The comparative study of two reusable phosphotungstic acid salts/reduced graphene oxides composites with enhanced photocatalytic activity

  • Junhong Li
  • Lijun LuoEmail author
  • Wei Tan
  • Hongbin Wang
  • Min Yang
  • Fengzhi Jiang
  • Wenrong Yang
Appropriate Technologies to Combat Water Pollution


In this work, two recyclable phosphotungstic acid salts/reduced graphene oxides were successfully prepared. The prepared samples were characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA), Raman spectroscopy, and photoluminescence spectroscopy (PL). The structure and catalytic performance of two composites were comparatively investigated, and the reduced graphene oxide mass ratios in K3[PW12O40]/reduced graphene oxide (denoted as KPW-RGO) and (NH4)3[PW12O40]/reduced graphene oxide (denoted as NH4PW-RGO) were optimized and their roles in them were explored. The results indicate that the Keggin structures of KPW and NH4PW are still kept after being anchored on the RGO surface, but their morphologies change a lot in composites. The photocatalytic activities of KPW-3RGO (0.01989 min−1) are 5.42 times than that of KPW (0.00367 min−1), and NH4PW-1RGO (0.0184 min−1) is 2.26 times than that of NH4PW (0.00814 min−1). The enhanced photocatalytic activity is mainly ascribed to photo-induced interfacial charge transfer on the heterojunction between RGO and NH4PW or KPW and strong adsorption ability of RGO towards MO. Moreover, NH4PW-1RGO and KPW-3RGO had much better photocatalytic activity, good recyclable ability, and stability compared to HPW-RGO, which cannot be recycled.


Photocatalysis Phosphotungstate Reduced oxide graphene Methyl orange 


Funding information

This work was financially supported by the Natural Science Foundation of China (No. 21767030 and 21763032), Natural Science Foundation of Yunnan Province (2016FB014), and Foundation of Education Bureau of Yunnan Province (2017ZZX087).


  1. Akhavan O, Abdolahad M, Esfandiar A, Mohatashamifar M (2010) Photodegradation of graphene oxide sheets by TiO2 nanoparticles after a photocatalytic reduction. J Phys Chem C 114:12955–12959CrossRefGoogle Scholar
  2. Antoniadis A, Takavakoglou V, Zalidis G, Darakas E, Poulios I (2010) Municipal wastewater treatment by sequential combination of photocatalytic oxidation with constructed wetlands. Catal Today 151:114–118CrossRefGoogle Scholar
  3. Chowdhury S, Balasubramanian R (2014) Graphene/semiconductor nanocomposites (GSNs) for heterogeneous photocatalytic decolorization of wastewaters contaminated with synthetic dyes: a review. Appl Catal B Environ 160–161:307–324CrossRefGoogle Scholar
  4. Corma A, Martinez A, Martinez C (1996) Acidic Cs+, NH4 +, and K+ salts of 12-tungstophosphoric Acid as solid catalysts for isobutane/2-butene alkylation. J Catal 164:422–432CrossRefGoogle Scholar
  5. Ding Y, Bai W, Sun J, Wu Y, Memon MA, Wang C, Liu CB, Huang Y, Geng JX (2016) Cellulose tailored anatase TiO2 nanospindles in three-dimensional graphene composites for high-performance supercapacitors. ACS Appl Mater Interfaces 8:12165–12175CrossRefGoogle Scholar
  6. Essayem N, Holmqvist A, Gayraud PY, Vedrine JC, Ben Taarit Y (2001) In situ FTIR studies of the protonic sites of H3PW12O40 and its acidic cesium salts MxH3-xPW12O40. J Catal 197:273–280CrossRefGoogle Scholar
  7. Feng C, Li Y, Liu X (2012) hotocatalytic degradation of imidacloprid by phosphotungstic acid supported on a mesoporous sieve MCM-41. Chin. J. Chem 30:127–132CrossRefGoogle Scholar
  8. He Y, Liu Y, Wu T, Ma J, Wang X, Gong Q, Kong W, Xing F, Liu Y, Gao J (2013) An environmentally friendly method for the fabrication of reduced graphene oxide foam with a super oil absorption capacity. J Hazard Mater 260:796–805CrossRefGoogle Scholar
  9. Holclajtner-Antunović I, Mioč UB, Todorović M, Jovanović Z, Davidović M, Bajuk-Bogdanović D, Laušević Z (2010) Characterization of potassium salts of 12-tungstophosphoric acid. Mater Res Bull 45:1679–1684CrossRefGoogle Scholar
  10. Hori H, Yamamoto A, Koike K, Kutsuna S, Murayama M, Yoshimoto A, Arakawa R (2008) Photocatalytic decomposition of a perfluoroether carboxylic acid by tungstic heteropolyacids in water. Appl Cataly B: Environ 82:58–66CrossRefGoogle Scholar
  11. Hummers WSOR (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339CrossRefGoogle Scholar
  12. Ji TH, Sun M, Han P (2014) A review of the preparation and applications of graphene/semiconductor composites. Carbon 70:319CrossRefGoogle Scholar
  13. Kanakaraju D, Glass BD, Oelgemöller M (2013) Titanium dioxide photocatalysis for pharmaceutical wastewater treatment. Environ Chem Lett 12:27–47CrossRefGoogle Scholar
  14. Khai TV, Kwak DS, Kwon YJ, Cho HY, Huan TN, Chung H, Ham H, Lee C, Dan NV, Tung NT, Kim HW (2013) Direct production of highly conductive graphene with a low oxygen content by a microwave-assisted solvothermal method. Chem Eng J 232:346–355CrossRefGoogle Scholar
  15. Kooti M, Kooshki F, Nasiri E, Sedeh AN (2018) H3PW12O40 anchored on graphene-grafted silica-coated MnFe2O4 as magnetic catalyst for Mannich reaction. J. Iranian. Chem Soc 15:943–953Google Scholar
  16. Kormali P, Troupis A, Triantis T, Hiskia A, Papaconstantinou E (2007) Photocatalysis by polyoxometallates and TiO2: a comparative study. Catal Today 124:149–155CrossRefGoogle Scholar
  17. Li H, Liu X, Qi S, Xu LL, Shi GS, Ding YH, Yan XY, Huang Y, Geng JX (2017a) Graphene oxide facilitates solvent-free synthesis of well-dispersed, faceted zeolite crystals. Angew Chem Int Ed 129:14090–14095CrossRefGoogle Scholar
  18. Li X, Xue H, Pang H (2017b) Facile synthesis and shape evolution of well-defined phosphotungstic acid potassium nanocrystals as a highly efficient visible-light-driven photocatalyst. Nanoscale 9:216–222CrossRefGoogle Scholar
  19. Linsebigler AL, Lu GQ, Yates JT (1995) Photocatalysis on TiO2 surfaces- principles, mechanism, and selected results. Chem Rev 95:735–758CrossRefGoogle Scholar
  20. Liu K, Chen T, Hou Z, Wang Y, Dai L (2013) Graphene oxide as support for the immobilization of phosphotungstic acid: application in the selective oxidation of benzyl alcohol. Catal Lett 144:314–319CrossRefGoogle Scholar
  21. Liu CG, Zheng T, Liu S, Zhang HY (2016) Photodegradation of malachite green dye catalyzed by Keggin-type polyoxometalates under visible-light irradiation: Transition metal substituted effects. J Mol Struct 1110:44–52CrossRefGoogle Scholar
  22. Luo G, Kang L, Zhu M, Dai B (2014a) Highly active phosphotungstic acid immobilized on amino-functionalized MCM-41 for the oxidesulfurization of dibenzothiophene. Fuel Process Technol 118:20–27CrossRefGoogle Scholar
  23. Luo LJ, Zhang XJ, Ma FJ, Zhang AL, Bian LC, Pan XJ, Jiang FZ (2014b) Photocatalytic degradation of bisphenol A by TiO2-reduced graphene oxide nanocomposites. React Kinet Mech Catal 114(1):311–322CrossRefGoogle Scholar
  24. Luo L, Yang Y, Zhang A, Wang M, Liu Y, Bian L, Jiang F, Pan X (2015) Hydrothermal synthesis of fluorinated anatase TiO2/reduced graphene oxide nanocomposites and their photocatalytic degradation of bisphenol A. Appl Surf Sci 353:469–479CrossRefGoogle Scholar
  25. Marsolek MD, Kirisits MJ, Gray KA, Rittmann BE (2014) Coupled photocatalytic-biodegradation of 2,4,5-trichlorophenol: effects of photolytic and photocatalytic effluent composition on bioreactor process performance, community diversity, and resistance and resilience to perturbation. Water Res 50:59–69CrossRefGoogle Scholar
  26. Méndez L, Torviso R, Pizzio L, Blanco M (2011) 2-Methoxynaphthalene acylation using aluminum or copper salts of tungstophosphoric and tungstosilicic acids as catalysts. Catal Today 173:32–37CrossRefGoogle Scholar
  27. Meyer JC, Geim AK, Katsnelson MI, Novoselov KS, Booth TJ, Roth S (2007) The structure of suspended graphene sheets. Nature 446:60–63CrossRefGoogle Scholar
  28. Moniz SJA, Shevlin SA, Martin DJ, Guo ZX, Tang J (2015) Visible-light driven heterojunction photocatalysts for water splitting-a critical review. Energy Environ Sci 8:731–759CrossRefGoogle Scholar
  29. Morales-Torres S, Pastrana-Martinez LM, Figueiredo JL, Faria JL, Silva AM (2012) Design of graphene-based TiO2 photocatalysts-a review. Environ Sci Pollut Res Int 19:3676–3687CrossRefGoogle Scholar
  30. Pelaez M, Nolan NT, Pillai SC, Seery MK, Falaras P, Kontos AG, Dunlop PSM, Hamilton JWJ, Byrne JA, O’Shea K, Entezari MH, Dionysiou DD (2012) A review on the visible light active titanium dioxide photocatalysts for environmental applications. Appl Catal B Environ 125:331–349CrossRefGoogle Scholar
  31. Rao R, Podila R, Tsuchikawa R, Katoch J, Tishler D, Rao A, Ishigami M (2011) Effects of layer stacking on the combination Raman modes in graphene. ACS Nano 5:1594–1599CrossRefGoogle Scholar
  32. Stankovich S, Dikin DA, Dommett GHB, Kohlhaas KM, Zimney EJ, Stach EA, Piner RD, Nguyen ST, Ruoff RS (2006) Graphene-based composite materials. Nature 442:282–286CrossRefGoogle Scholar
  33. Troupis A, Triantis TM, Gkika E, Hiskia A, Papaconstantinou E (2009) Photocatalytic reductive–oxidative degradation of Acid Orange 7 by polyoxometalates. Appl Catal B Environ 86:98–107CrossRefGoogle Scholar
  34. Wang XS, Huang YB, Lin ZJ, Cao R (2014) Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal-organic frameworks for catalytic oxidative desulfurization. Dalton Trans 43:11950–11958CrossRefGoogle Scholar
  35. Xia LH, Luo LJ, Li J, Fan Y, Tan W, Yang WR, Wang HB, Shu L (2017) The preparation and photocatalytic activity of phosphotungstic acid-reduced graphene oxide composites. Desalin Water Treat 96:178–185CrossRefGoogle Scholar
  36. Xiao J, Wu L, Wu Y, Liu B, Dai L, Li Z, Xia Q, Xi H (2014) Effect of gasoline composition on oxidative desulfurization using a phosphotungstic acid/activated carbon catalyst with hydrogen peroxide. Appl Energy 113:78–85CrossRefGoogle Scholar
  37. Xu J, Wang L, Zhu Y (2012) Decontamination of bisphenol A from aqueous solution by graphene adsorption. Langmuir 28:8418–8425CrossRefGoogle Scholar
  38. Yang J, Chen D, Zhu Y, Zhang Y, Zhu Y (2017) 3D-3D porous Bi2WO6/graphene hydrogel composite with excellent synergistic effect of adsorption-enrichment and photocatalytic degradation. Appl Catal B: Environ 205:228–237CrossRefGoogle Scholar
  39. Zhang WL, Choi HJ (2012) Silica-graphene oxide hybrid composite particles and their electroresponsive characteristics. Langmuir 28:7055–7062CrossRefGoogle Scholar
  40. Zhang Y, Tang ZR, Fu X, Xu YJ (2010) TiO2-graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant-Is TiO2-graphene truly different from other TiO2-carboncomposite materials? ACS Nano 4:7303–7314CrossRefGoogle Scholar
  41. Zhang L, Li S, Zhang Z, Tan L, Pang H, Ma H (2017) Facile fabrication of reduced graphene oxide and Keggin-type polyoxometalates nanocomposite film for high performance electrocatalytic oxidation of nitrite. J Electroanal Chem 807:97–103CrossRefGoogle Scholar
  42. Zhao L, Chi Y, Yuan Q, Li N, Yan W, Li X (2013) Phosphotungstic acid anchored to amino-functionalized core-shell magnetic mesoporous silica microspheres: a magnetically recoverable nanocomposite with enhanced photocatalytic activity. J Colloid Interface Sci 390:70–77CrossRefGoogle Scholar
  43. Zhu Y, Zhu M, Kang L, Yu F, Dai B (2015) Phosphotungstic acid supported on mesoporous graphitic carbon nitride as catalyst for oxidative desulfurization of fuel. Ind Eng Chem Res 54:2040–2047CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Junhong Li
    • 1
  • Lijun Luo
    • 1
    Email author
  • Wei Tan
    • 1
  • Hongbin Wang
    • 1
  • Min Yang
    • 1
  • Fengzhi Jiang
    • 2
  • Wenrong Yang
    • 3
  1. 1.Key Laboratory of Resource Clean Conversion in Ethnic Regions, Education Department of Yunnan, School of Chemistry and EnvironmentYunnan MinZu UniversityKunmingPeople’s Republic of China
  2. 2.Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and TechnologyYunnan UniversityKunmingPeople’s Republic of China
  3. 3.Centre for Chemistry and Biotechnology, School of Life and Environmental SciencesDeakin UniversityWaurn PondsAustralia

Personalised recommendations