Skip to main content
SpringerLink
Log in

Ferrites boosting photocatalytic hydrogen evolution over graphitic carbon nitride: a case study of (Co, Ni)Fe2O4 modification

  • Article
  • Materials Science
  • Published:
Science Bulletin

Abstract

The charge carrier separation and surface catalytic redox reactions are of primary importance as elementary steps in photocatalytic hydrogen evolution. In this study, both of these two processes in photocatalytic hydrogen evolution over graphitic carbon nitride (g-C3N4) were greatly promoted with the earth-abundant ferrites (Co, Ni)Fe2O4 modification. CoFe2O4 was further demonstrated to be a better modifier for g-C3N4 as compared to NiFe2O4, due to the more efficient charge carrier transfer as well as superior surface oxidative catalytic activity. When together loading CoFe2O4 and reductive hydrogen production electrocatalyst Pt onto g-C3N4, the obtained Pt/g-C3N4/CoFe2O4 photocatalyst achieved visible-light (λ > 420 nm) hydrogen production rate 3.5 times as high as Pt/g-C3N4, with the apparent quantum yield reaching 3.35 % at 420 nm.

摘要

光生载流子分离和表面催化反应是光催化分解水制氢过程的2个主要步骤,协同提高这两步速率必然能极大促进催化剂的制氢效率。本文以g-C3N4为研究对象,通过负载铁酸盐CoFe2O4或NiFe2O4,g-C3N4的光催化制氢性能得到大幅提高。研究结果表明,(Co, Ni)Fe2O4不仅能够有效地促进g-C3N4中的光生载流子的分离,而且能够有效地促进表面催化氧化半反应;与此同时,负载Pt作为产氢助催化剂,能促进表面催化还原产氢半反应。在光催化反应中,g-C3N4中的光生电子和空穴分别流向Pt和(Co, Ni)Fe2O4,电子在Pt上还原反应产生氢气,而空穴转移到(Co, Ni)Fe2O4上与牺牲剂反应。进一步研究结果发现,CoFe2O4对g-C3N4的载流子分离与氧化半反应催化效果均优于NiFe2O4。通过CoFe2O4和Pt共负载,Pt/g-C3N4/CoFe2O4光催化剂的催化制氢量子效率在420 nm处达到3.35 %,在可见光区(λ > 420 nm)的光催化制氢速率是未负载铁酸盐的Pt/g-C3N4的3.5倍。

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
Fig. 6

Similar content being viewed by others

References

  1. Fujishima A, Honda K (1972) Photolysis-decomposition of water at the surface of an irradiated semiconductor. Nature 238:37–38

    Article  Google Scholar 

  2. Chen XB, Shen SH, Guo LJ et al (2010) Semiconductor-based photocatalytic hydrogen generation. Chem Rev 110:6503–6570

    Article  Google Scholar 

  3. Yue D, Qian X, Zhao Y (2015) Photocatalytic remediation of ionic pollutant. Sci Bull 60:1791–1806

    Article  Google Scholar 

  4. Xia Z, Zhou X, Li J et al (2015) Protection strategy for improved catalytic stability of silicon photoanodes for water oxidation. Sci Bull 60:1395–1402

    Article  Google Scholar 

  5. Wang XC, Maeda K, Thomas A et al (2009) A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater 8:76–80

    Article  Google Scholar 

  6. Zhang GG, Zhang MW, Ye XX et al (2014) Iodine modified carbon nitride semiconductors as visible light photocatalysts for hydrogen evolution. Adv Mater 26:805–809

    Article  Google Scholar 

  7. Liu J, Wang HQ, Chen ZP et al (2015) Microcontact printing assisted access of graphitic carbon nitride films with favorable textures toward photoelectrochemical application. Adv Mater 27:712–718

    Article  Google Scholar 

  8. Chen J, Shen SH, Guo PH et al (2014) Spatial engineering of photo-active sites on g-C3N4 for efficient solar hydrogen generation. J Mater Chem A 2:4605–4612

    Article  Google Scholar 

  9. Xu L, Huang WQ, Wang LL et al (2015) Insights into enhanced visible-Light photocatalytic hydrogen evolution of g-C3N4 and highly reduced graphene oxide composite: the role of oxygen. Chem Mater 27:1612–1621

    Article  Google Scholar 

  10. Ma XG, Lv YH, Xu J et al (2012) A strategy of enhancing the photoactivity of g-C3N4 via doping of nonmetal elements: a first-principles study. J Phys Chem C 116:23485–23493

    Article  Google Scholar 

  11. Liu G, Niu P, Sun CH et al (2010) Unique electronic structure induced high photoreactivity of sulfur-doped graphitic C3N4. J Am Chem Soc 132:11642–11648

    Article  Google Scholar 

  12. Chen J, Shen SH, Guo PH et al (2014) In-situ reduction synthesis of nano-sized Cu2O particles modifying g-C3N4 for enhanced photocatalytic hydrogen production. Appl Catal B Environ 152–153:335–341

    Article  Google Scholar 

  13. Chen J, Shen SH, Wu P et al (2015) Nitrogen-doped CeO x nanoparticles modified graphitic carbon nitride for enhanced photocatalytic hydrogen production. Green Chem 17:509–517

    Article  Google Scholar 

  14. Yan HJ, Yang HX (2011) TiO2/g-C3N4 composite materials for photocatalytic H2 evolution under visible light irradiation. J Alloy Compd 509:26–29

    Article  Google Scholar 

  15. Zhu YP, Li M, Liu YL et al (2014) Carbon-doped ZnO hybridized homogeneously with graphitic carbon nitride nanocomposites for photocatalysis. J Phys Chem C 118:10963–10971

    Article  Google Scholar 

  16. Wang YJ, Shi R, Lin J et al (2011) Enhancement of photocurrent and photocatalytic activity of ZnO hybridized with graphite-like C3N4. Energy Environ Sci 4:2922–2929

    Article  Google Scholar 

  17. Zhou XS, Jin B, Li LD et al (2012) A carbon nitride/TiO2 nanotube array heterojunction visible-light photocatalyst: synthesis, characterization, and photoelectrochemical properties. J Mater Chem 22:17900–17905

    Article  Google Scholar 

  18. Yan SC, Lv SB, Li ZS et al (2010) Organic-inorganic composite photocatalyst of g-C3N4 and TaON with improved visible light photocatalytic activities. Dalton Trans 39:1488–1491

    Article  Google Scholar 

  19. Hu S, Xiang CX, Haussener S et al (2013) An analysis of the optimal band gaps of light absorbers in integrated tandem photoelectrochemical water-splitting systems. Energy Environ Sci 6:2984–2993

    Article  Google Scholar 

  20. Zhang K, Kim WJ, Ma M et al (2015) Tuning the charge transfer route by p-n junction catalysts embedded with CdS nanorods for simultaneous efficient hydrogen and oxygen evolution. J Mater Chem A 3:4803–4810

    Article  Google Scholar 

  21. Wang XC, Blechert S, Antonietti M (2012) Polymeric graphitic carbon nitride for heterogeneous photocatalysis. ACS Catal 2:1596–1606

    Article  Google Scholar 

  22. Maeda K, Wang XC, Nishihara Y et al (2009) Photocatalytic activities of graphitic carbon nitride powder for water reduction and oxidation under visible light. J Phys Chem C 113:4940–4947

    Article  Google Scholar 

  23. Hou YD, Laursen AB, Zhang JS et al (2013) Layered nanojunctions for hydrogen evolution catalysis. Angew Chem Int Ed 52:3621–3625

    Article  Google Scholar 

  24. Li M, Xiong YP, Liu T et al (2015) Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction. Nanoscale 7:8920–8930

    Article  Google Scholar 

  25. Shi YQ, Zhou KQ, Wang BB et al (2014) Ternary graphene-CoFe2O4/CdS nanohybrids: preparation and application as recyclable photocatalysts. J Mater Chem A 2:535–544

    Article  Google Scholar 

  26. Sathishkumar P, Mangalaraj RV, Anandan S et al (2013) CoFe2O4/TiO2 nanocatalysts for the photocatalytic degradation of Reactive Red 120 in aqueous solutions in the presence and absence of electron acceptors. Chem Eng J 220:302–310

    Article  Google Scholar 

  27. Xu SH, Feng DL, Li DX et al (2008) Preparation of magnetic photocatalyst TiO2 supported on NiFe2O4 and effect of magnetic carrier on photocatalytic activity. Chin J Chem 26:842–846

    Article  Google Scholar 

  28. Hong DC, Yamada Y, Sheehan M et al (2014) Mesoporous nickel ferrites with spinel structure prepared by an aerosol spray pyrolysis method for photocatalytic hydrogen evolution. ACS Sustain Chem Eng 2:2588–2594

    Article  Google Scholar 

  29. Al-Hoshan MS, Singh JP, Al-Mayouf AM et al (2012) Synthesis, physicochemical and electrochemical properties of nickel ferrite spinels obtained by hydrothermal method for the oxygen evolution reaction (OER). Int J Electrochem Sci 7:4959–4973

    Google Scholar 

  30. Liu SS, Bian WY, Yang ZR et al (2014) A facile synthesis of CoFe2O4/biocarbon nanocomposites as efficient bi-functional electrocatalysts for the oxygen reduction and oxygen evolution reaction. J Mater Chem A 2:18012–18017

    Article  Google Scholar 

  31. Xu YJ, Bian WY, Wu J et al (2015) Preparation and electrocatalytic activity of 3D hierarchical porous spinel CoFe2O4 hollow nanospheres as efficient catalyst for oxygen reduction reaction and oxygen evolution reaction. Electrochim Acta 151:276–283

    Article  Google Scholar 

  32. Cannas C, Falqui A, Musinu A et al (2006) CoFe2O4 nanocrystalline powders prepared by citrate-gel methods: synthesis, structure and magnetic properties. J Nanopart Res 8:255–267

    Article  Google Scholar 

  33. Zhu B, Yang CT, Xie QT et al (2013) Influence of rapid thermal annealing on the structure and magnetic properties of CoFe2O4 films prepared by sol-gel method. Ferroelectrics 445:18–25

    Article  Google Scholar 

  34. Montemayor SM, Garcia-Cerda LA, Torres-Lubian JR et al (2007) Comparative study of the synthesis of CoFe2O4 and NiFe2O4 in silica through the polymerized complex route of the sol-gel method. J Sol Gel Sci Technol 42:181–186

    Article  Google Scholar 

  35. Azadmanjiri J, Seyyed SAS (2004) Influence of stoichiometry and calcination condition on the microstructure and phase constitution of NiFe2O4 powders prepared by sol-gel autocombustion method. Phys Stat Sol 12:3414–3417

    Article  Google Scholar 

  36. Li YB, Zhang HM, Liu PR et al (2013) Cross-linked g-C3N4/rGO nanocomposites with tunable band structure and enhanced visible light photocatalytic activity. Small 9:3336–3344

    Google Scholar 

  37. Sun JW, Fu YS, Xiong P et al (2013) A magnetically separable P25/CoFe2O4/graphene catalyst with enhanced adsorption capacity and visible-light-driven photocatalytic activity. RSC Adv 3:22490–22497

    Article  Google Scholar 

  38. Zhang JL, Fu JC, Tan GG et al (2012) Nanoscale characterization and magnetic reversal mechanism investigation of electrospun NiFe2O4 multi-particle-chain nanofibres. Nanoscale 4:2754–2759

    Article  Google Scholar 

  39. Lin XP, Xing JC, Wang WD et al (2007) Photocatalytic activities of heterojunction semiconductors Bi2O3/BaTiO3: a strategy for the design of efficient combined photocatalysts. J Phys Chem C 111:18288–18293

    Article  Google Scholar 

  40. Holmes MA, Townsend TK, Osterloh FE et al (2012) Quantum confinement controlled photocatalytic water splitting by suspended CdSe nanocrystals. Chem Commun 48:371–373

    Article  Google Scholar 

  41. Choi JJ, Lim YF, Santiago-Berrios MB et al (2009) PbSe nanocrystal excitonic solar cells. Nano Lett 9:3749–3755

    Article  Google Scholar 

  42. Yang XG, Du C, Liu R et al (2013) Balancing photovoltage generation and charge-transfer enhancement for catalyst-decorated photoelectrochemical water splitting: a case study of the hematite/MnO x combination. J Catal 304:86–91

    Article  Google Scholar 

  43. Mao S, Wen ZH, Huang TZ et al (2014) High-performance bi-functional electrocatalysts of 3D crumpled graphene–cobalt oxide nanohybrids for oxygen reduction and evolution reactions. Energy Environ Sci 7:609–616

    Article  Google Scholar 

  44. Ding Q, Meng F, English CR et al (2014) Efficient photoelectrochemical hydrogen generation using heterostructures of Si and chemically exfoliated metallic MoS2. J Am Chem Soc 136:8504–8507

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (51323011 and 51236007), the Program for New Century Excellent Talents in University (NCET-13-0455), the Natural Science Foundation of Shaanxi Province (2014KW07-02), the Natural Science Foundation of Jiangsu Province (BK20141212) and the Nano Research Program of Suzhou City (ZXG201442 and ZXG2013003). Shaohua Shen was supported by the Foundation for the Author of National Excellent Doctoral Dissertation of China (201335), and the Fundamental Research Funds for the Central Universities.

Author information

Authors and Affiliations

  1. International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an, 710049, China

    Jie Chen, Daming Zhao, Zhidan Diao, Miao Wang & Shaohua Shen

Authors
  1. Jie Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Daming Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhidan Diao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Miao Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shaohua Shen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shaohua Shen.

Ethics declarations

Conflict of interest

All the authors declare that they have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 12801 kb)

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, J., Zhao, D., Diao, Z. et al. Ferrites boosting photocatalytic hydrogen evolution over graphitic carbon nitride: a case study of (Co, Ni)Fe2O4 modification. Sci. Bull. 61, 292–301 (2016). https://doi.org/10.1007/s11434-016-0995-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11434-016-0995-0

Keywords

Search

Navigation