Environmental Science and Pollution Research

, Volume 26, Issue 2, pp 1082–1093 | Cite as

Sonophotocatalytic degradation of bisphenol A and its intermediates with graphitic carbon nitride

  • Sharmini Sunasee
  • Kah Hon Leong
  • Kien Tiek Wong
  • Gooyong Lee
  • Saravanan Pichiah
  • InWook Nah
  • Byong-Hun Jeon
  • Yeomin Yoon
  • Min JangEmail author
Water Industry: Water-Energy-Health Nexus


Since bisphenol A (BPA) exhibits endocrine disrupting action and high toxicity in aqueous system, there are high demands to remove it completely. In this study, the BPA removal by sonophotocatalysis coupled with nano-structured graphitic carbon nitride (g-C3N4, GCN) was conducted with various batch tests using energy-based advanced oxidation process (AOP) based on ultrasound (US) and visible light (Vis-L). Results of batch tests indicated that GCN-based sonophotocatalysis (Vis-L/US) had higher rate constants than other AOPs and especially two times higher degradation rate than TiO2-based Vis-L/US. This result infers that GCN is effective in the catalytic activity in Vis-L/US since its surface can be activated by Vis-L to transport electrons from valence band (VB) for utilizing holes (h+VB) in the removal of BPA. In addition, US irradiation exfoliated the GCN effectively. The formation of BPA intermediates was investigated in detail by using high-performance liquid chromatography-mass spectrometry (HPLC/MS). The possible degradation pathway of BPA was proposed.


Sonophotocatalysis Bisphenol A Graphitic carbon nitride Ultrasound Visible light Intermediates 



This research was supported by a University of Malaya Research Grant (RP019B-13AET) and partly supported by the Geo-Advanced Innovative Action Project (2012000550002), funded by the Korea Ministry of Environment (MOE).

Supplementary material

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Figure S1 (DOCX 673 kb)
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Figure S2 (DOCX 55 kb)
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Table S1 (DOCX 17 kb)
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Table S2 (DOCX 16 kb)


  1. Ahmad S, Gupta A, Sharmin E, Alam M, Pandey S (2005) Synthesis, characterization and development of high performance siloxane-modified epoxy paints. Prog Org Coat 54:248–255CrossRefGoogle Scholar
  2. Barik AJ, Kulkarni SV, Gogate PR (2016) Degradation of 4-chloro 2-aminophenol using combined approaches based on microwave and photocatalysis. Sep Purif Technol 168:152–160CrossRefGoogle Scholar
  3. Bastami TR, Ahmadpour A (2016) Preparation of magnetic photocatalyst nanohybrid decorated by polyoxometalate for the degradation of a pharmaceutical pollutant under solar light. Environ Sci Pollut Res 23:8849–8860CrossRefGoogle Scholar
  4. Bautista-Toledo I, Ferro-Garcia M, Rivera-Utrilla J, Moreno-Castilla C, Vegas Fernández F (2005) Bisphenol A removal from water by activated carbon. Effects of carbon characteristics and solution chemistry. Environ Sci Technol 39:6246–6250CrossRefGoogle Scholar
  5. Beltran FJ, Aguinaco A, García-Araya JF, Oropesa A (2008) Ozone and photocatalytic processes to remove the antibiotic sulfamethoxazole from water. Water Res 42:3799–3808CrossRefGoogle Scholar
  6. Chang C, Fu Y, Hu M, Wang C, Shan G, Zhu L (2013) Photodegradation of bisphenol A by highly stable palladium-doped mesoporous graphite carbon nitride (Pd/mpg-C3N4) under simulated solar light irradiation. Appl Catal B 142:553–560CrossRefGoogle Scholar
  7. Chang F, Zhang J, Xie Y, Chen J, Li C, Wang J, Luo J, Deng B, Hu X (2014) Fabrication, characterization, and photocatalytic performance of exfoliated gC3N4–TiO2 hybrids. Appl Surf Sci 311:574–581CrossRefGoogle Scholar
  8. Chen S, Zhang H, Li S (2016) Investigation of mechanism involved in TiO2 and photo-Fenton photocatalytic degradation of emerging contaminant sucralose in aqueous media. Procedia Environ Sci 31:753–757CrossRefGoogle Scholar
  9. Desbrow C, Routledge E, Brighty G, Sumpter J, Waldock M (1998) Identification of estrogenic chemicals in STW effluent. 1. Chemical fractionation and in vitro biological screening. Environ Sci Technol 32:1549–1558CrossRefGoogle Scholar
  10. Du X, Zou G, Wang Z, Wang X (2015) A scalable chemical route to soluble acidified graphitic carbon nitride: an ideal precursor for isolated ultrathin gC 3 N 4 nanosheets. Nano 7:8701–8706Google Scholar
  11. Fukahori S, Ichiura H, Kitaoka T, Tanaka H (2003) Capturing of bisphenol A photodecomposition intermediates by composite TiO2–zeolite sheets. Appl Catal B 46:453–462CrossRefGoogle Scholar
  12. Ge L, Han C, Liu J (2011) Novel visible light-induced gC3N4/Bi2WO6 composite photocatalysts for efficient degradation of methyl orange. Appl Catal B 108:100–107CrossRefGoogle Scholar
  13. Gültekin I, Ince NH (2008) Ultrasonic destruction of bisphenol-A: the operating parameters. Ultrason Sonochem 15:524–529CrossRefGoogle Scholar
  14. Horikoshi S, Tokunaga A, Hidaka H, Serpone N (2004) Environmental remediation by an integrated microwave/UV illumination method: VII. Thermal/non-thermal effects in the microwave-assisted photocatalyzed mineralization of bisphenol-a. J Photochem Photobiol A 162:33–40CrossRefGoogle Scholar
  15. Hoshiyama N, Dabwan AH, Katsumata H, Suzuki T, Furukawa M, Kaneco S (2016) Enhanced photocatalytic degradation of bisphenol A in aqueous solution by Ag-doping ZnO. OJINM 6:13CrossRefGoogle Scholar
  16. Ioannidou E, Ioannidi A, Frontistis Z, Antonopoulou M, Tselios C, Tsikritzis D, Konstantinou I, Kennou S, Kondarides DI, Mantzavinos D (2016) Correlating the properties of hydrogenated titania to reaction kinetics and mechanism for the photocatalytic degradation of bisphenol A under solar irradiation. Appl Catal, B 188:65–76CrossRefGoogle Scholar
  17. Jain R, Mathur M, Sikarwar S, Mittal A (2007) Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments. J Environ Manag 85:956–964CrossRefGoogle Scholar
  18. Kaneco S, Rahman MA, Suzuki T, Katsumata H, Ohta K (2004) Optimization of solar photocatalytic degradation conditions of bisphenol A in water using titanium dioxide. J Photochem Photobiol A 163:419–424CrossRefGoogle Scholar
  19. Kaur S, Singh V (2007) Visible light induced sonophotocatalytic degradation of reactive red dye 198 using dye sensitized TiO2. Ultrason Sonochem 14:531–537CrossRefGoogle Scholar
  20. Kormann C, Bahnemann DW, Hoffmann MR (1988) Photocatalytic production of hydrogen peroxides and organic peroxides in aqueous suspensions of titanium dioxide, zinc oxide, and desert sand. Environ Sci Technol 22:798–806CrossRefGoogle Scholar
  21. Laganà A, Bacaloni A, De Leva I, Faberi A, Fago G, Marino A (2004) Analytical methodologies for determining the occurrence of endocrine disrupting chemicals in sewage treatment plants and natural waters. Anal Chim Acta 501:79–88CrossRefGoogle Scholar
  22. Li J, Shen B, Hong Z, Lin B, Gao B, Chen Y (2012) A facile approach to synthesize novel oxygen-doped g-C3N4 with superior visible-light photoreactivity. Chem Commun 48:12017–12019CrossRefGoogle Scholar
  23. Liu J, Zhang T, Wang Z, Dawson G, Chen W (2011) Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photocatalytic activity. J Mater Chem 21:14398–14401CrossRefGoogle Scholar
  24. Liu Y, Yu Y-X, Zhang W-D (2014) Photoelectrochemical study on charge transfer properties of nanostructured Fe2O3 modified by g-C3N4. Int J Hydrog Energy 39:9105–9113CrossRefGoogle Scholar
  25. Ma T, Bai J, Liang H, Wang J, Li C (2016) An efficient method for assembling layered g-C3N4 nanosheets grow on 1D pore channels carbon fibers as a composite photocatalyst by ultrasound-assisted exfoliation and hydrothermal method. Vacuum 134:130–135CrossRefGoogle Scholar
  26. Madhavan J, Grieser F, Ashokkumar M (2010) Combined advanced oxidation processes for the synergistic degradation of ibuprofen in aqueous environments. J Hazard Mater 178:202–208CrossRefGoogle Scholar
  27. Mamba G, Mishra A (2016) Graphitic carbon nitride (g-C3N4) nanocomposites: a new and exciting generation of visible light driven photocatalysts for environmental pollution remediation. Appl Catal B 198:347–377CrossRefGoogle Scholar
  28. Masih D, Ma Y, Rohani S (2017) Graphitic C3N4 based noble-metal-free photocatalyst systems: a review. Appl. Catal., BGoogle Scholar
  29. Mena E, Rey A, Rodríguez E, Beltrán F (2016) Nanostructured CeO2 as catalysts for different AOPs based in the application of ozone and simulated solar radiation. Catal. TodayGoogle Scholar
  30. Mrowetz M, Pirola C, Selli E (2003) Degradation of organic water pollutants through sonophotocatalysis in the presence of TiO2. Ultrason Sonochem 10:247–254CrossRefGoogle Scholar
  31. Nasalevich MA, Kozlova EA, Lyubina TP, Vorontsov AV (2012) Photocatalytic oxidation of ethanol and isopropanol vapors on cadmium sulfide. J Catal 287:138–148CrossRefGoogle Scholar
  32. Ohko Y, Ando I, Niwa C, Tatsuma T, Yamamura T, Nakashima T, Kubota Y, Fujishima A (2001) Degradation of bisphenol A in water by TiO2 photocatalyst. Environ Sci Technol 35:2365–2368CrossRefGoogle Scholar
  33. Ong W-J, Tan L-L, Ng YH, Yong S-T, Chai S-P (2016) Graphitic carbon nitride (g-C3N4)-based photocatalysts for artificial photosynthesis and environmental remediation: are we a step closer to achieving sustainability? Chem Rev 116:7159–7329CrossRefGoogle Scholar
  34. Sathishkumar P, Mangalaraja RV, Rozas O, Vergara C, Mansilla HD, Gracia-Pinilla M, Anandan S (2016) Sonophotocatalytic mineralization of norflurazon in aqueous environment. Chemosphere 146:216–225CrossRefGoogle Scholar
  35. Song L, Zhang S, Wu X, Wei Q (2012) A metal-free and graphitic carbon nitride sonocatalyst with high sonocatalytic activity for degradation methylene blue. Chem Eng J 184:256–260CrossRefGoogle Scholar
  36. Sun S, Wang W, Xu J, Wang L, Zhang Z (2011) Highly efficient photocatalytic oxidation of phenol over ordered mesoporous Bi2WO6. Appl Catal, B 106:559–564CrossRefGoogle Scholar
  37. Suslick KS, Flannigan DJ (2008) Inside a collapsing bubble: sonoluminescence and the conditions during cavitation. Annu Rev Phys Chem 59:659–683CrossRefGoogle Scholar
  38. Taghizadeh MT, Abdollahi R (2011) Sonolytic, sonocatalytic and sonophotocatalytic degradation of chitosan in the presence of TiO2 nanoparticles. Ultrason Sonochem 18:149–157CrossRefGoogle Scholar
  39. Taheri ME, Petala A, Frontistis Z, Mantzavinos D, Kondarides DI (2017) Fast photocatalytic degradation of bisphenol A by Ag3PO4/TiO2 composites under solar radiation. Catal Today 280:99–107CrossRefGoogle Scholar
  40. Torres RA, Nieto JI, Combet E, Pétrier C, Pulgarin C (2008a) Influence of TiO2 concentration on the synergistic effect between photocatalysis and high-frequency ultrasound for organic pollutant mineralization in water. Appl Catal B 80:168–175CrossRefGoogle Scholar
  41. Torres RA, Pétrier C, Combet E, Carrier M, Pulgarin C (2008b) Ultrasonic cavitation applied to the treatment of bisphenol A. Effect of sonochemical parameters and analysis of BPA by-products. Ultrason Sonochem 15:605–611CrossRefGoogle Scholar
  42. Vinoth R, Karthik P, Devan K, Neppolian B, Ashokkumar M (2016) TiO2–NiO p–n nanocomposite with enhanced sonophotocatalytic activity under diffused sunlight. Ultrason. SonochemGoogle Scholar
  43. Wang X, Yuan S, Chen G (2012) Facile synthesis of uniform CdS hollow spheres in an ethanol system and their enhanced photocatalytic activity. ChemPlusChem 77:455–461CrossRefGoogle Scholar
  44. Watanabe N, Horikoshi S, Kawabe H, Sugie Y, Zhao J, Hidaka H (2003) Photodegradation mechanism for bisphenol A at the TiO 2/H 2 O interfaces. Chemosphere 52:851–859CrossRefGoogle Scholar
  45. Wirth J, Neumann R, Antonietti M, Saalfrank P (2014) Adsorption and photocatalytic splitting of water on graphitic carbon nitride: a combined first principles and semiempirical study. Phys Chem Chem Phys 16:15917–15926CrossRefGoogle Scholar
  46. Wong C, Chu W (2003) The direct photolysis and photocatalytic degradation of alachlor at different TiO2 and UV sources. Chemosphere 50:981–987CrossRefGoogle Scholar
  47. Xiong J, Cheng G, Qin F, Wang R, Sun H, Chen R (2013) Tunable BiOCl hierarchical nanostructures for high-efficient photocatalysis under visible light irradiation. Chem Eng J 220:228–236CrossRefGoogle Scholar
  48. Yan S, Li Z, Zou Z (2010) Photodegradation of rhodamine B and methyl orange over boron-doped g-C3N4 under visible light irradiation. Langmuir 26:3894–3901CrossRefGoogle Scholar
  49. Yang S-F, Niu C-G, Huang D, Zhang H, Liang C, Zeng G (2017) SrTiO3 nanocubes decorated with Ag/AgCl nanoparticles as photocatalysts with enhanced visible-light photocatalytic activity towards the degradation of dyes, phenol and bisphenol A. Environ. Sci. NanoGoogle Scholar
  50. Yu K, Yang S, Liu C, Chen H, Li H, Sun C, Boyd SA (2012) Degradation of organic dyes via bismuth silver oxide initiated direct oxidation coupled with sodium bismuthate based visible light photocatalysis. Environ Sci Technol 46:7318–7326CrossRefGoogle Scholar
  51. Zhang S, Yang Y, Guo Y, Guo W, Wang M, Guo Y, Huo M (2013a) Preparation and enhanced visible-light photocatalytic activity of graphitic carbon nitride/bismuth niobate heterojunctions. J Hazard Mater 261:235–245CrossRefGoogle Scholar
  52. Zhang X, Liu X, Fan C, Wang Y, Wang Y, Liang Z (2013b) A novel BiOCl thin film prepared by electrochemical method and its application in photocatalysis. Appl Catal B 132:332–341CrossRefGoogle Scholar
  53. Zhang Y, Zhang N, Tang Z-R, Xu Y-J (2013c) Identification of Bi2WO6 as a highly selective visible-light photocatalyst toward oxidation of glycerol to dihydroxyacetone in water. Chem Sci 4:1820–1824CrossRefGoogle Scholar
  54. Zhang L, Huang F, Liang C, Zhou L, Zhang X, Pang Q (2016) Ultrasound exfoliation of g-C3N4 with assistance of cadmium ions and synthesis of CdS/g-C3N4 ultrathin nanosheets with efficient photocatalytic activity. J Taiwan Inst Chem Eng 60:643–650CrossRefGoogle Scholar
  55. Zhong X, Jin M, Dong H, Liu L, Wang L, Yu H, Leng S, Zhuang G, Li X, Wang J-g (2014) TiO2 nanobelts with a uniform coating of g-C3N4 as a highly effective heterostructure for enhanced photocatalytic activities. J Solid State Chem 220:54–59CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Sharmini Sunasee
    • 1
  • Kah Hon Leong
    • 2
  • Kien Tiek Wong
    • 3
  • Gooyong Lee
    • 1
  • Saravanan Pichiah
    • 4
  • InWook Nah
    • 5
  • Byong-Hun Jeon
    • 6
  • Yeomin Yoon
    • 7
  • Min Jang
    • 3
    Email author
  1. 1.Department of Civil EngineeringFaculty of Engineering, University of MalayaKuala LumpurMalaysia
  2. 2.Faculty of Engineering and Green TechnologyUniversiti Tunku Abdul Rahman, Jalan Universiti, Bandar BaratKamparMalaysia
  3. 3.Department of Environmental EngineeringKwangwoon UniversitySeoulRepublic of Korea
  4. 4.Department of Environmental Science & EngineeringIndian Institute of Technology (ISM) DhanbadDhanbadIndia
  5. 5.Korea Institute of Science and TechnologySeoulRepublic of Korea
  6. 6.Department of Earth Resources and Environmental EngineeringHanyang UniversitySeoulRepublic of Korea
  7. 7.Department of Civil and Environmental EngineeringUniversity of South CarolinaColumbiaUSA

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