et al (2016) Functionalization of TiO2 with graphene quantum dots for efficient hydrogen evolution. Superlattices Microstruct 94:237–244CrossRefGoogle Scholar
  3. 3.
    Li Y, Li H, Li Y et al (2018) Fe-B alloy coupled with Fe clusters as an efficient cocatalyst for photocatalytic hydrogen evolution. Chem Eng J 344:506–513CrossRefGoogle Scholar
  4. 4.
    Yang G, Ding H, Chen D et al (2018) Construction of urchin-like ZnIn2S4-Au-TiO2 heterostructure with enhanced activity for photocatalytic hydrogen evolution. Appl Catal B 234:260–267CrossRefGoogle Scholar
  5. 5.
    Song J, Zhao H, Sun R et al (2013) An efficient hydrogen evolution catalyst composed of palladium phosphorous sulphide (PdP ~ 0.33S ~ 1.67) and twin nanocrystal Zn0.5Cd0.5S solid solution with both homo-and hetero-junctions. Energy Environ Sci 10:225–235CrossRefGoogle Scholar
  6. 6.
    Yang H, Jin Z, Hu H et al (2017) Fabrication and behaviors of CdS on Bi2MoO6 thin film photoanodes. RSC Adv 7:10774–10781CrossRefGoogle Scholar
  7. 7.
    Zeng X, Xiao X, Chen J et al (2017) Carbon dots enhance the stability of CdS for visible-light-driven overall water splitting. Appl Catal B 216:114–121CrossRefGoogle Scholar
  8. 8.
    Marchal C, Cottineau T, Méndez-Medrano MG et al (2018) Au/TiO2-gC3N4 nanocomposites for enhanced photocatalytic H2 production from water under visible light irradiation with very low quantities of sacrificial agents. Adv Energy Mater 8(14):1702142CrossRefGoogle Scholar
  9. 9.
    Altomare M, Nguyen NT, Hejazi S et al (2017) A cocatalytic electron-transfer cascade site-selectively placed on TiO2 nanotubes yields enhanced photocatalytic H2 evolution. Adv Funct Mater 28(2):1704259CrossRefGoogle Scholar
  10. 10.
    Wang Z, Jin Z, Yuan H et al (2018) Orderly-designed functional Ni2P nanoparticles with spatially separated on g-C3N4 and UiO-66 for efficient solar water splitting. J Colloid Interface Sci 532:287–299CrossRefGoogle Scholar
  11. 11.
    Wang X, Zhou H, Zhang D et al (2018) Mn-doped NiP2, nanosheets as an efficient electrocatalyst for enhanced hydrogen evolution reaction at all pH values. J Power Sources 387:1–8CrossRefGoogle Scholar
  12. 12.
    Wang X-j, Tian X, Sun Y-j et al (2018) Enhanced Schottky effect of 2D–2D CoP/g-C3N4 interface for boosting photocatalytic H2 evolution. Nanoscale 10:12315–12321CrossRefGoogle Scholar
  13. 13.
    Zexing W, Wang J, Xia K et al (2017) MoS2–MoP heterostructured nanosheets on polymer-derived carbon as an electrocatalyst for hydrogen evolution reaction. J Mater Chem A 6:616–622Google Scholar
  14. 14.
    Liu D, Jin Z, Zhang Y et al (2018) Light Harvesting and Charge Management by Ni4S3 Modified MOF and rGO in the Process of Photocatalysis. J Colloid Interface Sci 529:44–52CrossRefGoogle Scholar
  15. 15.
    Chen Z, Sun P, Fan B et al (2014) In situ template-free ion-exchange process to prepare visible-light-active g-C3N4/NiS hybrid photocatalysts with enhanced hydrogen evolution activity. J Phys Chem C 118:7801–7807CrossRefGoogle Scholar
  16. 16.
    Liu Y, Xinyuan X, Zhang J et al (2018) Flower-like MoS2 on graphitic carbon nitride for enhanced photocatalytic and electrochemical hydrogen evolutions. Appl Catal B 239:334–344CrossRefGoogle Scholar
  17. 17.
    Chen L, Zhang J, Ren X et al (2017) A Ni(OH)2-CoS2 hybrid nanowire array: a superior non-noble-metal catalyst toward the hydrogen evolution reaction in alkaline media. Nanoscale 9:16632–16637CrossRefGoogle Scholar
  18. 18.
    Wang G, Jin Z (2019) Function of NiSe2 over CdS nanorods for enhancement of photocatalytic hydrogen production—from preparation to mechanism. Appl Surf Sci 467:1239–1248Google Scholar
  19. 19.
    Lian Z, Sakamoto M, Kobayashi Y et al (2018) Durian-shaped CdS@ZnSe Core@Mesoporous-shell nanoparticles for enhanced and sustainable photocatalytic hydrogen evolution. J Phys Chem Lett 9:2212–2217CrossRefGoogle Scholar
  20. 20.
    Kumar DP, Kim EH, Park H et al (2018) Tuning band alignments and charge-transport properties through MoSe2 bridging between MoS2 and cadmium sulfide for enhanced hydrogen production. ACS Appl Mater Interfaces 10:26153–26161CrossRefGoogle Scholar
  21. 21.
    Li W, Jaeckel F (2018) Size-controlled electron transfer rates determine hydrogen generation efficiency in colloidal Pt-decorated CdS quantum dots. Nanoscale 10:16153–16158CrossRefGoogle Scholar
  22. 22.
    Daia D, Wang L, Xiao N et al (2018) In-situ synthesis of Ni2P co-catalyst decorated Zn0.5Cd0.5S nanorods for high-quantum-yield photocatalytic hydrogen production under visible light irradiation. Appl Catal B 233:194–201CrossRefGoogle Scholar
  23. 23.
    Yang H, Jin Z, Liu D et al (2018) Visible light harvesting and spatial charge separation over creative Ni/CdS/Co3O4 photocatalyst. J Phys Chem C 122:10430–10441CrossRefGoogle Scholar
  24. 24.
    Wang H, Jin Z, Gan R et al (2018) Novel Strategy of Defect-Induced Graphite Nitride Carbon Preparation and Photocatalytic Performance. Catal Lett 148:1296–1308CrossRefGoogle Scholar
  25. 25.
    Peng S, An R, Li Y et al (2012) Remarkable enhancement of photocatalytic hydrogen evolution over Cd0.5Zn0.5S by bismuth-doping. Int J Hydrog Energy 37:1366–1374CrossRefGoogle Scholar
  26. 26.
    Chai Z, Zeng T-T, Li Q et al (2016) Efficient Visible Light-Driven Splitting of Alcohols into Hydrogen and Corresponding Carbonyl Compounds over a Ni-Modified CdS Photocatalyst. J Am Chem Soc 138:10128–10131CrossRefGoogle Scholar
  27. 27.
    Zhou M, Liu Z, Song Q et al (2019) Hybrid 0D/2D edamame shaped ZnIn2S4 photoanode modified by Co-Pi and Pt for charge management towards efficient photoelectrochemical water splitting. Appl Catal B 244:188–196CrossRefGoogle Scholar
  28. 28.
    Peng S, Yang Y, Tan J et al (2018) In situ loading of Ni2P on Cd0.5Zn0.5S with red phosphorus for enhanced visible light photocatalytic H2 evolution. Appl Surf Sci 447:822–828CrossRefGoogle Scholar
  29. 29.
    Zhang Y, Wang G, Ma W et al (2018) CdS p–n heterojunction co-boosting with Co3O4 and Ni-MOF-74 for photocatalytic hydrogen evolution. Dalton Trans 233:194–201Google Scholar
  30. 30.
    Simon T, Bouchonville N, Berr MJ et al (2014) Redox shuttle mechanism enhances photocatalytic H2 generation on Ni-decorated CdS nanorods. Nat Mater 13:1013–1018CrossRefGoogle Scholar
  31. 31.
    Ioannis V, Ioannis P, Theocharis T et al (2018) Visible-light photocatalytic H2 production activity of β-Ni(OH)2 modified CdS mesoporous nano-heterojunction networks. ACS Catal 8:8726–8738CrossRefGoogle Scholar
  32. 32.
    Hao X, Wang Y, Zhou J et al (2018) Zinc vacancy-promoted photocatalytic activity and photostability of ZnS for efficient visible-light-driven hydrogen evolution. Appl Catal B 221:302–311CrossRefGoogle Scholar
  33. 33.
    Li Y, Hou Y, Qinyu F et al (2017) Oriented growth of ZnIn2S4/In(OH)3 heterojunction by a facile hydrothermal transformation for efficient photocatalytic H2 production. Appl Catal B 206:726–733CrossRefGoogle Scholar
  34. 34.
    Xie YP, Yu ZB, Liu G et al (2014) CdS—mesoporous ZnS core–shell particles for efficient and stable photocatalytic hydrogen evolution under visible light. Energy Environ Sci 7:1895–1901CrossRefGoogle Scholar
  35. 35.
    Hu T, Li P, Zhang J et al (2018) Highly efficient direct Z-scheme WO3/CdS-diethylenetriamine photocatalyst and its enhanced photocatalytic H2, evolution under visible light irradiation. Appl Surf Sci 442:20–29CrossRefGoogle Scholar
  36. 36.
    Low J, Jiaguo Yu, Jaroniec M et al (2017) Heterojunction Photocatalysts. Adv Mater 29:1601694CrossRefGoogle Scholar
  37. 37.
    Li H, Yan X, Lin B et al (2018) Controllable spatial effect acting on photo-induced CdS@CoP@SiO2 ball-in-ball nano-photoreactor for enhancing hydrogen evolution. Nano Energy 47:481–493CrossRefGoogle Scholar
  38. 38.
    Yang P, Ou H, Fang Y et al (2017) A Facile steam reforming strategy to delaminate layered carbon Nitride semiconductors for photoredox catalysis. Angew Chem Int Ed 56:3992–3996CrossRefGoogle Scholar
  39. 39.
    Zhang W, Li Y, Peng S (2017) Template-free synthesis of hollow Ni/reduced graphene oxide composite for efficient H2 evolution. J Mater Chem A 5:13072–13078CrossRefGoogle Scholar
  40. 40.
    Lia Y, Han P, Hou Y et al (2019) Oriented ZnmIn2Sm+3@In2S3 heterojunction with hierarchical structure for efficient photocatalytic hydrogen evolution. Appl Catal B 244:604–611CrossRefGoogle Scholar
  41. 41.
    Xue C, Li H, An H et al (2018) NiSx quantum dots accelerate electrons transfer in Cd0.8Zn0.2S photocatalytic system via rGO nanosheet “Bridge” towards superior visible-light-driven hydrogen evolution. ACS Catal 8:1532–1545CrossRefGoogle Scholar
  42. 42.
    Sun C, Zhanga H, Liu H (2018) Enhanced activity of visible-light photocatalytic H2 evolution of sulfur-doped g-C3N4 photocatalyst via nanoparticle metal Ni as cocatalyst. Appl Catal B 235:66–74CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Chemistry and Chemical EngineeringNorth Minzu UniversityYinchuanPeople’s Republic of China
  2. 2.Ningxia Key Laboratory of Solar Chemical Conversion TechnologyNorth Minzu UniversityYinchuanPeople’s Republic of China
  3. 3.Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs CommissionNorth Minzu UniversityYinchuanPeople’s Republic of China

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