Browsing by Subject "Photocatalytic activities"

Now showing 1 - 14 of 14

Open Access
Bi2O3 and BiOCl electrospun nanosheets and morphology-dependent photocatalytic properties
(Royal Society of Chemistry, 2014) Babu, V. J.; Bhavatharini, R. S. R.; Ramakrishna, S.
BiOCl and Bi2O3 nanosheet like structures were produced by electrospinning. The morphological changes were observed by changing precursor (BiOCl3 and Bi(NO3)3·5H 2O) concentrations. These nanosheets were analyzed by XRD, which reveals that the crystal structures of BiOCl and Bi2O3 belonged to tetragonal and beta-phase systems respectively. Both nanostructures were employed for the photodegradation of Alizarin Red S (ARS) dye under UV light (<390 nm) irradiation. BiOCl nanosheet like structures exhibited superior photocatalytic activity (PCA) for the degradation of ARS dye and their half-life was estimated from the kinetic plots of PCA. A plausible reaction mechanism is proposed for the PCA and discussed in detail. © the Partner Organisations 2014.
Open Access
Comparative study of optically activated nanocomposites with photocatalytic TiO2 and ZnO nanoparticles for massive environmental decontamination
(S P I E - International Society for Optical Engineering, 2007) Tek, S.; Mutlugun, E.; Soganci, I. M.; Perkgoz, N. K.; Yucel, D.; Celiker, G.; Demir, Hilmi Volkan
Nanocomposites that incorporate TiO2 and ZnO nanoparticles separately in three-dimensional solgel matrices through full chemical integration are prepared to perform highly efficient photocatalytic activities for applications of environmental decontamination. Spectral responses of photocatalytic TiO2 and ZnO nanoparticles exposed to UV activation for self-cleaning process were obtained as also their optical relative spectral efficiency curves from 270 to 370 nm in the UV regime. Our investigations of the optimal conditions to increase their spectral photocatalytic efficiencies resulted in remarkably high levels of optical recovery and efficiency.
Open Access
Electrospun BiOI nano/microtectonic plate-like structure synthesis and UV-light assisted photodegradation of ARS dye
(Royal Society of Chemistry, 2014) Babu, V. J.; Bhavatharini, R. S. R.; Ramakrishna, S.
BiOI electrospun nanofibers were prepared by using PAN as a supporting polymer. Subsequent annealing at 500 °C for 5 h, with a ramp rate of about 5 °C min-1 in air, breaks the nanofibers down to tectonic plate-like nano/microstructures. The surface physical and chemical structural changes were then further characterized by FE-SEM, TEM, XRD and XPS. The results reveal that the morphology and crystallite size of BiOI vary strongly depending on the precursor concentration used in the synthesis method. These nanostructures were later employed for photocatalytic degradation of a synthetic textile dye, Alizarin Red S (ARS). The photocatalytic efficiencies were found to be about 93.34% after 100 min of UV-light (340 nm) illumination. Photocatalytic activity (PCA) performance depends on morphology and band alignment. All the compositions follow first order pseudo-kinetics, which was found to be 0.1197 min-1 for a doping concentration of 3%. The enhancement in photodegradation could be possibly by photocatalysis and a photosensitization phenomenon. This has been explained based on the band edge position. © the Partner Organisations 2014.
Open Access
Electrospun polymeric nanofibrous composites containing TiO2 short nanofibers
(2011) Deniz, A. E.; Celebioglu A.; Kayaci, F.; Uyar, Tamer
In this study, polymeric nanofibrous composites containing anatase TiO 2 short nanofibers (TiO2-SNF) were successfully produced via electrospinning. The fabrication of the nanofibrous composite structure includes two steps. First, anatase TiO2 nanofibers were obtained by calcination of electrospun PVP/TiO2 nanofibers and then crushed into short nanofibers ranging from few microns in length. Second, these TiO 2-SNF were dispersed into polymer solutions and then electrospun into nanofibrous composites. We obtained nanofibers containing TiO2-SNF from different polymer types including PMMA, PAN, PET and PC. The SEM and TEM imaging indicated that some of the TiO2-SNF were fully covered by the polymeric matrix whereas some TiO2-SNF were partially covered and/or stick on the surface of the fibers. The photocatalytic activity of nanofibrous composites containing TiO2-SNF was evaluated by monitoring the photocatalytic decomposition of a model dye (rhodamine-6G) under UV irradiation. © 2011 Elsevier B.V. All rights reserved.
Open Access
Enhanced photocatalytic activity of homoassembled ZnO nanostructures on electrospun polymeric nanofibers: a combination of atomic layer deposition and hydrothermal growth
(Elsevier, 2014) Kayaci, F.; Vempati S.; Ozgit Akgun, C.; Bıyıklı, Necmi; Uyar, Tamer
We report on the synthesis and photocatalytic activity (PCA) of electrospun poly(acrylonitrile) (PAN) nanofibrous mat decorated with nanoneedles of zinc oxide (ZnO). Apart from a detailed morphological and structural characterization, the PCA has been carefully monitored and the results are discussed elaborately when juxtaposed with the photoluminescence. The present hierarchal homoassembled nanostructures are a combination of two types of ZnO with diverse optical qualities, i.e. (a) controlled deposition of ZnO coating on nanofibers with dominant oxygen vacancies and significant grain boundaries by atomic layer deposition (ALD), and (b) growth of single crystalline ZnO nanoneedles with high optical quality on the ALD seeds via hydrothermal process. The needle structure (~25. nm in diameter with an aspect ratio of ~24) also supports the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. Furthermore, it is shown that enhanced PCA is because of the catalytic activity at surface defects (on ALD seed), valence band, and conduction band (of ZnO nanoneedles). PCA and durability of the PAN/ZnO nanofibrous mat have also been tested with aqueous solution of methylene blue and the results showed almost no decay in the catalytic activity of this material when reused.
Open Access
Fast and quick degradation properties of doped and capped ZnO nanoparticles under UV-Visible light radiations
(Elsevier Ltd, 2016) Mittal, M.; Sharma, M.; Pandey, O. P.
Undoped and Manganese (Mn) doped zinc oxide (ZnO) (Zn1- xMnxO, x=0.005, 0.01, 0.015 and 0.02) nanoparticles (NPs) capped with (1.0%) Thioglycerol (TG) has been successfully synthesized by co-precipitation method. Optical and morphological studies have been done for photophysical and structural analysis of synthesized materials. The photocatalytic activity of undoped and Mn doped ZnO NPs were investigated by degradation of crystal violet (CV) dye under UV-Visible light radiations. It has been found that Mn (1.0%) doping concentration is optimal for photophysical and photocatalytic properties. When the pH of as synthesized optimum doped ZnO NPs varied from natural pH i.e. from 6.7 to 8.0 and 10.0, the degradation of CV dye increases from 92% to 95% and 98% in 180min respectively. Further on increasing the pH of optimum doped synthesized NPs to 12.0, almost 100% degradation has been achieved in 150min. Optimum doped photocatalyst synthesized at pH-12.0 has also effectively degraded the CV dye solution in acidic and basic medium thus showed its utility in various industries. However, it has been found that 100% of CV dye quickly degraded in 30min when only 1.0% of hydrogen peroxide (H2O2) was introduced along with optimized NPs synthesized at pH-12. Kinetic studies show that the degradation of CV dye follows pseudo first and second-order kinetic law. Further an industrial anionic polyazo Sirius red F3B (SRF3B) dye has been degraded to 100% with optimized NPs synthesized at pH-12.0 in 15min only.
Open Access
Flexible organic-inorganic core-shell nanofibers by electrospinning and atomic layer deposition
(CRC Press, 2012) Kayacı, Fatma; Çağla, Özgit-Akgün; Dönmez, İnci; Bıyıklı, Necmi; Uyar, Tamer
Organic-inorganic core-shell nanofibers were fabricated by combining electrospinning and atomic layer deposition (ALD). In the first step, nylon66 (polymeric organic core) nanofibers having different average fiber diameters (∼100 nm, ∼250 nm and ∼650 nm) were electrospun by using different solvent systems and polymer concentrations. In the second step, uniform and conformal layer of zinc oxide (ZnO) (inorganic shell) with precise thickness (∼90 nm) and composition on the round surface of the nylon nanofibers were deposited by ALD. The core-shell nylon66-ZnO nanofibers have shown unique properties such as structural flexibility due to the polymeric core and photocatalytic activity due to the ZnO shell layer.
Open Access
Rational synthesis of Na and S co-catalyst TiO2-based nanofibers: presence of surface-layered TiS3 shell grains and sulfur-induced defects for efficient visible-light driven photocatalysis
(Royal Society of Chemistry, 2017) Ranjith, K. S.; Uyar, Tamer
Surface-modified TiO2 nanofibers (NFs) with tunable visible-light photoactive catalysts were synthesised through electrospinning, followed by a sulfidation process. The utilization of sodium-based sulfidation precursors effectively led to the diffusion and integration of sulfur impurities into TiO2, modifying its band function. The optical band function of the sulfur-modified TiO2 NFs can be easily manipulated from 3.17 eV to 2.28 eV through surface modification, due to the creation of oxygen vacancies through the sulfidation process. Sulfidating TiO2 NFs introduces Ti-S-based nanograins and oxygen vacancies on the surface that favor the TiO2-TiS3 core-shell interface. These defect states extend the photocatalytic activity of the TiO2 NFs under visible irradiation and improve effective carrier separation and the production of reactive oxygen species. The surface oxygen vacancies and the Ti-S-based surface nanograins serve as charge traps and act as adsorption sites, improving the carrier mobility and avoiding charge recombination. The diffused S-modified TiO2 NFs exhibit a degradation rate of 0.0365 cm-1 for RhB dye solution, which is 4.8 times higher than that of pristine TiO2 NFs under visible irradiation. By benefiting from the sulfur states and oxygen vacancies, with a narrowed band gap of 2.3 eV, these nanofibers serve as suitable localized states for effective carrier separation.
Open Access
Reduced recombination and enhanced UV-assisted photocatalysis by highly anisotropic titanates from electrospun TiO2-SiO2 nanostructures
(Royal Society of Chemistry, 2014) Babu, V. J.; Vempati S.; Ramakrishna, S.
The surface areas of electrospun fibers/rice grain-shaped nanostructures of TiO2-SiO2 composites were further enhanced after transforming them into thorn or sponge shaped titanates via selective leaching of SiO2, which was reported by our group previously [RSC Adv., 2012, 2, 992]. In this study, we report on their application in photocatalytic activity (PCA) when juxtaposed with photoluminescence (PL). Two defect related bands are observed in PL and their origin is discussed in relation to calcination, crystallization and nucleation effects. The relative PL intensity for sponge shapes was the lowest and hence had the lowest radiative recombination, which suggests carrier trapping at defect centers. This enables the charge carriers to migrate to the surface and participate in the PCA. The results of PCA suggested that the sponge-shaped titanate exhibits the highest degradation rate among all samples. A plausible mechanism for the differences in PCA is proposed based on the variation in the defect-densities. This journal is © the Partner Organisations 2014.
Open Access
Role of zinc interstitials and oxygen vacancies of ZnO in photocatalysis: a bottom-up approach to control the defect density
(Royal Society of Chemistry, 2014-06-09) Kayaci, F.; Vempati S.; Donmez, I.; Bıyıklı, Necmi; Uyar, Tamer
Oxygen vacancies (VOs) in ZnO are well-known to enhance photocatalytic activity (PCA) despite various other intrinsic crystal defects. In this study, we aim to elucidate the effect of zinc interstitials (Zn i) and VOs on PCA, which has applied as well as fundamental interest. To achieve this, the major hurdle of fabricating ZnO with controlled defect density requires to be overcome, where it is acknowledged that defect level control in ZnO is significantly difficult. In the present context, we fabricated nanostructures and thoroughly characterized their morphological (SEM, TEM), structural (XRD, TEM), chemical (XPS) and optical (photoluminescence, PL) properties. To fabricate the nanostructures, we adopted atomic layer deposition (ALD), which is a powerful bottom-up approach. However, to control defects, we chose polysulfone electrospun nanofibers as a substrate on which the non-uniform adsorption of ALD precursors is inevitable because of the differences in the hydrophilic nature of the functional groups. For the first 100 cycles, Znis were predominant in ZnO quantum dots (QDs), while the presence of VOs was negligible. As the ALD cycle number increased, VOs were introduced, whereas the density of Zni remained unchanged. We employed PL spectra to identify and quantify the density of each defect for all the samples. PCA was performed on all the samples, and the percent change in the decay constant for each sample was juxtaposed with the relative densities of Znis and VOs. A logical comparison of the relative defect densities of Znis and VOs suggested that the former are less efficient than the latter because of the differences in the intrinsic nature and the physical accessibility of the defects. Other reasons for the efficiency differences were elaborated.
Open Access
Selective isolation of the electron or hole in photocatalysis: ZnO–TiO2 and TiO2–ZnO core–shell structured heterojunction nanofibers via electrospinning and atomic layer deposition
(Royal Society of Chemistry, 2014-02-06) Kayaci, F.; Vempati S.; Ozgit Akgun, C.; Donmez, I.; Bıyıklı, Necmi; Uyar, Tamer
Heterojunctions are a well-studied material combination in photocatalysis studies, the majority of which aim to improve the efficacy of the catalysts. Developing novel catalysts begs the question of which photo-generated charge carrier is more efficient in the process of catalysis and the associated mechanism. To address this issue we have fabricated core-shell heterojunction (CSHJ) nanofibers from ZnO and TiO2 in two combinations where only the 'shell' part of the heterojunction is exposed to the environment to participate in the photocatalysis. Core and shell structures were fabricated via electrospinning and atomic layer deposition, respectively which were then subjected to calcination. These CSHJs were characterized and studied for photocatalytic activity (PCA). These two combinations expose electrons or holes selectively to the environment. Under suitable illumination of the ZnO-TiO 2 CSHJ, e/h pairs are created mainly in TiO2 and the electrons take part in catalysis (i.e. reduce the organic dye) at the conduction band or oxygen vacancy sites of the 'shell', while holes migrate to the core of the structure. Conversely, holes take part in catalysis and electrons diffuse to the core in the case of a TiO2-ZnO CSHJ. The results further revealed that the TiO2-ZnO CSHJ shows ∼1.6 times faster PCA when compared to the ZnO-TiO2 CSHJ because of efficient hole capture by oxygen vacancies, and the lower mobility of holes.
Open Access
Transformation of polymer-ZnO core-shell nanofibers into ZnO hollow nanofibers: Intrinsic defect reorganization in ZnO and its influence on the photocatalysis
(Elsevier, 2015) Kayaci, F.; Vempati S.; Ozgit Akgun, C.; Donmez, I.; Bıyıklı, Necmi; Uyar, Tamer
Photocatalytic activity (PCA) on semiconductors is known to be majorly influenced by specific surface area and intrinsic lattice defects of the catalyst. In this report, we tested the efficiencies of 1D ZnO catalysts of varying fiber diameter (80. nm and 650. nm of inner diameter) in two formats, viz. core-shell and hollow nanofibers, where the former is calcined to yield the latter. These nanofibrous catalysts were produced by combining electrospinning and atomic layer deposition processes which were then subjected to thorough characterization including photoluminescence (PL) unveiling the details of intrinsic defects/densities. During the thermal treatment, intrinsic defects are reorganized and as a result a new PL band is observed apart from some significant changes in the intensities of other emissions. The densities of various intrinsic defects from PL are compared for all samples and juxtaposed with the PCA. Careful scrutiny of the various results suggested an anti-correlation between surface area and PCA; i.e., higher surface area does not necessarily imply better PCA. Beyond a limit, the most deterministic factor would be the density of surface defects rather than the specific surface area. The results of this study enable the researchers to fabricate 1D semiconductor photocatalysts while striking the balance between surface area and density of defects.
Open Access
A versatile bio-inspired material platform for catalytic applications: Micron-sized "buckyball-shaped" TiO2 structures
(Royal Society of Chemistry, 2015) Erdogan, D. A.; Solouki, T.; Ozensoy, E.
A simple sol-gel synthesis method is presented for the production of micron-sized buckyball-like TiO2 architectures using naturally occurring Lycopodium clavatum (LC) spores as biotemplates. We demonstrate that by simply altering the calcination temperature and titanium(iv) isopropoxide : ethanol volume ratio, the crystal structure and surface composition of the buckyball-like TiO2 overlayer can be readily fine-tuned. After the removal of the biological scaffold, the unique surface morphology and pore structure of the LC biotemplate can be successfully transferred to the inorganic TiO2 overlayer. We also utilize photocatalytic degradation of Rhodamine B dye samples to demonstrate the photocatalytic functionality of these micron-sized buckyball-like TiO2 architectures. Moreover, we show that the photocatalytic activity of TiO2 overlayers can be modified in a controlled manner by varying the relative surface coverages of anatase and rutile domains. These results open a potential gateway for the synthesis of a variety of bio-inspired materials with unique surface properties and shapes comprised of reducible metal oxides, metal sulfides, mixed-metal oxides, and/or perovskites.
Open Access
ZnO nanostructures on electrospun nanofibers by atomic layer deposition/hydrothermal growth and their photocatalytic activity
(Materials Research Society, 2014) Kayaci, Fatma; Vempati, Sesha; Ozgit-Akgun, Cagla; Biyikli, Necmi; Uyar, Tamer
A hierarchy of nanostructured-ZnO was fabricated on the electrospun nanofibers by atomic layer deposition (ALD) and hydrothermal growth, subsequently. Firstly, we produced poly(acrylonitrile) (PAN) nanofibers via electrospinning, then ALD process provided a highly uniform and conformai coating of polycrystalline ZnO with a precise control on the thickness (50 nm). In the last step, this ZnO coating depicting dominant oxygen vacancies and significant grain boundaries was used as a seed on which single crystalline ZnO nanoneedles (average diameter and length of ∼25 nm and ∼600 nm, respectively) with high optical quality were hydrothermally grown. The detailed morphological and structural studies were performed on the resulting nanofibers, and the photocatalytic activity (PCA) was tested with reference to the degradation of methylene blue. The results of PCA were discussed in conjunction with photoluminescence response. The nanoneedle structures supported the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. The enhanced PCA, structural stability and reusability of the PAN/ZnO nanoneedles indicated that this hierarchical structure is a potential candidate for waste water treatment.