Property-performance relationship of core-shell structured black TiO₂ photocatalyst for environmental remediation

Abstract

● Properties and performance relationship of CSBT photocatalyst were investigated.

● Properties of CSBT were controlled by simply manipulating glycerol content.

● Performance was linked to semiconducting and physicochemical properties.

● CSBT (W:G ratio 9:1) had better performance with lower energy consumption.

● Phenols were reduced by 48.30% at a cost of $2.4127 per unit volume of effluent.

Understanding the relationship between the properties and performance of black titanium dioxide with core-shell structure (CSBT) for environmental remediation is crucial for improving its prospects in practical applications. In this study, CSBT was synthesized using a glycerol-assisted sol-gel approach. The effect of different water-to-glycerol ratios (W:G = 1:0, 9:1, 2:1, and 1:1) on the semiconducting and physicochemical properties of CSBT was investigated. The effectiveness of CSBT in removing phenolic compounds (PHCs) from real agro-industrial wastewater was studied. The CSBT synthesized with a W:G ratio of 9:1 has optimized properties for enhanced removal of PHCs. It has a distinct core-shell structure and an appropriate amount of Ti³⁺ cations (11.18%), which play a crucial role in enhancing the performance of CSBT. When exposed to visible light, the CSBT performed better: 48.30% of PHCs were removed after 180 min, compared to only 21.95% for TiO₂ without core-shell structure. The CSBT consumed only 45.5235 kWh/m³ of electrical energy per order of magnitude and cost $2.4127 per unit volume of treated agro-industrial wastewater. Under the conditions tested, the CSBT demonstrated exceptional stability and reusability. The CSBT showed promising results in the treatment of phenols-containing agro-industrial wastewater.

Graphical abstract

Keywords

Black TiO ₂ / Core-shell structure / Property-performance relationship / Agro-industrial effluent / Environmental remediation

References

[1] Alhaji M H, Sanaullah K, Salleh S F, Baini R, Lim S F, Rigit A R H, Said K A M, Khan A. (2018). Photo-oxidation of pre-treated palm oil mill effluent using cylindrical column immobilized photoreactor. Process Safety and Environmental Protection, 117: 180–189

[2] Ariyanti D, Mills L, Dong J, Yao Y, Gao W. (2017). NaBH₄ modified TiO₂: defect site enhancement related to its photocatalytic activity. Materials Chemistry and Physics, 199: 571–576

[3] Bakbolat B, Daulbayev C, Sultanov F, Beissenov R, Umirzakov A, Mereke A, Bekbaev A, Chuprakov I. (2020). Recent developments of TiO₂-based photocatalysis in the hydrogen evolution and photodegradation: a review. Nanomaterials (Basel, Switzerland), 10(9): 1790

[4] Balachandran U, Eror N. (1988). Electrical conductivity in non-stoichiometric titanium dioxide at elevated temperatures. Journal of Materials Science, 23(8): 2676–2682

[5] Bharti B, Kumar S, Lee H N, Kumar R. (2016). Formation of oxygen vacancies and Ti³⁺ state in TiO₂ thin film and enhanced optical properties by air plasma treatment. Scientific Reports, 6(1): 32355

[6] Billo T, Fu F Y, Raghunath P, Shown I, Chen W F, Lien H T, Shen T H, Lee J F, Chan T S, Huang K Y. . (2018). Ni-nanocluster modified black TiO₂ with dual active sites for selective photocatalytic CO₂ reduction. Nano. Micro. Small, 14(2): 1702928

[7] Charles A, Cheng C K. (2019). Photocatalytic treatment of palm oil mill effluent by visible light-active calcium ferrite: effects of catalyst preparation technique. Journal of Environmental Management, 234: 404–411

[8] Chen S, Wang Y, Li J, Hu Z, Zhao H, Xie W, Wei Z. (2018). Synthesis of black TiO₂ with efficient visible-light photocatalytic activity by ultraviolet light irradiation and low temperature annealing. Materials Research Bulletin, 98: 280–287

[9] Chen X, Liu L, Huang F. (2015). Black titanium dioxide (TiO₂) nanomaterials. Chemical Society Reviews, 44(7): 1861–1885

[10] Cheng C K, Derahman M R, Khan M R. (2015). Evaluation of the photocatalytic degradation of pre-treated palm oil mill effluent (POME) over Pt-loaded titania. Journal of Environmental Chemical Engineering, 3(1): 261–270

[11] Cheng C K, Deraman M R, Ng K H, Khan M R. (2016). Preparation of titania doped argentum photocatalyst and its photoactivity towards palm oil mill effluent degradation. Journal of Cleaner Production, 112: 1128–1135

[12] DieboldU (2003). The surface science of titanium dioxide. Surface Science Reports, 48(5–8): 53–229

[13] Dong H, Zeng G, Tang L, Fan C, Zhang C, He X, He Y. (2015). An overview on limitations of TiO₂-based particles for photocatalytic degradation of organic pollutants and the corresponding countermeasures. Water Research, 79: 128–146

[14] Eom J Y, Lim S J, Lee S M, Ryu W H, Kwon H S. (2015). Black titanium oxide nanoarray electrodes for high rate Li-ion microbatteries. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 3(21): 11183–11188

[15] Ergül F E, Sargın S, Öngen G, Sukan F V. (2011). Dephenolization and decolorization of olive mill wastewater through sequential batch and co-culture applications. World Journal of Microbiology & Biotechnology, 27(1): 107–114

[16] Finazzi E, Di Valentin C, Pacchioni G, Selloni A. (2008). Excess electron states in reduced bulk anatase TiO₂: comparison of standard GGA, GGA+ U, and hybrid DFT calculations. Journal of Chemical Physics, 129(15): 154113

[17] Fuentes K M, Venuti D, Betancourt P. (2020). Black titania with increased defective sites for phenol photodegradation under visible light. Reaction Kinetics, Mechanisms and Catalysis, 131(1): 423–435

[18] Gaya U I, Abdullah A H. (2008). Heterogeneous photocatalytic degradation of organic contaminants over titanium dioxide: a review of fundamentals, progress and problems. Journal of Photochemistry and Photobiology C, Photochemistry Reviews, 9(1): 1–12

[19] Gregg S J, Sing K S, Salzberg H W. (1967). Adsorption surface area and porosity. Journal of the Electrochemical Society, 11: 279Ca

[20] Harris L, Schumacher R. (1980). The influence of preparation on semiconducting rutile (TiO₂). Journal of the Electrochemical Society, 127(5): 1186–1188

[21] HendersonM A (2011). A surface science perspective on TiO₂ photocatalysis. Surface Science Reports, 66(6–7): 185–297

[22] Henderson M A, Epling W S, Peden C H, Perkins C L. (2003). Insights into photoexcited electron scavenging processes on TiO₂ obtained from studies of the reaction of O₂ with OH groups adsorbed at electronic defects on TiO₂ (110). Journal of Physical Chemistry B, 107(2): 534–545

[23] Hu H, Lin Y, Hu Y H. (2019). Synthesis, structures and applications of single component core-shell structured TiO₂: a review. Chemical Engineering Journal, 375: 122029

[24] Hu H, Lin Y, Hu Y H. (2020). Core-shell structured TiO₂ as highly efficient visible light photocatalyst for dye degradation. Catalysis Today, 341: 90–95

[25] Ilie A G, Scarisoareanu M, Morjan I, Dutu E, Badiceanu M, Mihailescu I. (2017). Principal component analysis of Raman spectra for TiO₂ nanoparticle characterization. Applied Surface Science, 417: 93–103

[26] Irfan M, Nawaz R, Khan J A, Ullah H, Haneef T, Legutko S, Rahman S, Józwik J, Alsaiari M A, Khan M K A. . (2021). Synthesis and characterization of manganese-modified black TiO₂ nanoparticles and their performance evaluation for the photodegradation of phenolic compounds from wastewater. Materials, 14: 7422

[27] JayL, ChirwaE (2018). Pathway analysis of phenol degradation by UV/TiO₂ photocatalysis utilising the C-13 isotopic labelling technique. Dissertation for Doctoral Degree. Pretoria. South Africa: University of Pretoria

[28] Kashif N, Ouyang F. (2009). Parameters effect on heterogeneous photocatalysed degradation of phenol in aqueous dispersion of TiO₂. Journal of Environmental Sciences-China, 21(4): 527–533

[29] Katryniok B, Paul S, Dumeignil F. (2013). Recent developments in the field of catalytic dehydration of glycerol to acrolein. ACS Catalysis, 3(8): 1819–1834

[30] KonwarL J, Mikkola J P, BordoloiN, SaikiaR, ChutiaR S, KatakiR (2018). Sidestreams from bioenergy and biorefinery complexes as a resource for circular bioeconomy. In: Bhaskar T, Pandey A, Mohan S V, Lee D J, Khanal S K, Editors. Waste Biorefinery. Amsterdam, Netherlands: Elsevier, 85–125

[31] Lin C, Lin K S. (2007). Photocatalytic oxidation of toxic organohalides with TiO₂/UV: the effects of humic substances and organic mixtures. Chemosphere, 66(10): 1872–1877

[32] Lin L, Ma Y, Wu J, Pang F, Ge J, Sui S, Yao Y, Qi R, Cheng Y, Duan C G, Chu J, Huang R. (2019). Origin of photocatalytic activity in Ti⁴⁺/Ti³⁺ core–shell titanium oxide nanocrystals. Journal of Physical Chemistry C, 123(34): 20949–20959

[33] Liu G, Yan X, Chen Z, Wang X, Wang L, Lu G Q, Cheng H M. (2009). Synthesis of rutile–anatase core–shell structured TiO₂ for photocatalysis. Journal of Materials Chemistry, 19(36): 6590–6596

[34] Lyu J, Shao J, Wang Y, Qiu Y, Li J, Li T, Peng Y, Liu F. (2019). Construction of a porous core-shell homojunction for the photocatalytic degradation of antibiotics. Chemical Engineering Journal, 358: 614–620

[35] MineroC, Vione D (2006). A quantitative evalution of the photocatalytic performance of TiO₂ slurries. Applied Catalysis B: Environmental, 67(3–4): 257–269

[36] Nawaz R, Haider S, Ullah H, Akhtar M S, Khan S, Junaid M, Khan N. (2022). Optimized remediation of treated agro-industrial effluent using visible light-responsive core-shell structured black TiO₂ photocatalyst. Journal of Environmental Chemical Engineering, 10(1): 106968

[37] Nawaz R, Kait C F, Chia H Y, Isa M H, Huei L W. (2019). Glycerol-mediated facile synthesis of colored titania nanoparticles for visible light photodegradation of phenolic compounds. Nanomaterials (Basel, Switzerland), 9(11): 1586

[38] Nawaz R, Kait C F, Chia H Y, Isa M H, Huei L W. (2020a). Structural elucidation of core–shell TiO₂ nanomaterials for environmental pollutants removal: a focused mini review. Environmental Technology & Innovation, 19: 101007

[39] Nawaz R, Kait C F, Chia H Y, Isa M H, Huei L W. (2020b). Photocatalytic remediation of treated palm oil mill effluent contaminated with phenolic compounds using TiO₂ nanomaterial. Desalination and Water Treatment, 183: 355–365

[40] Negi C, Kandwal P, Rawat J, Sharma M, Sharma H, Dalapati G, Dwivedi C. (2021). Carbon-doped titanium dioxide nanoparticles for visible light driven photocatalytic activity. Applied Surface Science, 554: 149553

[41] Ng K H, Cheng C K. (2015). A novel photomineralization of POME over UV-responsive TiO₂ photocatalyst: kinetics of POME degradation and gaseous product formations. RSC Advances, 5(65): 53100–53110

[42] Ng K H, Khan M R, Ng Y H, Hossain S S, Cheng C K. (2017). Restoration of liquid effluent from oil palm agroindustry in Malaysia using UV/TiO₂ and UV/ZnO Photocatalytic systems: a comparative study. Journal of Environmental Management, 196: 674–680

[43] Ng K H, Lee C H, Khan M R, Cheng C K. (2016). Photocatalytic degradation of recalcitrant POME waste by using silver doped titania: Photokinetics and scavenging studies. Chemical Engineering Journal, 286: 282–290

[44] Ng K H, Yuan L S, Cheng C K, Chen K, Fang C. (2019). TiO₂ and ZnO photocatalytic treatment of palm oil mill effluent (POME) and feasibility of renewable energy generation: A short review. Journal of Cleaner Production, 233: 209–225

[45] Nowotny J, Bak T, Nowotny M, Sheppard L. (2006). TiO₂ surface active sites for water splitting. Journal of Physical Chemistry B, 110(37): 18492–18495

[46] Oladipo A A. (2021). Rapid photocatalytic treatment of high-strength olive mill wastewater by sunlight and UV-induced CuCr₂O₄@CaFe–LDO. Journal of Water Process Engineering, 40: 101932

[47] Parent Y, Blake D, Magrini-bair K, Lyons C, Turchi C, Watt A, Wolfrum E, Prairie M. (1996). Solar photocatalytic processes for the purification of water: state of development and barriers to commercialization. Solar Energy, 56(5): 429–437

[48] Porter J F, Li Y G, Chan C K. (1999). The effect of calcination on the microstructural characteristics and photoreactivity of Degussa P-25 TiO₂. Journal of Materials Science, 34(7): 1523–1531

[49] RenT Z, Yuan Z Y, SuB L (2003). Surfactant-assisted preparation of hollow microspheres of mesoporous TiO₂. Chemical Physics Letters, 374(1–2): 170–175

[50] Shi J, Li J, Wang Y, Zhang C Y. (2022). TiO₂-based nanosystem for cancer therapy and antimicrobial treatment: a review. Chemical Engineering Journal, 431: 133714

[51] Shvab R, Hryha E, Nyborg L. (2017). Surface chemistry of the titanium powder studied by XPS using internal standard reference. Powder Metallurgy, 60(1): 42–48

[52] Sinhamahapatra A, Jeon J P, Yu J S. (2015). A new approach to prepare highly active and stable black titania for visible light-assisted hydrogen production. Energy & Environmental Science, 8(12): 3539–3544

[53] Sobczyński A, Duczmal Ł, Zmudziński W. (2004). Phenol destruction by photocatalysis on TiO₂: an attempt to solve the reaction mechanism. Journal of Molecular Catalysis A, Chemical, 213(2): 225–230

[54] Sun L, Li Z, Li Z, Hu Y, Chen C, Yang C, Du B, Sun Y, Besenbacher F, Yu M. (2017). Design and mechanism of core–shell TiO₂ nanoparticles as a high-performance photothermal agent. Nanoscale, 9(42): 16183–16192

[55] Taha M, Ibrahim A. (2014). Characterization of nano zero-valent iron (nZVI) and its application in sono-Fenton process to remove COD in palm oil mill effluent. Journal of Environmental Chemical Engineering, 2(1): 1–8

[56] Tan Y, Goh P, Lai G, Lau W, Ismail A. (2014). Treatment of aerobic treated palm oil mill effluent (AT-POME) by using TiO₂ photocatalytic process. Jurnal Teknologi-Sciences & Engineering, 70: 61–63

[57] Tian J, Hu X, Yang H, Zhou Y, Cui H, Liu H. (2016). High yield production of reduced TiO₂ with enhanced photocatalytic activity. Applied Surface Science, 360: 738–743

[58] Tian J, Leng Y, Cui H, Liu H. (2015). Hydrogenated TiO₂ nanobelts as highly efficient photocatalytic organic dye degradation and hydrogen evolution photocatalyst. Journal of Hazardous Materials, 299: 165–173

[59] Ullattil S G, Periyat P. (2016). A ‘one pot’ gel combustion strategy towards Ti³⁺ self-doped ‘black’ anatase TiO_2−x solar photocatalyst. Journal of Materials Chemistry. A, 4(16): 5854–5858

[60] Wagner W, Averback R, Hahn H, Petry W, Wiedenmann A. (1991). Sintering characteristics of nanocrystalline TiO₂: a study combining small angle neutron scattering and nitrogen absorption–BET. Journal of Materials Research, 6(10): 2193–2198

[61] Wang J, Wang Y, Wang W, Peng T, Liang J, Li P, Pan D, Fan Q, Wu W. (2020). Visible light driven Ti³⁺ self-doped TiO₂ for adsorption-photocatalysis of aqueous U(VI). Environmental Pollution, 262: 114373

[62] Wong K A, Lam S M, Sin J C. (2019). Wet chemically synthesized ZnO structures for photodegradation of pre-treated palm oil mill effluent and antibacterial activity. Ceramics International, 45(2): 1868–1880

[63] Wu M C, Chen C H, Huang W K, Hsiao K C, Lin T H, Chan S H, Wu P Y, Lu C F, Chang Y H, Lin T F, Hsu K H, Hsu J F, Lee K M, Shyue J J, Kordás K, Su W F. (2017). Improved solar-driven photocatalytic performance of highly crystalline hydrogenated TiO₂ nanofibers with core-shell structure. Scientific Reports, 7(1): 40896

[64] Xu J, Liu Z, Wang J, Liu P, Ahmad M, Zhang Q, Zhang B. (2022). Preparation of core-shell C@ TiO₂ composite microspheres with wrinkled morphology and its microwave absorption. Journal of Colloid and Interface Science, 607: 1036–1049

[65] Zhai M, Liu Y, Huang J, Wang Y, Chen K, Fu Y, Li H. (2019). Efficient suspension plasma spray fabrication of black titanium dioxide coatings with visible light absorption performances. Ceramics International, 45(1): 930–935

[66] Zhang L, Djellabi R, Su P, Wang Y, Zhao J. (2023). Through converting the surface complex on TiO₂ nanorods to generate superoxide and singlet oxygen to remove CN⁻. Journal of Environmental Sciences-China, 124: 300–309

[67] Zhou G, Shen L, Xing Z, Kou X, Duan S, Fan L, Meng H, Xu Q, Zhang X, Li L, Zhao M, Mi J, Li Z. (2017). Ti³⁺ self-doped mesoporous black TiO₂/graphene assemblies for unpredicted-high solar-driven photocatalytic hydrogen evolution. Journal of Colloid and Interface Science, 505: 1031–1038

[68] Zulfiqar M, Samsudin M F R, Sufian S. (2019). Modelling and optimization of photocatalytic degradation of phenol via TiO₂ nanoparticles: an insight into response surface methodology and artificial neural network. Journal of Photochemistry and Photobiology A, Chemistry, 384: 112039

RIGHTS & PERMISSIONS

Higher Education Press