Skip to main content
SpringerLink
Log in

Photocatalytic activity evaluation of TiO2 nanoparticles based on COD analyses for water treatment applications: a standardization attempt

  • Original Paper
  • Published:
International Journal of Environmental Science and Technology Aims and scope Submit manuscript

Abstract

Evaluation of the photocatalytic activities of TiO2 nanomaterials based on the chemical oxygen demand (COD) analyses under identical experimental conditions was not previously reported. In this work, COD has been selected as an adequate industrial water quality measure toward the establishment of a representative standard test method. The initial COD values of six organic pollutants representing dye, surfactants, phenols and alcohol were set at 30 ± 2 mg/L. Ten of different commercial and synthesized TiO2 samples representing anatase, rutile and mixed phases were used and characterized. The data of photocatalytic processes were compared to that obtained using the commonly widespread Degussa-P25 TiO2 (TD). The COD of all pollutants was completely removed by TD at UV exposure dose ≤9.36 mWh/cm2. Consequently, the maximum irradiation dose was set at this value in all experiments. The percentages of COD removal as well as the values of the accumulated UV doses required for complete removal of pollutants were measured using the different TiO2 samples. TiO2 samples show different performance abilities toward the various pollutants compared to TD. Based on the obtained data, TiO2 photocatalysts were divided into two categories according to the hydroxyl radical formation rates. Comparison with previous studies reveals that the photocatalytic efficiency evaluation depends on the method of measurement. COD is recommended to be used as an adequate technique of analysis that meets the purpose of water treatment applications.

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

Similar content being viewed by others

References

  • Ali I (2010) The quest for active carbon adsorbent substitutes: inexpensive adsorbents for toxic metal ions removal from wastewater. Sep Purif Rev 39:95–171

    Article  CAS  Google Scholar 

  • Ali I (2012) New generation adsorbents for water treatment. Chem Rev 112:5073–5091

    Article  CAS  Google Scholar 

  • Ali I (2014) Water treatment by adsorption columns: evaluation at ground level. Sep Purif Rev 43:175–2015

    Article  CAS  Google Scholar 

  • Ali I, Gupta VK (2006) Advances in water treatment by adsorption technology. Nature London 1:2661–2667

    CAS  Google Scholar 

  • Ali I, Asim M, Khan TA (2012) Low cost adsorbents for removal of organic pollutants from wastewater. J Environ Manag 113:170–183

    Article  CAS  Google Scholar 

  • Arbuj SS, Hawaldar RR, Mulik UP, Wani BN, Amalnerkar DP, Waghmode SB (2010) Preparation, characterization and photocatalytic activity of TiO2 towards methylene blue degradation. Mater Sci Eng, B 168:90–94

    Article  CAS  Google Scholar 

  • Asuha S, Zhou XG, Zhao S (2010) Adsorption of methyl orange and Cr(VI) on mesoporous TiO2 prepared by hydrothermal method. J Hazard Mater 181:204–210

    Article  CAS  Google Scholar 

  • Barakat MA (2011) Adsorption and photodegradation of procion yellow HEXL dye in textile wastewater over TiO2 suspension. J Hydro-Environ Res 5:137–142

    Article  Google Scholar 

  • Bessekhouad Y, Robert D, Weber J-V, Chaoui N (2004) Effect of alkaline-doped TiO2 on photocatalytic efficiency. J Photochem Photobiol, A 167:49–57

    Article  CAS  Google Scholar 

  • Černigoj U, Štangara UL, Trebšea P, Sarakha M (2009) Determination of catalytic properties of TiO2 coatings using aqueous solution of coumarin: standardization efforts. J Photochem Photobiol, A 201:142–150

    Article  Google Scholar 

  • EL Mekkawi D, Abdel-Mottaleb MSA (2005) The interaction and photostability of some xanthenes and selected azo sensitizing dyes with TiO2 nanoparticles. Int J Photoenergy 7:95–101

    Article  CAS  Google Scholar 

  • EL-Mekkawi DM, Galal H (2013) Removal of a synthetic dye “Direct Fast Blue B2RL” via adsorption and photocatalytic degradation using low cost rutile and Degussa P25 titanium dioxide. J Hydro-Environ Res 7:219–226

    Article  Google Scholar 

  • Eremektar G, Selcuk H, Meric S (2007) Investigation of the relation between COD fractions and the toxicity in a textile finishing industry wastewater: effect of preozonation. Desalination 211:314–320

    Article  CAS  Google Scholar 

  • Gupta VK, Jain R, Mittal A, Saleh TA, Nayak A, Agarwal S, Sikarwar S (2012) Photo-catalytic degradation of toxic dye amaranth on TiO2/UV in aqueous suspensions. Mater Sci Eng, C 32:12–17

    Article  CAS  Google Scholar 

  • Gupta VK, Kumar R, Nayak A, Saleh TA, Barakat MA (2013) Adsorptive removal of dyes from aqueous solution onto carbon nanotubes: a review. Adv Colloid Interface Sci 193–194:24–34

    Article  Google Scholar 

  • Hafez HS, Saif M, Mcleskey Jr JT, Abdel-Mottaleb MSA, Yahia IS, Story T, Knoff W (2009) Hydrothermal preparation of Gd3+-doped titanate nanotubes: magnetic properties and photovoltaic performance. Int J Photoenergy 2009:1-8

    Article  Google Scholar 

  • Henderson MA (2011) A surface science perspective on TiO2 photocatalysis. Surf Sci Rep 66:185–297

    Article  CAS  Google Scholar 

  • Huang D, Liao S, Quan S, Liu L, He Z, Wan J, Zhou W (2008) Synthesis and characterization of visible light responsive N-TiO2 mixed crystal by a modified hydrothermal process. J Non-Cryst Solids 354:3965–3972

    Article  CAS  Google Scholar 

  • Ishibashi K, Fujishima A, Watanabe T (2000) Hashimoto K, detection of active oxidative species in TiO2 photocatalysis using the fluorescence technique. Electrochem Commun 2:207–210

    Article  CAS  Google Scholar 

  • ISO 10676 (2010) Fine ceramics, advanced technical ceramics—test method for water purification of semiconducting photocatalytic materials by measurement of forming ability of active oxygen. ISO, Geneva 2010

    Google Scholar 

  • ISO 10678 (2010) Fine ceramics, advanced technical ceramics—determination of photocatalytic activity of surfaces in an aqueous medium by degradation of methylene blue. ISO, Geneva 2010

    Google Scholar 

  • Kaczala F, Marques M, Hogland W (2010) Biotreatability of wastewater generated during machinery washing in a wood-based industry: COD, formaldehyde and nitrogen removal. Bioresour Technol 101:8975–8983

    Article  CAS  Google Scholar 

  • Karthikeyan S, Anandan C, Subramanian J, Sekaran G (2013) Characterization of iron impregnated polyacrylamide catalyst and its application to the treatment of municipal wastewater. RSC Adv 3:15044–15057

    Article  CAS  Google Scholar 

  • Law 4 (The Egyptian environment law number 4 and its executive regulation) (1994) Egypt

  • Law 93 (The Egyptian environmental law number 93) (1962) Discharge of liquid waste to sewage networks, as amended by Decree No. 44/2000, Egypt

  • Li G, Park S, Rittamnn BE (2012a) Degradation of reactive dyes in a photocatalytic circulating-bed biofilm reactor. Biotechnol Bioeng 109:884–893

    Article  CAS  Google Scholar 

  • Li G, Park S, Rittmann BE (2012b) Developing an efficient TiO2-coated biofilm carrier for intimate coupling of photocatalysis and biodegradation. Water Res 46:6489–6496

    Article  CAS  Google Scholar 

  • Luo Y, Tai WS, Seo HO, Kim K-D, Kim MJ, Dey NK, Kim YD, Choi KH, Lim DC (2010) Adsorption and photocatalytic decomposition of toluene on TiO2 surfaces. Catal Lett 138:76–81

    Article  CAS  Google Scholar 

  • Mahmoodian H, Moradi O, Shariatzadeha B, Salehf TA, Tyagi I, Maity A, Asif M, Gupta VK (2015) Enhanced removal of methyl orange from aqueous solutions by poly HEMA–chitosan-MWCNT nano-composite. J Mol Liq 202:189–198

    Article  CAS  Google Scholar 

  • Mills A, Morris S (1993) Photomineralization of 4-chlorophenol sensitized by titanium dioxide: a study of the initial kinetics of carbon dioxide photogenerationJ. Photochem Photobiol A 71:75–83

    Article  CAS  Google Scholar 

  • Mills A, Hill C, Robertson PKJ (2012) Overview of the current ISO tests for photocatalytic materials. J Photochem Photobiol, A 237:7–23

    Article  CAS  Google Scholar 

  • Murgolo S, Petronella F, Ciannarella R, Comparelli R, Agostiano A, Curri ML, Mascolo G (2015) UV and solar-based photocatalytic degradation of organic pollutants by nano-sized TiO2 on carbon nanotubes. Catal Today 240:114–124

    Article  CAS  Google Scholar 

  • Papageorgiou N, Barbé C, Graetzel M (1998) Morphology and adsorbate dependence of ionic transport in dye sensitized mesoporous TiO2 Films. J Phys Chem B 102:4156–4164

    Article  CAS  Google Scholar 

  • Patterson AL (1939) The Scherrer formula for X-ray particle size determination. Phys Rev 56:978–982

    Article  CAS  Google Scholar 

  • Ryu J, Choi W (2008) Substrate-specific photocatalytic activities of TiO2 and multiactivity test for water treatment application. Environ Sci Technol 42:294–300

    Article  CAS  Google Scholar 

  • Sabin F, Tiirk T, Vogler A (1992) Photo-oxidation of organic compounds in the presence of titanium dioxide: determination of the efficiency. J Photochem Photobiol A Chem 63:99–106

    Article  CAS  Google Scholar 

  • Saif M, Aboul-Fotouh SMK, El-Molla SA, Ibrahim MM, Ismail LFM (2012) Improvement of the structural, morphology, and optical properties of TiO2 for solar treatment of industrial wastewater. J Nanopart Res 14:1227

    Article  Google Scholar 

  • Saif M, El-Molla SA, Aboul-Fotouh SMK, Hafez H, Ibrahim MM, Abdel-Mottaleb MSA, Ismail LFM (2013) Synthesis of highly active thin film based on TiO2 nanomaterial for self-cleaning application. Spectrochim Acta Mol Biomol 112:46–51

    Article  CAS  Google Scholar 

  • Saleh TA (2015) Isotherm, kinetic, and thermodynamic studies on Hg(II) adsorption from aqueous solution by silica- multiwall carbon nanotubes. Sci Pollut Res, Environ. doi:10.1007/s11356-015-4866-z

    Google Scholar 

  • Saleh TA, Gupta VK (2011) Functionalization of tungsten oxide into MWCNT and its application for sunlight-induced degradation of rhodamine B. J Colloid Interface Sci 362(2):337–344

    Article  CAS  Google Scholar 

  • Saleh TA, Gupta VK (2012a) Column with CNT/magnesium oxide composite for lead (II) removal from water. Environ Sci Pollut Res 19:1224–1228

    Article  CAS  Google Scholar 

  • Saleh TA, Gupta VK (2012b) Photo-catalyzed degradation of hazardous dye methyl orange by use of a composite catalyst consisting of multi-walled carbon nanotubes and titanium dioxide. J Colloid Interface Sci 371(1):101–106

    Article  CAS  Google Scholar 

  • Saleh TA, Al-Saadi AA, Gupta VK (2014) Carbonaceous adsorbent prepared from waste tires: Experimental and computational evaluations of organic dye methyl orange. J Mol Liq 191:85–91

    Article  CAS  Google Scholar 

  • Serpone N, Sauvé G, Koch R, Tahiri H, Pichat P, Piccinini P, Pelizzetti E, Hidaka H (1996) Standardization protocol of process efficiencies and activation parameters in heterogeneous photocatalysis: relative photonic efficiencies ζr. J Photochem Photobiol A Chem 94:191–203

    Article  CAS  Google Scholar 

  • Silvestre CIC, Frigerio C, Santos JLM, Lima JLFC (2011) Quantum dots assisted photocatalysis for the chemiluminometric determination of chemical oxygen demand using a single interface flow system. Anal Chim Acta 69:193–197

    Article  Google Scholar 

  • Sirtori C, Zapata A, Oller I, Gernjak W, Agüera A, Malato S (2009) Decontamination industrial pharmaceutical wastewater by combining solar photo-Fenton and biological treatment. Water Res 43:661–668

    Article  CAS  Google Scholar 

  • Takashi J (2003) Dye adsorption behavior of anatase- and rutile-type TiO2 nanoparticles modified by various heat-treatments. J Mater Sci 38:1695–1702

    Article  Google Scholar 

  • Theurich J, Lindner M, Bahnemann DW (1996) Photocatalytic degradation of 4-chlorophenol in aerated aqueous titanium dioxide suspensions: a kinetic and mechanistic study. Langmuir 12:6368–6376

    Article  CAS  Google Scholar 

  • Torimoto T, Nakamura N, Ikeda S, Ohtani B (2002) Discrimination of the active crystalline phases in anatase-rutile mixed titanium(IV) oxide photocatalysts through action spectrum analyses. Phys Chem Chem Phys 4:5910–5914

    Article  CAS  Google Scholar 

  • Tryba B, Toyoda M, Morawski AW, Nonaka R, Inagaki M (2007) Photocatalytic activity and OH radical formation on TiO2 in the relation to crystallinity. Appl Catal B 71:163–168

    Article  CAS  Google Scholar 

  • Xiang Q, Yu J, Wong PK (2011) Quantitative characterization of hydroxyl radicals produced by various photocatalysts. J Colloid Interface Sci 357:163–167

    Article  CAS  Google Scholar 

  • Xiao Q, Si Z, Zhang J, Xiao C, Tan X (2008) Photoinduced hydroxyl radical and photocatalytic activity of samarium-doped TiO2 nanocrystalline. J Hazard Mater 150:62–67

    Article  CAS  Google Scholar 

  • Zhou Y, Jing T, Hao Q, Zhou Y, Mei S (2012) A sensitive and environmentally friendly method for determination of chemical oxygen demand using NiCu alloy electrode. Electrochim Acta 74:165–170

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Research Centre of Egypt, NRC, 9th plan (research point grant no. P90901).

Author information

Authors and Affiliations

  1. Physical Chemistry Department, National Research Centre, NRC, 33 EL Bohouth st-, Dokki-Giza-, P. O. 12622, Egypt

    D. M. EL-Mekkawi & R. M. Abd EL Wahab

  2. Inorganic Chemistry Department, National Research Centre, NRC, 33 EL Bohouth st.-, Dokki-Giza-, P. O. 12622, Egypt

    H. R. Galal & W. A. A. Mohamed

Authors
  1. D. M. EL-Mekkawi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. H. R. Galal
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. R. M. Abd EL Wahab
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. W. A. A. Mohamed
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to D. M. EL-Mekkawi.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

EL-Mekkawi, D.M., Galal, H.R., Abd EL Wahab, R.M. et al. Photocatalytic activity evaluation of TiO2 nanoparticles based on COD analyses for water treatment applications: a standardization attempt. Int. J. Environ. Sci. Technol. 13, 1077–1088 (2016). https://doi.org/10.1007/s13762-016-0944-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13762-016-0944-0

Keywords

Search

Navigation