One-step electrospinning route of SrTiO3-modified Rutile TiO2nanofibers and its photocatalytic properties
© The Author(s). 2017
Received: 13 April 2017
Accepted: 8 May 2017
Published: 25 May 2017
The SrTiO3 modified rutile TiO2 composite nanofibers were synthesized by a simple electrospinning technique. The result of XRD, SEM and TEM indicate that the SrTiO3/TiO2 heterojuction has been prepared successfully. Compared with the TiO2 and SrTiO3, the photocatalytic activity of the SrTiO3/TiO2 (rutile) for the degradation of methyl orange exhibits an obvious enhancement under UV illumination. which is almost 2 times than that of bare TiO2 (rutile) nanofiber. Further, the high crystallinity and photon-generated carrier separation of the SrTiO3/TiO2 heterojuction are considered as the main reason for this enhancement.
As a prototypical semiconductor with environment friendly and high photoelectric property, Titanium oxide (TiO2) is widely used in optics, solar cells, sensors etc. [1–4], and also considered as a most promising photocatalyst in wastewater treatments , due to its low cost, highly physical-chemical stability and nontoxicity. As previous literature reported, though the anatase TiO2 exhibit better photocatalysis than the Rutile TiO2, but the band gap of anatase TiO2 (3.2 eV) is wider than the rutile TiO2 (3.0 eV), which may restrict the luminous energy utilization ratio in photocatalytic application. What’s more, compare with the metastable anatase TiO2, the rutile TiO2 exhibit more highly physical-chemical stability, which is beneficial for cyclic utilization in pollution treatment. With these unique advantages, how to improve the photocatalytic efficiency of the rutile TiO2 would be a significant issue. As known, the photocatalysis mainly depend on specific surface area or mobility and lifetime of photon-generated carriers, so lots of work have been reported. For specific surface area, lots of excellent morphology have been prepared, such as nanosheets , nanobelts , nanorods , nanofibers , and microflowers , all of them shows a inspiring results [11–14]. On the other hand, the surface noble metal modified or preparation of heterostructure are considered as useful ways to adjust the band structure for improving the mobility and lifetime of photon-generated carriers. However, compared with the high cost of the noble metal modified, the heterostructure is deemed as a efficient-low cost way. Lots of relevant researches have been reported, such as ZnO/TiO2 [15–17], CdS/ZnO [18–20], CeO2/graphene etc . Among those semiconductors, the strontium titanate (SrTiO3) has catched researchers attention due to the thermal stability and resistance to photocorrosion , and has been extensively applied in H2 generation , removal of NO , water splitting , and photocatalyst decomposition of dye [26–28]. In particular, as heterostructures composite photocatalyst attracted more attention, such as, Core-shell SrTiO3/TiO2 and heterostructures SrTiO3/TiO2 had showed much higher photocatalytic activity than the pure TiO2, which is attributed to heterostructures promote the separation of photogenerated carriers [29, 30]. So the SrTiO3 is considered as a good candidate for coupling with the anatase phase of TiO2 for adjusting the band structure to enhance its photocatalytic activity. However, there are rare reports about the SrTiO3-modified rutile TiO2 composites nanofibers for the degradation of dye pollutants because of the cumbersome process, so how to simplify the preparation of SrTiO3/TiO2 nano-heterojunction would be an important issue for its practical application. As known, the electrospining is a convenient and efficient method to prepared nanomaterials, which could easily prepare the precursor into nanofibers at the prelusion and then form to series of nanostructure in subsequent annealing, which has been reported in lots literatures [31–36].
In the present study, we report on a simple one-step synthesis of SrTiO3 modified rutile TiO2 nano-heterojunction with high photocatalysis via the electrospinning. Then the mechanism of the photocatalytic enhancement of the heterojuction has been studied.
Analytical grade acetic acid, N,N-Dimethylformamide (DMF, Aladdin, 99.5%), Tetra butyl titanate (TBT, Aladdin, 99.0%), Strontium acetate (Aladdin, 99.97%), Polyvinylpyrrolidone (PVP, MW = 1,300,000) were obtained from Shanghai Macklin Biochemical Co. Ltd.
Preparation of SrTiO3/TiO2 (rutile) Composite Nanofiber
The surface morphology of the as-prepared samples was investigated by the Field-emission scanning electron microscope (FESEM, Hitachi S-4800) equipped with Energy- dispersive X-ray spectroscopy (EDS), and the microstructure of the as-prepared samples was observed by a transmission electron microscope (TEM, JEM-2100, 200 kV); Crystal structures of the as-prepared samples were characterized by Bruker/D8-advance with Cu Kα radiation (λ = 1.518 Å) at the scanning rate of 0.2 sec/step in the range of 10-80°. The absorption spectrum of the as-prepared samples were recorded using by a UV–visibles pectrophotometer (U-3900Hitachi).
Measurement of photocatalytic activity
A 50 mL methyl orange (MO) solution with an initial concentration of 15 mg/L in the presence of sample(30 mg) was filled in a quartz reactor. The light source was provided by a UV − C mercury lamp (Philips Holland, 25 W). Prior to irradiation, the solution was continuously kept in dark for 30 min to reach an adsorption–desorption equilibrium between organic substrates and the photocatalysts. At given intervals (t = 10 min) of irradiation, the samples of the reaction solution were taken out and analyzed. The concentrations of the remnant dye were measured with a spectrophotometer at λ = 464 nm.
Results and discussion
The selected area electron diffraction (SAED) as shown in Fig. 4c, which indicates that the nano-heterojuction owns a high crystallinity. The FESEM EDX in Fig. 4d futher confirms that ST-3 heteroarchitectures contain the Ti, Sr, O elements and corresponds to the XRD.
In order to be convenient for long-term photocatalytic use in the treatment of dye wastewater, the cycling stability is one of the most important factor, and was shown in Fig. 5c. As shown in Fig. 5c, after 5 cycles, there is negligible loss of MO photodegradation, which could be ascribed to the lost of photocatalyst in centrifugal process and further illustrate that the ST-3 composite photocatalysts possess highly stability and cyclicity.
Therefore, the SrTiO3/TiO2 (rutile) composite nanofibers could be considered as an economical and continuable photocatalyst in future application.
In summary, we have prepared the SrTiO3/TiO2 (rutile) composite nanofibers via a simple route of electrospinning and displayed its excellent ability to degrade methyl orange, which could be mainly ascribed to the remarkable heterojuction and the high crystallinity. What’s more, the novel 3D structure could increase the specific surface area efficiently, which is also an important reason for the photocatalysis. Thus excellent photocatalyst could afford a new sight for design of the future catalyst.
This work was supported by Zhejiang Provincial Natural Science Foundation of China (No. LY17E020001, LQ17F040004 and LY15E030011), Natural Science Foundation of China (No. 51672249, 51603187 and 91122022), Taizhou science and technology project of China (1601KY73).
WJZ performed the all sample preparation steps and drafted the manuscript. JZ participated in the design of the study. JQP carried out the analysis. JFQ and JTN participated in the measurements. CRL supervised the entire research and polished the manuscript. All the authors have read and approved the final manuscript.
The authors declare that they have no competing interests.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
- Nafisah S, Saad SKM, Umar AA, Plucinski K, Lis M, Maciaga A, Miedzinski R (2015) Laser stimulated nonlinear optics of Ag nanoparticle-loaded poriferous TiO2 microtablet. Appl Opt 45:263–271Google Scholar
- Ma QL, Cui YQ, Deng XY, Cheng XW, Cheng QF, Li B (2017) Controllable Fabrication of TiO2 Nanobelts/Nanotubes Photoelectrode for Dye Sensitized Solar Cells. J Nanosci Nanotechnol 17:2072–2078View ArticleGoogle Scholar
- Mishra AK, Huang LP (2015) TiO2-Decorated Graphite Nanoplatelet Nanocomposites for High-Temperature Sensor Applications. Small 11:361–366View ArticleGoogle Scholar
- Zhao WJ, Zhang ZC, Zhang J, Wu HG, Xi LM, Ruan CH (2016) Synthesis of Ag/TiO2/graphene and its photocatalytic properties under visible light. Mater Lett 171:182–186View ArticleGoogle Scholar
- Zhou SM, Ma DK, Cai P, Chen W, Huang SM (2014) TiO2/Bi2(BDC)3/BiOCl nanoparticles decorated ultrathin nanosheets with excellent photocatalytic reaction activity and selectivity. Mater Res Bull 60:64–71View ArticleGoogle Scholar
- Zhao DD, Yu YL, Gao DZ, Cao YA (2015) Properties and Photocatalytic Activity of Rutile TiO2 Nanosheets. J Inorg Mater 31:1–6Google Scholar
- Pang LX, Wang XY, Tang XD (2015) Enhanced photocatalytic performance of porous TiO2 nanobelts with phase junctions. Solid State Sci 39:29–33View ArticleGoogle Scholar
- Sun MX, Fang YL, Wang Y, Sun SF, He J, Yan Z (2015) Synthesis of Cu2O/graphene/rutile TiO2 nanorod ternary composites with enhanced photocatalytic activity. J Alloy Compd 650:520–527View ArticleGoogle Scholar
- Jung HJ, Kim YL, Jang H, Choia MY, Kimb MH (2016) Pulse laser irradiation of electrospun TiO2 nanofibers for the crystalline phase control and enhanced photocatalytic activity. Mater Lett 181:59–62View ArticleGoogle Scholar
- Nair RV, Jijith M, Gummaluri VS, Vijayan C (2016) A novel and efficient surfactant-free synthesis of Rutile TiO2 microflowers with enhanced photocatalytic activity. Opt Mater 55:38–43View ArticleGoogle Scholar
- Lai LL, Wen W, Wu JM (2016) Ni-doped rutile TiO2 nanoflowers: lowtemperature solution synthesis and enhanced photocatalytic efficiency. RSC Adv 6:25511–25518View ArticleGoogle Scholar
- Sheikh FA, Appiah-Ntiamoah R, Zargar MA, Chandradass J, Chung WJ, Kim H (2016) Photocatalytic properties of Fe2O3-modified rutile TiO2 nanofibers formed by electrospinning technique. Mater Chem Phys 172:62–68View ArticleGoogle Scholar
- Lavanya T, Dutta M, Satheesh K (2016) Graphene wrapped porous tubular rutile TiO2 nanofibers with superior interfacial contact for highly efficient photocatalytic performance for water treatment. Sep Purif Technol 168:284–293View ArticleGoogle Scholar
- Lu YY, Zhang YY, Zhang J, Shi Y, Li Z, Feng ZC, Li C (2016) In situ loading of CuS nanoflowers on rutile TiO2 surface and their improved photocatalytic performance. Appl Surf Sci 370:312–319View ArticleGoogle Scholar
- Kwiatkowski M, Chassagnon R, Heintz O, Geoffroy N, Skompska M, Bezverkhyy I (2017) Improvement of photocatalytic and photoelectrochemical activity of ZnO/TiO2 core/shell system through additional calcination: Insight into the mechanism. Appl Catal B: Environ 204:200–208View ArticleGoogle Scholar
- Zalfani M, Schueren B, Mahdouani M, Bourguiga R, Yu WB, Wu M, Deparis O, Li Y, Su BL (2016) ZnO quantum dots decorated 3DOM TiO2 nanocomposites: Symbiose of quantum size effects and photonic structure for highly enhanced photocatalytic degradation of organic pollutants. Appl Catal B: Environ 199:187–198View ArticleGoogle Scholar
- Gondal MA, Ilyas AM, Baig U (2016) Pulsed laser ablation in liquid synthesis of ZnO/TiO2 nanocomposite catalyst with enhanced photovoltaic and photocatalytic performance. Ceram Int 42:13151–13160View ArticleGoogle Scholar
- Dumbrava A, Berger D, Prodan G, Moscalu F (2016) Functionalized ZnO/CdS Composites: Synthesis, Characterization and Photocatalytic Applications. Chalcogenide Lett 13:105–115Google Scholar
- Ge SS, Zhang QX, Wang XT, Qian S, Bao LW, Rui D, Liu QY (2016) Bacteria-Directed Construction of ZnO/CdS Hollow Rods and Their Enhanced Photocatalytic Activity. J Nanosci Nanotechnol 16:4929–4935View ArticleGoogle Scholar
- Huo PW, Zhou MJ, Tang YF, Liu XL, Ma CC, Yu LB, Yan YS (2016) Incorporation of N–ZnO/CdS/Graphene oxide composite photocatalyst for enhanced photocatalytic activity under visible light. J Alloy Compd 670:198–209View ArticleGoogle Scholar
- Jiang LH, Yao MG, Liu B, Li QJ, Liu R, Lv H, Lu SC, Gong C, Zou B, Cui T, Liu BB (2012) Controlled Synthesis of CeO2/Graphene Nanocomposites with Highly Enhanced Optical and Catalytic Properties. J Phys Chem C 116:11741–11745View ArticleGoogle Scholar
- Ohno T, Tsubota T, Nakamura Y, Sayama K (2005) Preparation of S, C cation-codoped SrTiO3 and its photocatalytic activity under visible light. Appl Catal A Gen 288:74–79View ArticleGoogle Scholar
- Cho YJ, Moon GH, Kanazawa T, Maeda K, Choi W (2016) Selective dual-purpose photocatalysis for simultaneous H2 evolution and mineralization of organic compounds enabled by a Cr2O3 barrier layer coated on Rh/SrTiO3. Chem Commun 52:9636–9639View ArticleGoogle Scholar
- Li HH, Yin S, Wang YH, Sekino T, Lee SW, Sato T (2013) Roles of Cr3+ doping and oxygen vacancies in SrTiO3 photocatalysts with high visible light activity for NO removal. J Catal 297:65–69View ArticleGoogle Scholar
- Chen W, Liu H, Li XY, Liu S, Gao L, Mao LQ, Fan ZY, Shangguan WF, Fang WJ, Liu YS (2016) Polymerizable complex synthesis of SrTiO3:(Cr/Ta) photocatalysts to improve photocatalytic water splitting activity under visible light. Appl Catal B: Environ 192:145–151View ArticleGoogle Scholar
- Jing PP, Lan W, Su Q, Xie EQ (2015) High photocatalytic activity of V-doped SrTiO3 porous nanofibers produced from a combined electrospinning and thermal diffusion process. Beilstein J Nanotechnol 6:1281–1286View ArticleGoogle Scholar
- Jing PP, Du JL, Wang JB, Lan W, Pan LN, Li JN, Wei JW, Cao DR, Zhang XL, Zhao CB, Liu QF (2015) Hierarchical SrTiO3/NiFe2O4 composite nanostructures with excellent light response and magnetic performance synthesized toward enhanced photocatalytic activity. Nanoscale 7:14738–14746View ArticleGoogle Scholar
- Xian T, Yang H, Di LJ, Ma JY, Zhang HM, Dai JF (2014) Photocatalytic reduction synthesis of SrTiO3-graphene nanocomposites and their enhanced photocatalytic activity. Nanoscale Res Lett 9:327–335View ArticleGoogle Scholar
- Zhao W, Liu NQ, Wang HX, Mao LH (2017) Sacrificial template synthesis of core-shell SrTiO3/TiO2heterostructured microspheres photocatalyst. Ceram Int 43:4807–4813View ArticleGoogle Scholar
- Cao TP, Li YJ, Wang CH, Shao CL, Liu YC (2011) A Facile in Situ Hydrothermal Method to SrTiO3/TiO2 Nanofiber Heterostructures with High Photocatalytic Activity. Langmuir 27:2946–2952View ArticleGoogle Scholar
- Sedghia R, Moazzamib HR, Davarania SSH, Nabida MR, Keshtkar AR (2017) A one step electrospinning process for the preparation of polyaniline modified TiO2/polyacrylonitile nanocomposite with enhanced photocatalytic activity. J Alloy Compd 695:1073–1079View ArticleGoogle Scholar
- Tian FY, Hou DF, Hu FC, Xie K, Qiao XQ, Li DS (2017) Pouous TiO2 nanofibers decorated CdS nanoparticles by SILAR method for enhanced visible-light-driven photocatalytic activity. Appl Surf Sci 391:295–302View ArticleGoogle Scholar
- Wang XQ, Dou LY, Yang L, Yu JY, Ding B (2017) Hierarchical structured MnO2@SiO2 nanofibrous membranes with superb flexibility and enhanced catalytic performance. J Hazard Mater 324:203–212View ArticleGoogle Scholar
- Xu TF, Ni DJ, Chen X, Wu F, Ge PF, Lu WY, Hu HG, Zhu ZX, Chen WX (2016) Self-floating graphitic carbon nitride/zinc phthalocyanine nanofibers for photocatalytic degradation of contaminants. J Hazard Mater 317:17–26View ArticleGoogle Scholar
- Pant B, Pant HR, Park M (2014) Electrospun CdS-TiO2 doped carbonnanofibers for visible-light-induced photocatalytic hydrolysis of ammonia borane. Catal Commun 50:63–68View ArticleGoogle Scholar
- Hou DF, Hu XL, Ho WK, Hu P, Huang YH (2015) Facile fabrication of porous Cr-doped SrTiO3 nanotubes by electrospinning and their enhanced visible-light-driven photocatalytic properties. J Mater Chem A 3:3935–3943View ArticleGoogle Scholar
- Zhang XC, Zhang SY, You Y, Li YL (2012) Effect of the Steam Activation Thermal Treatment on the Microstructure of Continuous TiO2 Fibers. J Nanomater 2012:1–7Google Scholar