Synthesis of defect-rich hierarchical sponge-like TiO₂ nanoparticles and their improved photocatalytic and photoelectrochemical performance

Abstract

Defect-rich hierarchical sponge-like TiO₂ nanoparticles were successfully synthesized via the combined one-step hydrothermal method and chemical reduction approach. SEM and TEM images showed their porous structure densely packed with even smaller TiO₂ particles, while photocatalytic results manifested their superior photocatalytic performance and high stability. The RhB solution (10 ppm) could be absolutely degraded in 60 min, and the degradation rate was twice that of the sample without the treatment by NaBH₄. Besides, the TC solution (10 ppm) could be removed by 74.3% in 20 min. PEC measurements also displayed that the photoelectrode based on such defect-rich TiO₂ nanoparticles had small resistance and improved charge transfer rate. The improved performance can be assigned to rich defects and phase junctions, which was supported by characterization results. The presence of rich defects and phase junctions could not only promote the separation of photogenerated charge carriers, but also accelerate the electron transfer, beneficial for both the photocatalytic and the PEC performance. It is expected that the obtained hierarchical sponge-like TiO₂ nanoparticles with rich defects have great potential for photocatalytic applications.

Keywords

TiO₂ / hydrothermal method / nanoparticles / photocatalytic performance / photoelectrochemical performance / defects

References

[1] Chu J, Sun Y, Han X, . Mixed titanium oxide strategy for enhanced photocatalytic hydrogen evolution. ACS Applied Materials & Interfaces, 2019, 11(20): 18475–18482

[2] Reheman A, Kadeer K, Okitsu K, . Facile photo-ultrasonic assisted reduction for preparation of rGO/Ag₂CO₃ nanocomposites with enhanced photocatalytic oxidation activity for tetracycline. Ultrasonics Sonochemistry, 2019, 51: 166–177

[3] Tsai C E, Yeh S M, Chen C H, . Flexible photocatalytic paper with Cu₂O and Ag nanoparticle-decorated ZnO nanorods for visible light photodegradation of organic dye. Nanoscale Research Letters, 2019, 14(1): 204

[4] Cendula P, Mayer M T, Luo J, . Correction: Elucidation of photovoltage origin and charge transport in Cu₂O heterojunctions for solar energy conversion. Sustainable Energy & Fuels, 2019, 3(10): 2633–2641

[5] Zhang W, Xiao X, Zheng L, . Fabrication of TiO₂/MoS₂ composite photocatalyst and its photocatalytic mechanism for degradation of methyl orange under visible light. Canadian Journal of Chemical Engineering, 2015, 93(9): 1594–1602

[6] Li Y, Wang X, Gao L. Construction of binary BiVO₄/g-C₃N₄ photocatalyst and their photocatalytic performance for reactive blue 19 reduction from aqueous solution coupling with H₂O₂. Journal of Materials Science: Materials in Electronics, 2019, 30(17): 16015–16029

[7] Liu S, Chen J, Liu D, . Improved visible light photocatalytic performance through an in situ composition-transforming synthesis of BiVO₄/BiOBr photocatalyst. Journal of Nanoparticle Research, 2019, 21(8): 191–200

[8] Zhang C, Zhou Y, Bao J, . Hierarchical honeycomb Br-, N-codoped TiO₂ with enhanced visible-light photocatalytic H₂ production. ACS Applied Materials & Interfaces, 2018, 10(22): 18796–18804

[9] Cai J, Huang J, Ge M, . Immobilization of Pt nanoparticles via rapid and reusable electropolymerization of dopamine on TiO₂ nanotube arrays for reversible SERS substrates and nonenzymatic glucose sensors. Small, 2017, 13(19): 1604240–1604251

[10] Cai J, Huang J, Lai Y. 3D Au-decorated BiMoO₆ nanosheet/TiO₂ nanotube array heterostructure with enhanced UV and visible-light photocatalytic activity. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2017, 5(31): 16412–16421

[11] Shang M, Wang W, Zhang L, . 3D Bi₂WO₆/TiO₂ hierarchical heterostructure: controllable synthesis and enhanced visible photocatalytic degradation performances. The Journal of Physical Chemistry C, 2009, 113(33): 14727–14731

[12] Sauvage F, Di Fonzo F, Li Bassi A, . Hierarchical TiO₂ photoanode for dye-sensitized solar cells. Nano Letters, 2010, 10(7): 2562–2567

[13] Xiang X B, Yu Y, Wen W, . Construction of hierarchical Ag@TiO₂@ZnO nanowires with high photocatalytic activity. New Journal of Chemistry, 2018, 42(1): 265–271

[14] Duan Y, Zhou S, Chen Z, . Hierarchical TiO₂ nanowire/microflower photoanode modified with Au nanoparticles for efficient photoelectrochemical water splitting. Catalysis Science & Technology, 2018, 8(5): 1395–1403

[15] Chen S, Liang H, Shen M, . Yolk-like Fe₃O₄@C–Au@void@TiO₂–Pd hierarchical microspheres with visible light-assisted enhanced photocatalytic degradation of dye. Applied Physics A: Materials Science & Processing, 2018, 124(4): 305–320

[16] Zhou Y, Zhang Y, Xiang Y, . Solvothermal synthesis of hexagonal multi-walled tubular hierarchical structure TiO₂ with co-exposed {0 1 0} and {1 0 1} plane for high photocatalytic activity. Journal of Materials Science: Materials in Electronics, 2019, 30(9): 8259–8267

[17] Yan X, Xing Z, Cao Y, . In-situ C–N–S-tridoped single crystal black TiO₂ nanosheets with exposed {0 0 1} facets as efficient visible-light-driven photocatalysts. Applied Catalysis B: Environmental, 2017, 219: 572–579

[18] Zhang W, He H, Tian Y, . Synthesis of uniform ordered mesoporous TiO₂ microspheres with controllable phase junctions for efficient solar water splitting. Chemical Science, 2019, 10(6): 1664–1670

[19] Liu X, Zhu G, Wang X, . Progress in black titania: a new material for advanced photocatalysis. Advanced Energy Materials, 2016, 6(17): 1600452–1600480

[20] Xin X, Xu T, Yin J, . Management on the location and concentration of Ti³⁺ in anatase TiO₂ for defects-induced visible-light photocatalysis. Applied Catalysis B: Environmental, 2015, 176: 354–362

[21] Tan H, Zhao Z, Niu M, . A facile and versatile method for preparation of colored TiO₂ with enhanced solar-driven photocatalytic activity. Nanoscale, 2014, 6(17): 10216–10223

[22] Tian J, Hu X, Yang H, . High yield production of reduced TiO₂ with enhanced photocatalytic activity. Applied Surface Science, 2016, 360: 738–743

[23] Ariyanti D, Mills L, Dong J, . NaBH₄ modified TiO₂: Defect site enhancement related to its photocatalytic activity. Materials Chemistry and Physics, 2017, 199: 571–576

[24] Zhang W, He H, Tian Y, . Defect-engineering of mesoporous TiO₂ microspheres with phase junctions for efficient visible-light driven fuel production. Nano Energy, 2019, 66: 104113–104140

[25] Liu L, Jiang Y, Zhao H, . Engineering coexposed {0 0 1} and {1 0 1} facets in oxygen-deficient TiO₂ nanocrystals for enhanced CO₂ photoreduction under visible light. ACS Catalysis, 2016, 6(2): 1097–1108

[26] Yang Y, Jin Q, Mao D, . Dually ordered porous TiO₂–rGO composites with controllable light absorption properties for efficient solar energy conversion. Advanced Materials, 2017, 29(4): 1604795–1604801

[27] Takle S P, Apine O A, Ambekar J D, . Solar-light-active mesoporous Cr–TiO₂ for photodegradation of spent wash: an in-depth study using QTOF LC-MS. RSC Advances, 2019, 9(8): 4226–4238

[28] Dutta S, Patra A K, De S, . Self-assembled TiO₂ nanospheres by using a biopolymer as a template and its optoelectronic application. ACS Applied Materials & Interfaces, 2012, 4(3): 1560–1564

[29] Thaik N, Kooptarnond K, Meesane J, . Effect of anodizing time on morphology and wettability of TiO₂ nanotubes prepared by carbon cathode. Materials Science Forum, 2019, 962: 145–150

[30] Xiong J, He L. Influence of Na⁺ content on the structure and morphology of TiO₂ nanoparticles prepared by hydrothermal transformation of alkaline titanate nanotubes. Journal of Experimental Nanoscience, 2017, 12(1): 384–393

[31] Johari N D, Mohd Rosli Z, Juoi J M, . Influence of sol–gel pH and soaking time on the morphology, phases and grain size of TiO₂ coating. Solid State Phenomena, 2017, 268: 219–223

[32] Hu Z, Quan H, Chen Z, . New insight into an efficient visible light-driven photocatalytic organic transformation over CdS/TiO₂ photocatalysts. Photochemical & Photobiological Sciences, 2018, 17(1): 51–59

[33] Gaur L K, Kumar P, Kushavah D, . Laser induced phase transformation influenced by Co doping in TiO₂ nanoparticles. Journal of Alloys and Compounds, 2019, 780: 25–34

[34] Wang W, Liu Y, Qu J, . Nitrogen-doped TiO₂ microspheres with hierarchical micro/nanostructures and rich dual-phase junctions for enhanced photocatalytic activity. RSC Advances, 2016, 6(47): 40923–40931

[35] Fang W, Xing M, Zhang J. A new approach to prepare Ti³⁺ self-doped TiO₂ via NaBH₄ reduction and hydrochloric acid treatment. Applied Catalysis B: Environmental, 2014, 160: 240–246

[36] Pan X, Yang M Q, Fu X, . Defective TiO₂ with oxygen vacancies: synthesis, properties and photocatalytic applications. Nanoscale, 2013, 5(9): 3601–3614

[37] Wu Y, Fu Y, Zhang L, . Study of oxygen vacancies on different facets of anatase TiO₂. Chinese Journal of Chemistry, 2019, 37(9): 922–928

[38] Melnyk V, Shymanovska V, Puchkovska G, . Low-temperature luminescence of different TiO₂ modifications. Journal of Molecular Structure, 2005, 744: 573–576

[39] Zhou J, Zhang Y, Zhao X S, . Photodegradation of benzoic acid over metal-doped TiO₂. Industrial & Engineering Chemistry Research, 2006, 45(10): 3503–3511

[40] Kernazhitsky L, Shymanovska V, Gavrilko T, . Room temperature photoluminescence of anatase and rutile TiO₂ powders. Journal of Luminescence, 2014, 146: 199–204

[41] Zhao X, Jiang C, Wang Y. Photocatalytic degradation of tetracycline hydrochloride using mesoporous TiO₂ modified by PVA-I. Chemical Engineering Journal, 2014, 8(10): 4060–4066

[42] Bouafıa-Chergui S, Zemmouri H, Chabani M, . TiO₂-photocatalyzed degradation of tetracycline: kinetic study, adsorption isotherms, mineralization and toxicity reduction. Desalination and Water Treatment, 2016, 57(35): 16670–16677

[43] Li D, Jia J, Zhang Y, . Preparation and characterization of nano-graphite/TiO₂ composite photoelectrode for photoelectrocatalytic degradation of hazardous pollutant. Journal of Hazardous Materials, 2016, 315: 1–10

[44] Ruiz-Camacho B, Vera J C B, Medina-Ramírez A, . EIS analysis of oxygen reduction reaction of Pt supported on different substrates. International Journal of Hydrogen Energy, 2017, 42(51): 30364–30373

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant No. 21405105), the Shanghai Natural Science Foundation (14ZR1429300), and the State Key Laboratory of Green Catalysis of Sichuan Institutes of Higher Education (LZJ1703).

RIGHTS & PERMISSIONS

2020 Higher Education Press