Abstract
A carbon/carbon-doped titanium dioxide double-layer hollow microsphere (C/TiO2 microsphere) photocatalyst was prepared by hydrolysis of thermal expendable microspheres (TEMs) and a TiO2 sol–gel process. The thickness of the TiO2 and carbon layers was controlled by the concentration of sulfuric acid used for hydrolyzing the TEMs. The photocatalytic activity of the samples was studied with rhodamine B as a target degradation product. The result showed that the photocatalytic activity was affected by the thickness of the carbon and TiO2 layers significantly. The C/TiO2 microspheres obtained with 65% H2SO4 possessed the best photocatalytic activity. Compared with pure TiO2, the visible light absorption range of the C/TiO2 microspheres was expanded to 643 nm; the specific surface area was more than five times of the pure TiO2; the response intensity of photocurrent was ten times of the pure TiO2. The degradation rate of rhodamine B caused by the photocatalysis of the C/TiO2 microspheres was 96% in 140 min, and kept 83% after three times of reuse. The C/TiO2 microspheres were easy for recycling and showed great potential in wastewater treatment.
Highlights
-
Polyacrylonitrile thermal expandable microsphere was used for the first time to prepare C/TiO2 double-layer hollow microspheres.
-
The thickness of the TiO2 and carbon layers was controlled by the concentration of sulfuric acid.
-
The C/TiO2 microspheres showed excellent photocatalytic activity affected by the thickness of the carbon and TiO2 layers significantly.
-
The C/TiO2 microspheres were easy for recycling and showed great potential in wastewater treatment.
Similar content being viewed by others
References
Wang R, Hashimoto K, Fujishima A, Chikuni M, Kojima E, Kitamura A, Shimohigoshi M, Watanabe T (1997) Light-induced amphiphilic surfaces. Nature 388:431–432
Pelaez M, Nolan NT, Pillai SC, Seery MK, Falaras P, Kontos AG, Dunlop PSM, Hamilton JWJ, Byrne JA, O’Shea K (2012) A review on the visible light active titanium dioxide photocatalysts for environmental applications. Appl Catal B- Environ 125:331–349
Zhao J, Chen C, Ma W (2005) Photocatalytic degradation of organic pollutants under visible light irradiation. Top Catal 35:269–278
Pendergast MTM, Hoek EMV (2011) A review of water treatment membrane nanotechnologies. Energy Environ Sci 4:1946–1971
Chowdhury P, Moreira J, Gomaa H, Ray AK (2012) Visible-solar-light-driven photocatalytic degradation of phenol with dye-sensitized TiO2: parametric and kinetic study. Ind Eng Chem Res 51:4523–4532
Youssef Z, Colombeau L, Yesmurzayeva N, Baros F, Vanderesse R, Hamieh T, Toufaily J, Frochot C, Roques-Carmes T, Acherar S (2018) Dye-sensitized nanoparticles for heterogeneous photocatalysis: cases studies with TiO2, ZnO, fullerene and graphene for water purification. Dyes Pigments 159:49–71
Li L, Huang X, Zhang J, Zhang W, Ma F, Xiao Z, Gai S, Wang D, Li N (2015) Multi-layer three-dimensionally ordered bismuth trioxide/titanium dioxide nanocomposite: synthesis and enhanced photocatalytic activity. J Colloid Interface Sci 443:13–22
Li Y, Wang P, Huang C, Yao W, Wu Q, Xu Q (2017) Synthesis and photocatalytic activity of ultrafine Ag3 PO4 nanoparticles on oxygen vacated TiO2. Appl Catal B-Environ 205:489–497
Chen X, Zhang J, Jiang X, Wang H, Kong Z, Xi J, Ji Z (2018) Curved surface TiO2 nanodrums coupled with MoS2 as heterojunction photocatalysts with enhancing photocatalytic activity. Mater Lett 229:277–280
Wang W, Liu X, Fang J, Lu C (2019) TiO2@g-C3N4 heterojunction with directional charge migration behavior for photodegradation of tetracycline antibiotics. Mater Lett 236:622–624
Zhang J, Chen X, Yu W, Zeng J, Shi Y, Lin S, Huang G, Zhang L, Wang H, Kong Z, Xi J, Ji Z (2019) Photocatalytic study of a novel crystal facets sensitive heterojunction between Sb8O11Cl2 and anatase TiO2 with different exposed facets. Dyes Pigments 160:530–539
Chen MJ, Lo SL, Lee YC, Huang CC (2015) Photocatalytic decomposition of perfluorooctanoic acid by transition-metal modified titanium dioxide. J Hazard Mater 288:168–175
Hunge YM (2017) Sunlight assisted photoelectrocatalytic degradation of benzoic acid using stratified WO3/TiO2 thin films. Ceram Int 43:10089–10096
Phatyenchuen S, Pongthawornsakun B, Panpranot J, Praserthdam P (2018) Effect of transition metal dopants (M=Nb, La, Zr, and Y) on the M-TiO2 supported V2O5 catalysts in the selective oxidation of H2S to elemental sulfur. J Environ Chem Eng 6:5655–5661
Boningari T, Inturi SNR, Suidan M, Smirniotis PG (2018) Novel one-step synthesis of sulfur doped-TiO2 by flame spray pyrolysis for visible light photocatalytic degradation of acetaldehyde. Chem Eng J 339:249–258
Castellanos-Leal EL, Acevedo-Peña P, Güiza-Argüello VR, Córdoba-Tuta EM (2017) N and F Codoped TiO2 thin films on stainless steel for photoelectrocatalytic removal of cyanide ions in aqueous solutions. Mater Res 20:487–495
Duan Y, Chen X, Zhang X, Xiang W, Wu C (2018) Influence of carbon source on the anatase and brookite mixed phase of the C-doped TiO2 nanoparticles and their photocatalytic activity. Solid State Sci 86:12–18
Colomer MT, del Campo A (2019) Preparation of nanostructured TiO2 films with high catalytic activity and their 3D spatial distribution of anatase and rutile phases. J Mater Sci 54:9414–9425
Yao Y, Yuan J, Chen X, Tan L, Gu Q, Zhao W, Chen J (2019) In situ construction and sensing mechanism of TiO2–WO3 composite coatings based on the semiconductor heterojunctions. J Mater Res Technol 8:3580–3588
Mittal A, Mari B, Sharma S, Kumari V, Maken S, Kumari K, Kumar N (2019) Non-metal modified TiO2: a step towards visible light photocatalysis. J Mater Sci 30:3186–3207
Di C, Valentin, Pacchioni G, Selloni A (2005) Theory of carbon doping of titanium dioxide. Chem Mater 17:6656–6665
Sakthivel S, Kisch H (2003) Daylight photocatalysis by carbon-modified titanium dioxide. Angew Chem Int Ed Engl 42:4908–4911
Zhang Y, Zhao Z, Chen J, Cheng L, Chang J, Sheng W, Hu C, Cao S (2015) C-doped hollow TiO2 spheres: in situ synthesis, controlled shell thickness, and superior visible-light photocatalytic activity. Appl Catal B-Environ 165:715–722
Wang H, Wu Z, Yue L (2009) A simple two-step template approach for preparing carbon-doped mesoporous TiO2 hollow microspheres. J Phys Chem C 113:13317–13324
Yang Z, Niu Z, Lu Y, Hu Z, Han CC (2003) Templated synthesis of inorganic hollow spheres with a tunable cavity size onto core-shell gel particles. Angew Chem Int Ed Engl 42:1943–1945
Liu J, Zhu W, Yu S, Yan X (2014) Three dimensional carbogenic dots/TiO2 nanoheterojunctions with enhanced visible light-driven photocatalytic activity. Carbon 79:369–379
Tian J, Zhao Z, Kumar A, Boughton RI, Liu H (2014) Recent progress in design, synthesis, and applications of one-dimensional TiO2 nanostructured surface heterostructures: a review. Chem Soc Rev 43:6920–6937
Qian X, Ren M, Yue D, Zhu Y, Han Y, Bian Z, Zhao Y (2017) Mesoporous TiO2 films coated on carbon foam based on waste polyurethane for enhanced photocatalytic oxidation of VOCs. Appl Catal B-Environ 212:1–6
Ji L, Wang W, Stevens MM, Zhou S, Zhu A, Liang J (2015) A general strategy for the preparation of aligned multiwalled carbon nanotube/inorganic nanocomposites and aligned nanostructures. Mater Res Bull 61:453–458
Wu X, Yin S, Dong Q, Guo C, Li H, Kimura T, Sato T (2013) Synthesis of high visible light active carbon doped TiO2 photocatalyst by a facile calcination assisted solvothermal method. Appl Catal B-Environ 142:450–457
Ji L, Zhang Y, Miao S, Gong M, Liu X (2017) In situ synthesis of carbon doped TiO2 nanotubes with an enhanced photocatalytic performance under UV and visible light. Carbon 125:544–550
Yu X, Liu J, Yu Y, Zuo S, Li B (2014) Preparation and visible light photocatalytic activity of carbon quantum dots/TiO2 nanosheet composites. Carbon 68:718–724
Mohamed MA, Wan Salleh WN, Jaafar J, Rosmi MS, Mohd. Hir ZA, Abd Mutalib M, Ismail AF, Tanemura M (2017) Carbon as amorphous shell and interstitial dopant in mesoporous rutile TiO2: Bio-template assisted sol-gel synthesis and photocatalytic activity. Appl Surf Sci 393:46–59
Li M, Lu B, Ke QF, Guo YJ, Guo YP (2017) Synergetic effect between adsorption and photodegradation on nanostructured TiO2/activated carbon fiber felt porous composites for toluene removal. J Hazard Mater 333:88–98
Sampaio MJ, Bacsa RR, Benyounes A, Axet R, Serp P, Silva CG, Silva AMT, Faria JL (2015) Synergistic effect between carbon nanomaterials and ZnO for photocatalytic water decontamination. J Catal 331:172–180
Zhang J, Vasei M, Sang Y, Liu H, Claverie JP (2016) TiO2@carbon photocatalysts: the effect of carbon thickness on catalysis. ACS Appl Mater Interfaces 8:1903–1912
Jiang Z, Wei W, Mao D, Chen C, Shi Y, Lv X, Xie J (2015) Silver-loaded nitrogen-doped yolk-shell mesoporous TiO2 hollow microspheres with enhanced visible light photocatalytic activity. Nanoscale 7:784–797
Shao J, Sheng W, Wang M, Li S, Chen J, Zhang Y, Cao S (2017) In situ synthesis of carbon-doped TiO2 single-crystal nanorods with a remarkably photocatalytic efficiency. Appl Catal B-Environ 209:311–319
Xiong Z, Zhao XS (2012) Nitrogen-doped titanate-anatase core-shell nanobelts with exposed {101} anatase facets and enhanced visible light photocatalytic activity. J Am Chem Soc 134:5754–5757
Wang DH, Jia L, Wu XL, Lu LQ, Xu AW (2012) One-step hydrothermal synthesis of N-doped TiO2/C nanocomposites with high visible light photocatalytic activity. Nanoscale 4:576–584
Funding
This work is supported by the Natural Science Foundation of Jiangsu Province (No. BK20131226), the National Natural Science Foundation of China (No. 51273171), and a project is funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Ji, L., Liu, X., Xu, T. et al. Preparation and photocatalytic properties of carbon/carbon-doped TiO2 double-layer hollow microspheres. J Sol-Gel Sci Technol 93, 380–390 (2020). https://doi.org/10.1007/s10971-019-05176-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10971-019-05176-z