Efficient photodegradation of phenol assisted by persulfate under visible light irradiation via a nitrogen-doped titanium-carbon composite

Abstract

To realize the utilization of visible light and improve the photocatalytic efficiency of organic pollutant degradation in wastewater, a nitrogen-doped titanium-carbon composite (N-TiO₂/AC) prepared by sol-gel methods was applied in the photodegradation of phenol assisted by persulfate under visible light irradiation (named N-TiO₂/AC/PS/VIS). The results show that a synergistic effect exists between visible-light photocatalysis and persulfate activation. Compared with TiO₂/PS/VIS, the phenol degradation rate was found to be observably improved by 65% in the N-TiO₂/AC/PS/VIS system. This significant increase in degradation rate was mainly attributed to the following two factors: 1) The N and C doping can change the crystal structure of TiO₂, which extends the TiO₂ absorption wavelength range to the visible light region. 2) As an electron acceptor, PS can not only prevent electrons and holes from recombining with each other but can also generate strong oxidizing radicals such as ∙SO₄^– and ∙OH to accelerate the reaction dynamics. The process of phenol degradation was found to be consistent with the Langmuir pseudo-first-order kinetic model with an apparent rate constant k of 1.73 min^–1. The N-TiO₂/AC/PS/VIS process was proven to be a facile method for pollutant degradation with high pH adaptability, excellent visible-light utilization and good application prospects.

Graphical abstract

Keywords

N-TiO₂/AC / visible light / photocatalysis / persulfate activation / phenol

References

[1] Lu J W, Lan L, Liu X T T, Wang N, Fan X L. Plasmonic Au nanoparticles supported on both sides of TiO₂ hollow spheres for maximising photocatalytic activity under visible light. Frontiers of Chemical Science and Engineering, 2019, 13(4): 665–671

[2] Zhang T H, Liu Y J, Rao Y D, Li X P, Yuan D L, Tang S F, Zhao Q X. Enhanced photocatalytic activity of TiO₂ with acetylene black and persulfate for degradation of tetracycline hydrochloride under visible light. Chemical Engineering Journal, 2020, 384: 123350

[3] Yang L, Xu L, Bai X, Jin P. Enhanced visible-light activation of persulfate by Ti³⁺ self-doped TiO₂/graphene nanocomposite for the rapid and efficient degradation of micropollutants in water. Journal of Hazardous Materials, 2019, 365: 107–117

[4] Grilla E, Matthaiou V, Frontistis Z, Oller I, Polo I, Malato S, Mantzavinos D. Degradation of antibiotic trimethoprim by the combined action of sunlight, TiO₂ and persulfate: a pilot plant study. Catalysis Today, 2019, 328: 216–222

[5] He L, Dong Y N, Zheng Y N, Jia Q M, Shan S Y, Zhang Y Q. A novel magnetic MIL-101(Fe)/TiO₂ composite for photo degradation of tetracycline under solar light. Journal of Hazardous Materials, 2019, 361: 85–94

[6] Hou L Q, Yang W, Xu X W, Deng B J, Chen Z, Wang S, Tian J B, Yang F, Li Y F. In-situ activation endows the integrated Fe₃C/Fe@ nitrogen-doped carbon hybrids with enhanced pseudocapacitance for electrochemical energy storage. Chemical Engineering Journal, 2019, 375: 10

[7] Kakavandi B, Bahari N, Kalantary R R, Fard E D. Enhanced sono-photocatalysis of tetracycline antibiotic using TiO₂ decorated on magnetic activated carbon (MAC@T) coupled with US and UV: a new hybrid system. Ultrasonics Sonochemistry, 2019, 55: 75–85

[8] Liu D D, Wu Z S, Tian F, Ye B C, Tong Y B. Synthesis of N and La co-doped TiO₂/AC photocatalyst by microwave irradiation for the photocatalytic degradation of naphthalene. Journal of Alloys and Compounds, 2016, 676: 489–498

[9] Yang X L, Qian F F, Wang Y, Li M L, Lu J R, Li Y M, Bao M T. Constructing a novel ternary composite (C₁₆H₃₃(CH₃)₃N)₄W₁₀O₃₂/g-C₃N₄/rGO with enhanced visible-light-driven photocatalytic activity for degradation of dyes and phenol. Applied Catalysis B: Environmental, 2017, 200: 283–296

[10] Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y. Visible-light photocatalysis in nitrogen-doped titanium oxides. Science, 2001, 293(5528): 269–271

[11] Hoang S, Berglund S P, Hahn N T, Bard A J, Mullins C B. Enhancing visible light photo-oxidation of water with TiO₂ nanowire arrays via cotreatment with H₂ and NH₃: synergistic effects between Ti³⁺ and N. Journal of the American Chemical Society, 2012, 134(8): 3659–3662

[12] Martins A C, Cazetta A L, Pezoti O, Souza J R B, Zhang T, Pilau E J, Asefa T, Almeida V C. Sol-gel synthesis of new TiO₂/activated carbon photocatalyst and its application for degradation of tetracycline. Ceramics International, 2017, 43(5): 4411–4418

[13] Rimoldi L, Pargoletti E, Meroni D, Falletta E, Cerrato G, Turco F, Cappelletti G. Concurrent role of metal (Sn, Zn) and N species in enhancing the photocatalytic activity of TiO₂ under solar light. Catalysis Today, 2018, 313: 40–46

[14] Park J H, Kim S, Bard A J. Novel carbon-doped TiO₂ nanotube arrays with high aspect ratios for efficient solar water splitting. Nano Letters, 2006, 6(1): 24–28

[15] Wang H, Lewis J P. Effects of dopant states on photoactivity in carbon-doped TiO₂. Journal of Physics Condensed Matter, 2005, 17(21): 209–213

[16] Wang C, Jia S Y, Zhang Y C, Nian Y, Wang Y, Han Y, Liu Y, Ren H T, Wu S H, Yao K X, Han X. Catalytic reactivity of Co₃O₄ with different facets in the hydrogen abstraction of phenol by persulfate. Applied Catalysis B: Environmental, 2020, 270: 12

[17] Sanches S, Crespo M T B, Pereira V J. Drinking water treatment of priority pesticides using low pressure UV photolysis and advanced oxidation processes. Water Research, 2010, 44(6): 1809–1818

[18] Chiou C H, Wu C Y, Juang R S. Influence of operating parameters on photocatalytic degradation of phenol in UV/TiO₂ process. Chemical Engineering Journal, 2008, 139(2): 322–329

[19] Dominguez J R, Beltran J, Rodriguez O. Vis and UV photocatalytic detoxification methods (using TiO₂, TiO₂/H₂O₂, TiO₂/O₃, TiO₂/S₂O₈^2–, O₃, H₂O₂, S₂O₈^2–, Fe³⁺/H₂O₂ and Fe³⁺/H₂O₂/C₂O₄^2–) for dyes treatment. Catalysis Today, 2005, 101(3-4): 389–395

[20] Garcia J C, Oliveira U, Silva A E C, Oliveira C C, Nozaki J, de Souza N E. Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO₂/H₂O₂ and UV/Fe²⁺/H₂O₂ systems. Journal of Hazardous Materials, 2007, 147(1-2): 105–110

[21] Harir M, Gaspar A, Kanawati B, Fekete A, Frommberger M, Martens D, Kettrup A, El Azzouzi M, Schmitt-Kopplin P. Photocatalytic reactions of imazamox at TiO₂, H₂O₂ and TiO₂/H₂O₂ in water interfaces: kinetic and photoproducts study. Applied Catalysis B: Environmental, 2008, 84(3-4): 524–532

[22] Hazime R, Nguyen Q H, Ferronato C, Salvador A, Jaber F, Chovelon J M. Comparative study of imazalil degradation in three systems: UV/TiO₂, UV/K₂S₂O₈ and UV/TiO₂/K₂S₂O₈. Applied Catalysis B: Environmental, 2014, 144: 286–291

[23] Momenia M M, Hosseini M G. Photo-electrocatalytic activity of TiO₂ nanotubes prepared with two-step anodization and treated under UV light irradiation. Nanochemistry Research, 2016, 1(1): 9–18

[24] Liu G S, You S J, Tan Y, Ren N Q. In situ photochemical activation of sulfate for enhanced degradation of organic pollutants in water. Environmental Science & Technology, 2017, 51(4): 2339–2346

[25] Ahmed B, Anjum D H, Hedhili M N, Gogotsi Y, Alshareef H N. H₂O₂ assisted room temperature oxidation of Ti₂C MXene for Li-ion battery anodes. Nanoscale, 2016, 8(14): 7580–7587

[26] Lewin E, Persson P O A, Lattemann M, Stuber M, Gorgoi M, Sandell A, Ziebert C, Schadfers F, Braun W, Halbritter J, On the origin of a third spectral component of C1s XPS-spectra for nc-TiC/a-C nanocomposite thin films. Surface and Coatings Technology, 2008, 202(15): 3563–3570

[27] Kodtharin N, Vongwatthaporn R, Nutariya J, Sricheewin C, Timah E N, Sivaleitporn K, Thumthana O, Tipparach U. Structures and properties of N-doped TiO₂ nanotubes arrays synthesized by the anodization method for hydrogen production. Materials Today: Proceedings, 2018, 5(6): 14091–14098

[28] Soto G. AES, EELS and XPS characterization of Ti(C, N, O) films prepared by PLD using a Ti target in N₂, CH₄, O₂ and CO as reactive gases. Applied Surface Science, 2004, 233(1/4): 115–122

[29] Huang H S, Song Y, Li N J, Chen D Y, Xu Q F, Li H, He J H, Lu J M. One-step in-situ preparation of N-doped TiO₂@C derived from Ti₃C₂ MXene for enhanced visible-light driven photodegradation. Applied Catalysis B: Environmental, 2019, 251: 154–161

[30] Li H, Hao Y, Lu H, Liang L, Wang Y, Qiu J, Shi X, Wang Y, Yao J. A systematic study on visible-light N-doped TiO₂ photocatalyst obtained from ethylenediamine by sol-gel method. Applied Surface Science, 2015, 344: 112–118

[31] Liu X F, Xing Z P, Zhang Y, Li Z Z, Wu X Y, Tan S Y, Yu X J, Zhu Q, Zhou W. Fabrication of 3D flower-like black N-TiO_2−x@MoS₂ for unprecedented-high visible-light-driven photocatalytic performance. Applied Catalysis B: Environmental, 2017, 201: 119–127

[32] Chen X Y, Wang W P, Xiao H, Hong C L, Zhu F X, Yao Y L, Xue Z Y. Accelerated TiO₂ photocatalytic degradation of acid orange 7 under visible light mediated by peroxymonosulfate. Chemical Engineering Journal, 2012, 193: 290–295

[33] Guo Y, Zeng Z, Liu Y, Huang Z, Cui Y, Yang J. One-pot synthesis of sulfur doped activated carbon as a superior metal-free catalyst for the adsorption and catalytic oxidation of aqueous organics. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(9): 4055–4067

[34] Guo Y, Zeng Z, Zhu Y, Huang Z, Cui Y, Yang J. Catalytic oxidation of aqueous organic contaminants by persulfate activated with sulfur-doped hierarchically porous carbon derived from thiophene. Applied Catalysis B: Environmental, 2018, 220: 635–644

[35] Gao Y W, Li S M, Li Y X, Yao L Y, Zhang H. Accelerated photocatalytic degradation of organic pollutant over metal-organic framework MIL-53(Fe) under visible LED light mediated by persulfate. Applied Catalysis B: Environmental, 2017, 202: 165–174

[36] Duan X G, Sun H Q, Wang Y X, Kang J, Wang S B. N-Doping-induced nonradical reaction on single-walled carbon nanotubes for catalytic phenol oxidation. ACS Catalysis, 2015, 5(2): 553–559

[37] Li X, Liao F, Ye L, Yeh L. Controlled pyrolysis of MIL-88A to prepare iron/carbon composites for synergistic persulfate oxidation of phenol: catalytic performance and mechanism. Journal of Hazardous Materials, 2020, 398: 122938

RIGHTS & PERMISSIONS

Higher Education Press