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Efficient photocatalytic degradation of nitrobenzene by copper-doped TiO2: kinetic study, degradation pathway, and mechanism

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Abstract

Cu-doped TiO2 (0.1, 0.25, and 0.5% Cu-TiO2) photocatalyst was prepared by sol–gel method and was characterized by powder XRD, FTIR, TEM, SEM, EDX, UV–vis diffuse reflectance (DRS), photoluminescence (PL), and Raman spectroscopy. The XRD spectrum shows tetragonal anatase phase. TEM analysis indicate that the nanoparticles were spherical with sizes 12–13 nm. The degradation of NB was studied, and an optimal degradation time of 180 min led to 98.6% NB abatement of NB = 0.05 mM, pH = 4, and catalyst loading = 50 mg/100 mL, under visible light. The degradation of NB follows the pseudo-first-order kinetics. The reusability studies indicated the excellent stability of 0.25% Cu-TiO2.

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References

  • Agorku ES, Mamba BB, Pandey AC, Mishra AK (2014): Sulfur/gadolinium-codoped TiO2 nanoparticles for enhanced visible-light photocatalytic performance. Journal of Nanomaterials 2014

  • Araújo AB, Amarante Junior OP, Vieira EM, Valente JPS, Padilha PM, Florentino AO (2006) Photodegradation of soluble and emulsive cutting fluids using TiO2 as catalyst. J Braz Chem Soc 17:737–740

    Article  Google Scholar 

  • Baghriche O, Rtimi S, Pulgarin C, Sanjines R, Kiwi J (2012) Innovative TiO2/Cu nanosurfaces inactivating bacteria in the minute range under low-intensity actinic light. ACS Appl Mater Interfaces 4:5234–5240

    Article  CAS  Google Scholar 

  • Baghriche O, Rtimi S, Pulgarin C, Sanjines R, Kiwi J (2013) Effect of the spectral properties of TiO2, Cu, TiO2/Cu sputtered films on the bacterial inactivation under low intensity actinic light. J Photochem Photobiol A Chem 251:50

    Article  CAS  Google Scholar 

  • Bandara J, Kiwi J, Pulgarin C, Peringer P, Pajonk G-M, Elaloui A, Albers P (1996) Novel cyclic process mediated by copper oxides active in the degradation of nitrophenols: implications for the natural cycle. Environ Sci Technol 30:1261–1267

    Article  CAS  Google Scholar 

  • Biyoghe Bi Ndong L, Ibondou MP, Gu X, Lu S, Qiu Z, Sui Q, Mbadinga SM (2014) Enhanced photocatalytic activity of TiO2 nanosheets by doping with Cu for chlorinated solvent pollutants degradation. Ind Eng Chem Res 53:1368–1376

    Article  CAS  Google Scholar 

  • Chen X, Mao SS (2007) Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chem Rev 107:2891–2959

    Article  CAS  Google Scholar 

  • Chen H, Nanayakkara CE, Grassian VH (2012) Titanium dioxide photocatalysis in atmospheric chemistry. Chem Rev 112:5919–5948

    Article  CAS  Google Scholar 

  • Choi HC, Jung YM, Kim SB (2005) Size effects in the Raman spectra of TiO2 nanoparticles. Vib Spectrosc 37:33–38

    Article  CAS  Google Scholar 

  • Choudhury B, Dey M, Choudhury A (2013b) Defect generation, d-d transition, and band gap reduction in Cu-doped TiO 2 nanoparticles. Int Nano Lett 3:1–8

    Article  CAS  Google Scholar 

  • Choudhury B, Dey M, Choudhury A (2013a): Defect generation, d-d transition, and band gap reduction in Cu-doped TiO2 nanoparticles. International Nano Letters 3

  • Daneshvar N, Salari D, Khataee A (2004) Photocatalytic degradation of azo dye acid red 14 in water on ZnO as an alternative catalyst to TiO2. J Photochem Photobiol, A 162:317–322

    Article  CAS  Google Scholar 

  • Du Y, Rabani J (2003) The measure of TiO2 photocatalytic efficiency and the comparison of different photocatalytic titania. J Phys Chem B 107:11970–11978

    Article  CAS  Google Scholar 

  • Duan H, Liu Y, Yin X, Bai J, Qi J (2016) Degradation of nitrobenzene by Fenton-like reaction in a H2O2/schwertmannite system. Chem Eng J 283:873–879

    Article  CAS  Google Scholar 

  • Ganesh I, Gupta A, Kumar P, Sekhar P, Radha K, Padmanabham G, Sundararajan G (2012): Preparation and Characterization of Ni-Doped T i O 2 Materials for photocurrent and photocatalytic applications. The Scientific World Journal 2012

  • Griboval A, Blanchard P, Gengembre L, Payen E, Fournier M, Dubois J, Bernard J (1999) Hydrotreatment catalysts prepared with heteropolycompound: characterisation of the oxidic precursors. J Catal 188:102–110

    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 

  • Han Y, Qi M, Zhang L, Sang Y, Liu M, Zhao T, Niu J, Zhang S (2019) Degradation of nitrobenzene by synchronistic oxidation and reduction in an internal circulation microelectrolysis reactor. J Hazard Mater 365:448–456

    Article  CAS  Google Scholar 

  • Irie H, Kamiya K, Shibanuma T, Miura S, Tryk DA, Yokoyama T, Hashimoto K (2009) Visible light-sensitive Cu (II)-grafted TiO2 photocatalysts: activities and X-ray absorption fine structure analyses. J Phys Chem C 113:10761–10766

    Article  CAS  Google Scholar 

  • Janczarek M, Kowalska E (2017) On the origin of enhanced photocatalytic activity of copper-modified titania in the oxidative reaction systems. Catalysts 7:317

    Article  Google Scholar 

  • Jeong S, Lee H, Park H, Jeon K-J, Park Y-K, Jung S-C (2018) Rapid photocatalytic degradation of nitrobenzene under the simultaneous illumination of UV and microwave radiation fields with a TiO2 ball catalyst. Catal Today 307:65–72

    Article  CAS  Google Scholar 

  • Karthik K, Pandian SK, Jaya NV (2010) Effect of nickel doping on structural, optical and electrical properties of TiO2 nanoparticles by sol–gel method. Appl Surf Sci 256:6829–6833

    Article  CAS  Google Scholar 

  • Khan TT, Bari GA, Kang H-J, Lee T-G, Park J-W, Hwang HJ, Hossain SM, Mun JS, Suzuki N, Fujishima A (2021) Synthesis of N-Doped TiO2 for Efficient Photocatalytic Degradation of Atmospheric NOx. Catalysts 11:109

    Article  CAS  Google Scholar 

  • Leyland NS, Podporska-Carroll J, Browne J, Hinder SJ, Quilty B, Pillai SC (2016) Highly efficient F, Cu doped TiO 2 anti-bacterial visible light active photocatalytic coatings to combat hospital-acquired infections. Sci Rep 6:24770

    Article  CAS  Google Scholar 

  • Li G, Dimitrijevic NM, Chen L, Rajh T, Gray KA (2008) Role of surface/interfacial Cu2+ sites in the photocatalytic activity of coupled CuO− TiO2 nanocomposites. J Phys Chem C 112:19040–19044

    Article  CAS  Google Scholar 

  • Mu Y, Rozendal RA, Rabaey K, Keller Jr (2009) Nitrobenzene removal in bioelectrochemical systems. Environ Sci Technol 43, 8690-8695

  • Nagaraju G, Nagabhushana H, Basavaraj R, Raghu G, Suresh D, Rajanaika H, Sharma S (2016) Green, nonchemical route for the synthesis of ZnO superstructures, evaluation of its applications toward photocatalysis, photoluminescence, and biosensing. Cryst Growth Des 16:6828–6840

    Article  Google Scholar 

  • Nakhate G, Nikam V, Kanade K, Arbuj S, Kale B, Baeg J (2010) Hydrothermally derived nanosized Ni-doped TiO2: a visible light driven photocatalyst for methylene blue degradation. Mater Chem Phys 124:976–981

    Article  CAS  Google Scholar 

  • Nithyaa N, Jaya NV (2018) Structural, optical, and magnetic properties of Gd-doped TiO 2 nanoparticles. J Supercond Novel Magn 31:4117–4126

    Article  CAS  Google Scholar 

  • Patle L, Huse V, Chaudhari A (2017) Band edge movement and structural modifications in transition metal doped TiO2 nanocrystals for the application of DSSC. Mater Res Express 4:105045

    Article  Google Scholar 

  • Petala A, Ioannidou E, Georgaka A, Bourikas K, Kondarides DI (2015) Hysteresis phenomena and rate fluctuations under conditions of glycerol photo-reforming reaction over CuOx/TiO2 catalysts. Appl Catal B 178:201–209

    Article  CAS  Google Scholar 

  • Rajeshwar K, Osugi M, Chanmanee W, Chenthamarakshan C, Zanoni MVB, Kajitvichyanukul P, Krishnan-Ayer R (2008) Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media. J Photochem Photobiol, C 9:171–192

    Article  CAS  Google Scholar 

  • Reddy NL, Shankar M, Sharma S, Nagaraju G (2020) One-pot synthesis of Cu–TiO2/CuO nanocomposite: application to photocatalysis for enhanced H2 production, dye degradation & detoxification of Cr (VI). Int J Hydrogen Energy 45:7813–7828

    Article  Google Scholar 

  • Reynoso-Soto EA, Pérez-Sicairos S, Reyes-Cruzaley AP, Castro-Riquelme CL, Félix-Navarro RM, Paraguay-Delgado F, Alonso-Núñez G, Lin-Ho SW (2013) Photocatalytic degradation of nitrobenzene using nanocrystalline TiO2 photocatalyst doped with Zn ions. J Mex Chem Soc 57:298–305

    CAS  Google Scholar 

  • Robert D, Dongui B, Weber J-V (2003) Heterogeneous photocatalytic degradation of 3-nitroacetophenone in TiO2 aqueous suspension. J Photochem Photobiol, A 156:195–200

    Article  CAS  Google Scholar 

  • Rtimi S, Baghriche O, Pulgarin C, Lavanchy J-C, Kiwi J (2013) Growth of TiO2/Cu films by HiPIMS for accelerated bacterial loss of viability. Surf Coat Technol 232:804–813

    Article  CAS  Google Scholar 

  • Rtimi S, Giannakis S, Sanjines R, Pulgarin C, Bensimon M, Kiwi J (2016) Insight on the photocatalytic bacterial inactivation by co-sputtered TiO2–Cu in aerobic and anaerobic conditions. Appl Catal B 182:277–285

    Article  CAS  Google Scholar 

  • Sahu M, Biswas P (2011) Single-step processing of copper-doped titania nanomaterials in a flame aerosol reactor. Nanoscale Res Lett 6:1–14

    Article  Google Scholar 

  • Sajjad S, Leghari SAK, Zhang J (2013) Copper impregnated ionic liquid assisted mesoporous titania: visible light photocatalyst. RSC Adv 3:12678–12687

    Article  CAS  Google Scholar 

  • Shaban M, Ahmed AM, Shehata N, Betiha MA, Rabie AM (2019) Ni-doped and Ni/Cr co-doped TiO2 nanotubes for enhancement of photocatalytic degradation of methylene blue. J Colloid Interface Sci 555:31–41

    Article  CAS  Google Scholar 

  • Stock NL, Peller J, Vinodgopal K, Kamat PV (2000) Combinative sonolysis and photocatalysis for textile dye degradation. Environ Sci Technol 34:1747–1750

    Article  CAS  Google Scholar 

  • Subbaramaiah V, Srivastava VC, Mall ID (2014) Catalytic oxidation of nitrobenzene by copper loaded activated carbon. Sep Purif Technol 125:284–290

    Article  Google Scholar 

  • Sun Z, Zhao M, Li F, Wang T, Xu L (2014) Nanocomposite film of TiO2 nanotube and polyoxometalate towards photocatalytic degradation of nitrobenzene. Mater Res Bull 60:524–529

    Article  CAS  Google Scholar 

  • Tian F, Zhang Y, Zhang J, Pan C (2012) Raman spectroscopy: a new approach to measure the percentage of anatase TiO2 exposed (001) facets. J Phys Chem C 116:7515–7519

    Article  CAS  Google Scholar 

  • Wei W, Sun R, Cui J, Wei Z (2010) Removal of nitrobenzene from aqueous solution by adsorption on nanocrystalline hydroxyapatite. Desalination 263:89–96

    Article  CAS  Google Scholar 

  • Xu J, Ao Y, Fu D, Yuan C (2009) Synthesis of Gd-doped TiO2 nanoparticles under mild condition and their photocatalytic activity. Colloids Surf, A 334:107–111

    Article  CAS  Google Scholar 

  • Yu J, Kiwi J, Wang T, Pulgarin C, Rtimi S (2019) Evidence for a dual mechanism in the TiO2/CuxO photocatalyst during the degradation of sulfamethazine under solar or visible light: critical issues. J Photochem Photobiol, A 375:270–279

    Article  CAS  Google Scholar 

  • Zhao X-K, Yang G-P, Gao X-C (2003) Studies on the sorption behaviors of nitrobenzene on marine sediments. Chemosphere 52:917–925

    Article  CAS  Google Scholar 

  • Zhao L, Ma W, Ma J, Wen G, Liu Q (2015) Relationship between acceleration of hydroxyl radical initiation and increase of multiple-ultrasonic field amount in the process of ultrasound catalytic ozonation for degradation of nitrobenzene in aqueous solution. Ultrason Sonochem 22:198–204

    Article  CAS  Google Scholar 

  • Zuas O, Budiman H (2013) Synthesis of nanostructured copper-doped titania and its properties. Nano-Micro Letters 5:26–33

    Article  CAS  Google Scholar 

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Acknowledgements

Authors are grateful to the National University of Sciences and Technology for funding and providing all the required facilities to carry out the project.

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Authors and Affiliations

  1. School of Natural Sciences, National University of Sciences and Technology, H-12, Islamabad, 44000, Pakistan

    Tehmina Akhtar, Habib Nasir, Effat Sitara, Syeda Aqsa Batool Bukhari, Sharif Ullah & Rana Muhammad Arslan Iqbal

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  1. Tehmina Akhtar
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  2. Habib Nasir
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  3. Effat Sitara
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  4. Syeda Aqsa Batool Bukhari
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  5. Sharif Ullah
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  6. Rana Muhammad Arslan Iqbal
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Contributions

Tehmina Akhtar: conceptualization, investigation, visualization, writing (original draft), and writing (review and editing)

Habib Nasir: conceptualization, supervision, and project administration

Effat Sitara and Syeda Aqsa Batool Bukhari: methodology and mechanism analysis

Sharif Ullah and Rana Muhammad Arslan Iqbal: formal analysis and investigation

All authors read and approved the final manuscript

Corresponding author

Correspondence to Habib Nasir.

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Communicated by Sami Rtimi.

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Highlights

• Pristine and copper-doped TiO2 (0.1, 0.25, and 0.5% Cu-TiO2) photocatalysts were prepared by the sol–gel method.

• The bandgap was reduced, and absorption was enhanced by Cu ions

• 0.25% copper-doped TiO2 (0.25% Cu-TiO2) has less e− and h+ recombination rate.

• Nitrobenzene (NB) is a carcinogenic pollutant extensively used in industry and poses a serious threat to human health and the environment.

• The synthesized photocatalyst and 0.25% copper-doped TiO2 efficiently degrade the nitrobenzene (98.68%) in 180 min under visible light.

Responsible Editor: Sami Rtimi

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Akhtar, T., Nasir, H., Sitara, E. et al. Efficient photocatalytic degradation of nitrobenzene by copper-doped TiO2: kinetic study, degradation pathway, and mechanism. Environ Sci Pollut Res 29, 49925–49936 (2022). https://doi.org/10.1007/s11356-022-19422-5

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