Please wait a minute...
Shopping Cart Email List Chinese
Advanced Search Fig/Tab
Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

Postal Subscription Code 80-974

2018 Impact Factor: 1.701

Featured Articles  |  Most Downloaded  |  Most Reading
Online Submission Subscribe to Our RSS Content Feed
Front. Mater. Sci.    2020, Vol. 14 Issue (2) : 163-176    https://doi.org/10.1007/s11706-020-0506-8
RESEARCH ARTICLE
Large-sized nano-TiO2/SiO2 mesoporous nanofilm-constructed macroporous photocatalysts with excellent photocatalytic performance
Zhiyu ZHANG, Lixia HU, Hui ZHANG, Liping YU, Yunxiao LIANG()
State Key Laboratory Base of Novel Functional Materials and Preparation Science, School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China
 Download: PDF(3123 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
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-TiO2      degradation of organic pollutant     
Corresponding Author(s): Yunxiao LIANG   
Online First Date: 15 May 2020    Issue Date: 27 May 2020
 Cite this article:   
Zhiyu ZHANG,Lixia HU,Hui ZHANG, et al. Large-sized nano-TiO2/SiO2 mesoporous nanofilm-constructed macroporous photocatalysts with excellent photocatalytic performance[J]. Front. Mater. Sci., 2020, 14(2): 163-176.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-020-0506-8
https://academic.hep.com.cn/foms/EN/Y2020/V14/I2/163
Fig.1  Scheme 1 The formation of TiO2/LMNCMS photocatalysts.
Fig.2  (a)(b) SEM images of LMNCMS. (c) An optical image of TiO2/LMNCMS (the inset showing the thickness). (d)(e)(f) SEM images of TS5.1-600. (g)(h) TEM images of TS5.1-600. (i) An HRTEM image revealing anatase TiO2.
Fig.3  (a) FTIR spectra of LMNCMS and TS5.1-600. (b) XRD patterns of TS5.1-t samples. (c) Nitrogen adsorption–desorption isotherms. (d) BJH pore-size distribution curves. (e) UV-vis DRS results of TSw-600 photocatalysts. (f) UV-vis transmittance spectra of water-filled LMNCMS and TS5.1-600.
Fig.4  Effects of (a) the TiO2 content, (b) the calcination temperature, (c) the initial pH value, and (d) the catalyst dosage on the MB photodegradation. (e) Circulating runs in the decomposition of MB. (f) Photocatalytic activities in presence of different scavengers, H2O2 and oxygen.
Photocatalyst k(MB)/h−1 a) Refs.
TiO2/MacroMeso-SiO2 0.40 [19]
Commercial P25 1.02 [39]
TiO2 supported on graphene-like bamboo charcoal 3.05 [39]
TiO2/LMNCMS 3.19 this work
Tab.1  Comparison of the MB degradation performance for TiO2/LMNCMS with some reported TiO2-based photocatalysts
Fig.5  Effects of (a) the initial pH value and (b) the catalyst dosage on the phenol photodegradation. (c) Total removal rates of TOC corresponding to different catalyst dosages. (d) The effect of oxygen on the phenol photodegradation (inset showing the apparent rate constant).
Sample SBET/(m2·g−1) MAPS/nm a) MPV/(cm3·g−1) b) TiO2 content/wt.% c)
S0 487.5 5.92 0.22 0.0
TS3.3-600 474.3 5.81 0.24 3.3
TS5.1-600 470.4 5.83 0.20 5.1
TS7.0-600 464.8 5.86 0.18 7.0
TS11.2-600 438.2 4.88 0.27 11.2
TS15.4-600 393.6 4.71 0.22 15.4
  Table S1 Effects of the TiO2 content on physical properties of as-prepared samples
Calcination temperature/°C Anatase crystallite size/nm
400 –
500 11.9
600 23.9
700 32.7
800 36.3
  Table S2 Anatase crystallite sizes of TS5.1-t samples under different calcination temperatures
  Fig. S1 The semilog transformation to test the first-order kinetic reaction rate towards different TiO2 contents.
  Fig. S2 The semilog transformation to test the first-order kinetic reaction rate towards different calcination temperatures.
  Fig. S3 The semilog transformation to test the first-order kinetic reaction rate towards different initial pH values.
  Fig. S4 The semilog transformation to test the first-order kinetic reaction rate towards different catalyst dosages.
  Fig. S5 FTIR spectra of the TS photocatalyst before and after 5 runs.
  Fig. S6 Typical absorption spectra of the MB aqueous solution treated for different time (inset showing the change in color with time).
  Fig. S7 Total removal rates of phenol under different pH values.
  Fig. S8 The semilog transformation to test the first-order kinetic reaction rate towards different initial pH values.
  Fig. S9 The semilog transformation to test the first-order kinetic reaction rate towards different catalyst dosages.
1 W Wang, M O Tadé, Z Shao. Nitrogen-doped simple and complex oxides for photocatalysis: A review. Progress in Materials Science, 2018, 92: 33–63
https://doi.org/10.1016/j.pmatsci.2017.09.002
2 H Dong, G Zeng, L Tang, et al.. An overview on limitations of TiO2-based particles for photocatalytic degradation of organic pollutants and the corresponding countermeasures. Water Research, 2015, 79: 128–146
https://doi.org/10.1016/j.watres.2015.04.038 pmid: 25980914
3 K Rabé, L Liu, N A Nahyoon, et al.. 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
https://doi.org/10.1016/j.jtice.2018.12.016
4 Q Xu, J Yu, J Zhang, et al.. Cubic anatase TiO2 nanocrystals with enhanced photocatalytic CO2 reduction activity. Chemical Communications, 2015, 51(37): 7950–7953
https://doi.org/:10.1039/c5cc01087j pmid: 25864947
5 J Fu, S Cao, J Yu, et al.. Enhanced photocatalytic CO2-reduction activity of electrospun mesoporous TiO2 nanofibers by solvothermal treatment. Dalton Transactions, 2014, 43(24): 9158–9165
https://doi.org/10.1039/c4dt00181h pmid: 24809306
6 J Yu, J Low, W Xiao, et al.. 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
https://doi.org/10.1021/ja5044787 pmid: 24918628
7 Q Wang, L Qiu, X Tan, et al.. 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
https://doi.org/10.1016/j.jtice.2019.05.007
8 A M Soylu, M Polat, D A Erdogan, et al.. TiO2–Al2O3 binary mixed oxide surfaces for photocatalytic NOx abatement. Applied Surface Science, 2014, 318: 142–149
https://doi.org/10.1016/j.apsusc.2014.02.065
9 N Todorova, T Giannakopoulou, S Karapati, et al.. Composite TiO2/clays materials for photocatalytic NOx oxidation. Applied Surface Science, 2014, 319: 113–120
https://doi.org/10.1016/j.apsusc.2014.07.020
10 H Wang, X Zhang, Y Su, et al.. Photoelectrocatalytic oxidation of aqueous ammonia using TiO2 nanotube arrays. Applied Surface Science, 2014, 311: 851–857
https://doi.org/10.1016/j.apsusc.2014.05.195
11 M Sendra, I Moreno-Garrido, M P Yeste, et al.. 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
https://doi.org/10.1016/j.envpol.2017.04.053 pmid: 28454020
12 D Farrusseng, A Tuel. Perspectives on zeolite-encapsulated metal nanoparticles and their applications in catalysis. New Journal of Chemistry, 2016, 40(5): 3933–3949
https://doi.org/10.1039/c5nj02608c
13 N R Nalid, A Majid, M B Tahir, et al.. Carbonaceous-TiO2 nanomaterials for photocatalytic degradation of pollutants: A review. Ceramics International, 2017, 43(17): 14552–14571
https://doi.org/10.1016/j.ceramint.2017.08.143
14 S Silvestri, B Hennemann, N Zanatta, et al.. Photocatalytic efficiency of TiO2 supported on raw red clay disks to discolour Reactive Red 141. Water, Air, & Soil Pollution, 2018, 229(2): 40 
https://doi.org/10.1007/s11270-018-3700-x
15 R Tang, S Zhou, Z Yuan, et al.. Metal-organic framework derived Co3O4/TiO2/Si heterostructured nanorod array photoanodes for efficient photoelectrochemical water oxidation. Advanced Functional Materials, 2017, 27(37): 1701102
https://doi.org/10.1002/adfm.201701102
16 Z Ding, X J Hu, P L Yue, et al.. Synthesis of anatase TiO2 supported on porous solids by chemical vapor deposition. Catalysis Today, 2001, 68(1–3): 173–182
https://doi.org/10.1016/S0920-5861(01)00298-X
17 X Qian, K Fuku, Y Kuwahara, et al.. Design and functionalization of photocatalytic systems within mesoporous silica. ChemSusChem, 2014, 7(6): 1528–1536
https://doi.org/10.1002/cssc.201400111 pmid: 24828540
18 S Yaparatne, C P Tripp, A Amirbahman. Photodegradation of taste and odor compounds in water in the presence of immobilized TiO2–SiO2 photocatalysts. Journal of Hazardous Materials, 2018, 346: 208–217
https://doi.org/10.1016/j.jhazmat.2017.12.029 pmid: 29275110
19 T Kamegawa, Y Ishiguro, H Seto, et al.. 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
https://doi.org/10.1039/c4ta06020b
20 T Kamegawa, Y Ishiguro, H Yamashita. 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
https://doi.org/10.1016/j.cattod.2018.06.055
21 Y Liu, Y Feng, J Yao. Recent advances in the direct fabrication of millimeter-sized hierarchical porous materials. RSC Advances, 2016, 6(84): 80840–80846
https://doi.org/10.1039/c6ra17018h
22 A Galarneau, A Sachse, B Said, et al.. 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
https://doi.org/10.1016/j.crci.2015.05.017
23 A El Kadib, R Chimenton, A Sachse, et al.. Functionalized inorganic monolithic microreactors for high productivity in fine chemicals catalytic synthesis. Angewandte Chemie International Edition, 2009, 48(27): 4969–4972
https://doi.org/10.1002/anie.200805580 pmid: 19479911
24 W Cheng, K Tao, Y Wu, et al.. Preparation of hierarchical porous S-1/silica monoliths by steaming crystallization. ChemistrySelect, 2019, 4(13): 3741–3744
https://doi.org/10.1002/slct.201900223
25 C Anderson, A J Bard. Improved photocatalytic activity and characterization of mixed TiO2/SiO2 and TiO2/Al2O3 materials. The Journal of Physical Chemistry B, 1997, 101(14): 2611–2616
https://doi.org/10.1021/jp9626982
26 G Dong, W Ho, Y Li, et al.. Facile synthesis of porous graphene-like carbon nitride (C6N9H3) with excellent photocatalytic activity for NO removal. Applied Catalysis B: Environmental, 2015, 174: 477–485
https://doi.org/10.1016/j.apcatb.2015.03.035
27 F Dong, Z Zhao, T Xiong, et al.. 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
https://doi.org/10.1021/am403653a pmid: 24144400
28 J Yu, S Wang, J Low, et al.. 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
https://doi.org/10.1039/c3cp53131g pmid: 23999576
29 D Shen, L Chen, J Yang, et al.. 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
https://doi.org/10.1021/acsami.5b04992 pmid: 26192924
30 Y Chen, W Huang, D He, et al.. 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
https://doi.org/10.1021/am503674e pmid: 25089850
31 J Yu, J Ran. Facile preparation and enhanced photocatalytic H2-production activity of Cu(OH)2 cluster modified TiO2. Energy & Environmental Science, 2011, 4(4): 1364–1371
https://doi.org/10.1039/c0ee00729c
32 M M Khan, S A Ansari, D Pradhan, et al.. 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 
https://doi.org/10.1039/c3ta14052k
33 X Mao, X Lang, Z Wang, et al.. Band-gap states of TiO2(1 1 0): Major contribution from surface defects. Journal of Physical Chemistry Letters, 2013, 4(22): 3839–3844
https://doi.org/10.1021/jz402053p
34 B Choudhury, A Choudhury. 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
https://doi.org/10.1016/j.physe.2013.10.014
35 H Lin, C P Huang, W Li, et al.. 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
https://doi.org/10.1016/j.apcatb.2006.07.018
36 X Wang, L Sø, R Su, et al.. The influence of crystallite size and crystallinity of anatase nanoparticles on the photo-degradation of phenol. Journal of Catalysis, 2014, 310(SI): 100–108
https://doi.org/10.1016/j.jcat.2013.04.022
37 Y Zhang, Z Chen, S Liu, et al.. 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
https://doi.org/10.1016/j.apcatb.2013.04.059
38 R Hao, G Wang, H Tang, et al.. 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
https://doi.org/10.1016/j.apcatb.2016.01.026
39 F Wu, W Liu, J Qiu, et al.. Enhanced photocatalytic degradation and adsorption of methylene blue via TiO2 nanocrystals supported on graphene-like bamboo charcoal. Applied Surface Science, 2015, 358: 425–435
https://doi.org/10.1016/j.apsusc.2015.08.161
40 M J Sampaio, C G Silva, A M T Silva, et al.. Carbon-based TiO2 materials for the degradation of Microcystin-LA. Applied Catalysis B: Environmental, 2015, 170: 74–82
https://doi.org/10.1016/j.apcatb.2015.01.013
41 Y Ye, Y Feng, H Bruning, et al.. 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
https://doi.org/10.1016/j.apcatb.2017.08.040
42 C Minero, M Lucchiari, D Vione, et al.. Fe(III)-enhanced sonochemical degradation of methylene blue in aqueous solution. Environmental Science & Technology, 2005, 39(22): 8936–8942
https://doi.org/10.1021/es050314s pmid: 16323797
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed