Large-sized nano-TiO₂/SiO₂ mesoporous nanofilm-constructed macroporous photocatalysts with excellent photocatalytic performance

Abstract

Novel large-sized mesoporous nanofilm-constructed macroporous SiO₂ (LMNCMS) with two sets of well-defined 3D continuous pass-through macropores (pore size of 0.5–1.0 μm, wall thickness of 40–50 nm) was prepared through a dual-templating approach, and used as an advanced support for TiO₂ nanocrystalline photocatalyst. The structural and optical properties of the as-prepared materials were investigated by various characterization techniques in order to explore the connections between catalysts’ features and catalytic performance. The photocatalytic activities were evaluated by degradations of methylene blue (MB) and phenol under the simulated sunlight irradiation. To gain insight into the impact of preparation and operation conditions on photocatalytic degradation processes, experiments were conducted at wide ranges of the TiO₂ loading content, calcination temperature, solution pH, and photocatalyst dosage. Nano-TiO₂/LMNCMS exhibited high photocatalytic activity and stability. Rapid matter transport, good accessibility of pollutants to TiO₂ and high light harvesting could mainly account for the superior photocatalytic performance. The trapping experiments were performed to identify the main reactive species in the catalytic reactions.

Keywords

mesoporous nanofilm / hierarchical porous silica / templating fabrication / nano-TiO ₂ / degradation of organic pollutant

References

[1] Wang W, Tadé M O, Shao Z. Nitrogen-doped simple and complex oxides for photocatalysis: A review. Progress in Materials Science, 2018, 92: 33–63

[2] Dong H, Zeng G, Tang L, . An overview on limitations of TiO₂-based particles for photocatalytic degradation of organic pollutants and the corresponding countermeasures. Water Research, 2015, 79: 128–146

[3] Rabé K, Liu L, Nahyoon N A, . Fabrication of high efficiency visible light Z-scheme heterostructure photocatalyst g-C₃N₄/Fe⁰(1%)/TiO₂ and degradation of rhodamine B and antibiotics. Journal of the Taiwan Institute of Chemical Engineers, 2019, 96: 463–472

[4] Xu Q, Yu J, Zhang J, . Cubic anatase TiO₂ nanocrystals with enhanced photocatalytic CO₂ reduction activity. Chemical Communications, 2015, 51(37): 7950–7953

[5] Fu J, Cao S, Yu J, . Enhanced photocatalytic CO₂-reduction activity of electrospun mesoporous TiO₂ nanofibers by solvothermal treatment. Dalton Transactions, 2014, 43(24): 9158–9165

[6] Yu J, Low J, Xiao W, . Enhanced photocatalytic CO₂-reduction activity of anatase TiO₂ by coexposed {0 0 1} and {1 0 1} facets. Journal of the American Chemical Society, 2014, 136(25): 8839–8842

[7] Wang Q, Qiu L, Tan X, . Amorphous TiO₂ granular nanodisks on porous Ti foam for highly effective solar cells and photocatalysts. Journal of the Taiwan Institute of Chemical Engineers, 2019, 102: 85–91

[8] Soylu A M, Polat M, Erdogan D A, . TiO₂–Al₂O₃ binary mixed oxide surfaces for photocatalytic NO_x abatement. Applied Surface Science, 2014, 318: 142–149

[9] Todorova N, Giannakopoulou T, Karapati S, . Composite TiO₂/clays materials for photocatalytic NO_x oxidation. Applied Surface Science, 2014, 319: 113–120

[10] Wang H, Zhang X, Su Y, . Photoelectrocatalytic oxidation of aqueous ammonia using TiO₂ nanotube arrays. Applied Surface Science, 2014, 311: 851–857

[11] Sendra M, Moreno-Garrido I, Yeste M P, . Toxicity of TiO₂, in nanoparticle or bulk form to freshwater and marine microalgae under visible light and UV-A radiation. Environmental Pollution, 2017, 227: 39–48

[12] Farrusseng D, Tuel A. Perspectives on zeolite-encapsulated metal nanoparticles and their applications in catalysis. New Journal of Chemistry, 2016, 40(5): 3933–3949

[13] Nalid N R, Majid A, Tahir M B, . Carbonaceous-TiO₂ nanomaterials for photocatalytic degradation of pollutants: A review. Ceramics International, 2017, 43(17): 14552–14571

[14] Silvestri S, Hennemann B, Zanatta N, . Photocatalytic efficiency of TiO₂ supported on raw red clay disks to discolour Reactive Red 141. Water, Air, & Soil Pollution, 2018, 229(2): 40 

[15] Tang R, Zhou S, Yuan Z, . Metal-organic framework derived Co₃O₄/TiO₂/Si heterostructured nanorod array photoanodes for efficient photoelectrochemical water oxidation. Advanced Functional Materials, 2017, 27(37): 1701102

[16] Ding Z, Hu X J, Yue P L, . Synthesis of anatase TiO₂ supported on porous solids by chemical vapor deposition. Catalysis Today, 2001, 68(1–3): 173–182

[17] Qian X, Fuku K, Kuwahara Y, . Design and functionalization of photocatalytic systems within mesoporous silica. ChemSusChem, 2014, 7(6): 1528–1536

[18] Yaparatne S, Tripp C P, Amirbahman A. Photodegradation of taste and odor compounds in water in the presence of immobilized TiO₂–SiO₂ photocatalysts. Journal of Hazardous Materials, 2018, 346: 208–217

[19] Kamegawa T, Ishiguro Y, Seto H, . Enhanced photocatalytic properties of TiO₂-loaded porous silica with hierarchical macroporous and mesoporous architectures in water purification. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2015, 3(5): 2323–2330

[20] Kamegawa T, Ishiguro Y, Yamashita H. Photocatalytic properties of TiO₂-loaded porous silica with hierarchical macroporous and mesoporous architectures in the degradation of gaseous organic molecules. Catalysis Today, 2019, 332(SI): 222–226

[21] Liu Y, Feng Y, Yao J. Recent advances in the direct fabrication of millimeter-sized hierarchical porous materials. RSC Advances, 2016, 6(84): 80840–80846

[22] Galarneau A, Sachse A, Said B, . Hierarchical porous silica monoliths: A novel class of microreactors for process intensification in catalysis and adsorption. Comptes Rendus Chimie, 2016, 19(1–2): 231–247

[23] El Kadib A, Chimenton R, Sachse A, . Functionalized inorganic monolithic microreactors for high productivity in fine chemicals catalytic synthesis. Angewandte Chemie International Edition, 2009, 48(27): 4969–4972

[24] Cheng W, Tao K, Wu Y, . Preparation of hierarchical porous S-1/silica monoliths by steaming crystallization. ChemistrySelect, 2019, 4(13): 3741–3744

[25] Anderson C, Bard A J. Improved photocatalytic activity and characterization of mixed TiO₂/SiO₂ and TiO₂/Al₂O₃ materials. The Journal of Physical Chemistry B, 1997, 101(14): 2611–2616

[26] Dong G, Ho W, Li Y, . Facile synthesis of porous graphene-like carbon nitride (C₆N₉H₃) with excellent photocatalytic activity for NO removal. Applied Catalysis B: Environmental, 2015, 174: 477–485

[27] Dong F, Zhao Z, Xiong T, . In situ construction of g-C₃N₄/g-C₃N₄ metal-free heterojunction for enhanced visible-light photocatalysis. ACS Applied Materials & Interfaces, 2013, 5(21): 11392–11401

[28] Yu J, Wang S, Low J, . Enhanced photocatalytic performance of direct Z-scheme g-C₃N₄–TiO₂ photocatalysts for the decomposition of formaldehyde in air. Physical Chemistry Chemical Physics, 2013, 15(39): 16883–16890

[29] Shen D, Chen L, Yang J, . Ultradispersed palladium nanoparticles in three-dimensional dendritic mesoporous silica nanospheres: Toward active and stable heterogeneous catalysts. ACS Applied Materials & Interfaces, 2015, 7(31): 17450–17459

[30] Chen Y, Huang W, He D, . Construction of heterostructured g-C₃N₄/Ag/TiO₂ microspheres with enhanced photocatalysis performance under visible-light irradiation. ACS Applied Materials & Interfaces, 2014, 6(16): 14405–14414

[31] Yu J, Ran J. Facile preparation and enhanced photocatalytic H₂-production activity of Cu(OH)₂ cluster modified TiO₂. Energy & Environmental Science, 2011, 4(4): 1364–1371

[32] Khan M M, Ansari S A, Pradhan D, . Band gap engineered TiO₂ nanoparticles for visible light induced photoelectrochemical and photocatalytic studies. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(3): 637–644 

[33] Mao X, Lang X, Wang Z, . Band-gap states of TiO₂(1 1 0): Major contribution from surface defects. Journal of Physical Chemistry Letters, 2013, 4(22): 3839–3844

[34] Choudhury B, Choudhury A. Oxygen defect dependent variation of band gap, Urbach energy and luminescence property of anatase, anatase–rutile mixed phase and of rutile phases of TiO₂ nanoparticles. Physica E: Low-Dimensional Systems & Nano-structures, 2014, 56: 364–371

[35] Lin H, Huang C P, Li W, . Size dependency of nanocrystalline TiO₂ on its optical property and photocatalytic reactivity exemplified by 2-chlorophenol. Applied Catalysis B: Environmental, 2006, 68(1–2): 1–11

[36] Wang X, Sø L, Su R, . The influence of crystallite size and crystallinity of anatase nanoparticles on the photo-degradation of phenol. Journal of Catalysis, 2014, 310(SI): 100–108

[37] Zhang Y, Chen Z, Liu S, . Size effect induced activity enhancement and anti-photocorrosion of reduced graphene oxide/ZnO composites for degradation of organic dyes and reduction of Cr(VI) in water. Applied Catalysis B: Environmental, 2013, 140: 598–607

[38] Hao R, Wang G, Tang H, . Template-free preparation of macro/mesoporous g-C₃N₄/TiO₂ heterojunction photocatalysts with enhanced visible light photocatalytic activity. Applied Catalysis B: Environmental, 2016, 187: 47–58

[39] Wu F, Liu W, Qiu J, . Enhanced photocatalytic degradation and adsorption of methylene blue via TiO₂ nanocrystals supported on graphene-like bamboo charcoal. Applied Surface Science, 2015, 358: 425–435

[40] Sampaio M J, Silva C G, Silva A M T, . Carbon-based TiO₂ materials for the degradation of Microcystin-LA. Applied Catalysis B: Environmental, 2015, 170: 74–82

[41] Ye Y, Feng Y, Bruning H, . Photocatalytic degradation of metoprolol by TiO₂ nanotube arrays and UV-LED: Effects of catalyst properties, operational parameters, commonly present water constituents, and photo-induced reactive species. Applied Catalysis B: Environmental, 2018, 220: 171–181

[42] Minero C, Lucchiari M, Vione D, . Fe(III)-enhanced sonochemical degradation of methylene blue in aqueous solution. Environmental Science & Technology, 2005, 39(22): 8936–8942

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