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1.
J Hazard Mater ; 380: 120866, 2019 12 15.
Artículo en Inglés | MEDLINE | ID: mdl-31326834

RESUMEN

Herein, the effect of material structure on photocatalytic activity in the decomposition of nocuous organic gases (1,3,5-trimethylbenzene (TMB) and o-xylene (XYL)) was investigated by synthesizing tricomposite photocatalysts of N-doped carbon quantum dots, ZnFe2O4, and BiOBr (NCQDs/ZFO/BOB) with different junctions. The NCQDs/ZFO/BOB material (NCQDs/ZFO/BOB1) synthesized using a one-pot method revealed the highest photocatalytic efficiency. The NCQDs in NCQDs/ZFO/BOB1 exhibited photoluminescence property that expanded the photo-absorption nature and acted as a mediator to enhance the Z-scheme charge transfer between ZFO and BOB. The photocatalytic activity exhibited by NCQDs/ZFO/BOB1 was higher than that exhibited by the selected reference materials (CQDs/ZFO/BOB, NCQDs/BOB, ZFO/BOB, BOB, NCQDs/ZFO, and ZFO). Results showed that the decomposition efficiencies of TMB and XYL in the presence of NCQDs/ZFO/BOB1 under specified operational conditions were 94.5% and 72.5%, respectively. Moreover, the synthesized NCQDs/ZFO/BOB photocatalysts displayed excellent stability. Herein, the conversion ratios of TMB and XYL into CO2 with NCQDs/ZFO/BOB1 and the intermediates formed during photocatalysis were assessed. Furthermore, a potential mechanism for the NCQDs/ZFO/BOB1-catalyzed organic gas decomposition was proposed. The hybridization access introduced herein thus provides a method for the intelligent synthesis of a new type of multicomponent nanocomposites for environmental remediation.

2.
J Hazard Mater ; 368: 778-787, 2019 04 15.
Artículo en Inglés | MEDLINE | ID: mdl-30739031

RESUMEN

In this study, we fabricate a novel ternary heterojunction comprising CoAl-layered double hydroxide, g-C3N4, and reduced graphene oxide (LDH/CN/RGO) with a notable 2D/2D/2D configuration using a simple one-step hydrothermal method. The visible-light-induced LDH/CN/RGO ternary heterojunctions displayed significantly enhanced photocatalytic performance towards the degradation of aqueous Congo red (CR, dye) and tetracycline (TC, antibiotic) contaminants, which is far superior to that observed for pristine CN (base material), LDH, P25 (reference), and binary CN/RGO and LDH/CN heterojunctions. In particular, the LDH/CN/RGO ternary heterojunction with RGO and LDH contents of 1 wt.% and 15 wt.%, respectively, exhibited the highest degradation activity among all the fabricated catalysts, and it also displayed exceptional stability during recycling experiments. The significant enhancement in the photocatalytic performance and good stability of existing LDH/CN/RGO ternary heterojunctions were primarily attributed to the large intimate interfacial contact between constituent CN, LDH, and RGO prompted by their exceptional 2D/2D/2D arrangement, which accelerates the interfacial charge-transfer processes to effectively hinder the recombination of photoexcited charge carriers. The present study provides new insights into the rational design and fabrication of novel g-C3N4-based 2D/2D/2D layered ternary heterojunctions as high-performance photocatalysts, and promotes their application in addressing diverse energy and environmental issues.

3.
J Hazard Mater ; 361: 64-72, 2019 01 05.
Artículo en Inglés | MEDLINE | ID: mdl-30176417

RESUMEN

To address the environmental hazard posed by the discharge of textile industry wastewater, we combined n-type (CdSe) and n-type (Ag3PO4) visible-light-responsive semiconductors to produce a photochemically stable n-n type heterostructured nanohybrid comprising metallic Ag (CdSe/Ag/Ag3PO4, CAA) and employed this material as a catalyst for the decomposition of phenol and rhodamine B (RhB). The physicochemical properties of CAA and reference photocatalysts were investigated using instrumental techniques. Compared to individual Ag3PO4 and CdSe, CAA showed an elevated photocatalytic decomposition efficiency for both target pollutants, which was mainly attributed to increased charge separation efficiency and explained by the operation of the Z-scheme reaction mechanism. Moreover, we probed the effects of initial pollutant concentration, AgNO3:NaH2PO4 molar ratio, and the CdSe:Ag3PO4 mass ratio of CAA on catalytic performance. Recycling tests revealed the high photochemical stability of CAA, which was ascribed to the prevention of Ag3PO4 photoreduction by electrons. Finally, a Z-scheme mechanism with vectorial charge transfer suggested for the visible-light-driven decomposition of pollutants over CAA nanohybrids was systematically discussed based on the results of scavenger tests and photoluminescence emission spectra analysis, and an explanation of the role of metallic Ag as a charge mediator was provided.

4.
J Hazard Mater ; 357: 19-29, 2018 09 05.
Artículo en Inglés | MEDLINE | ID: mdl-29859461

RESUMEN

Herein, highly efficient composite photocatalysts comprising black Cu-doped TiO2 nanoparticles (BCT) encapsulated within hierarchical flower-like NiAl-layered double hydroxide (LDH) microspheres were fabricated via a one-step hydrothermal route. Cu-doping and subsequent reduction treatment led to extended visible-light absorption of TiO2 in the resulting composites, as confirmed by ultraviolet-visible diffuse reflectance spectral analysis. Moreover, thorough investigations confirmed the strong interactions between LDH and BCT in the resulting BCT/LDH composites. Notably, the BCT/LDH composites exhibited remarkable performance in the degradation of hazardous materials (methyl orange and isoniazid), superior to that of the individual components, reference P25, and P25/LDH under visible-light irradiation. Moreover, the BCT/LDH composite containing 30 wt% of BCT displayed the highest photocatalytic performance among the synthesized photocatalysts and also exhibited high stability during recycling tests with no obvious change in the activity. The superior photodegradation activity of the BCT/LDH composites was primarily attributed to efficient transfer and separation of the photoinduced charge carriers, resulting from the intimate contact interfaces between LDH and BCT. This approach represents a promising route for the rational design of highly efficient and visible-light-active LDH-based composite photocatalysts for application in energy harvesting and environmental protection.

5.
Sci Total Environ ; 635: 741-749, 2018 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-29680764

RESUMEN

The efficient photocatalytic degradation of harmful organic pollutants (isoniazid (ISN) and 1,4-dioxane (DX)) via the Z-scheme electron transfer mechanism was accomplished using a photostable composite photocatalyst consisting of BiVO4, CdS, and reduced graphene oxide (RGO). Compared to their pristine counterparts, the RGO-mediated Z-scheme CdS/BiVO4 (CdS/RGO-BiVO4) nanocomposites exhibited superior degradation activities, mainly attributed to the prolonged charge separation. RGO was found to be involved in visible-light harvesting and acted as a solid-state electron mediator at the CdS/BiVO4 interface to realize an effective Z-scheme electron transfer pathway, avoid photocatalyst self-oxidation, and lengthen the life span of charge carriers. The results of reactive species scavenging experiments, photoluminescence measurements, and transient photocurrent measurements, as well as the calculated band potentials of the synthesized photocatalysts, supported the Z-scheme electron/hole pair separation mechanism. Additionally, the intermediates formed during the degradation of ISN and DX were identified, and a possible fragmentation pattern was proposed. This systematic work aims to develop photostable Z-scheme composites as unique photocatalytic systems for the efficient removal of harmful organic pollutants.


Asunto(s)
Bismuto/química , Contaminantes Ambientales/química , Grafito/química , Modelos Químicos , Nanocompuestos/química , Compuestos Orgánicos/química , Vanadatos/química , Catálisis , Procesos Fotoquímicos
6.
Chemosphere ; 202: 184-190, 2018 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-29571138

RESUMEN

Herein, a plug-flow reactor coated with one-dimensional (1D) TiO2 nanotube (TNT) heterostructures incorporated with g-C3N4 (CN) and metallic Cu (CN/Cu/TNT) nanocomposite and irradiated by a daylight lamp was newly applied for the mitigation of harmful indoor organic vapors. The CN/Cu/TNT catalyst showed high mitigation efficiency for all target pollutants, followed by Cu-incorporated TNT (Cu/TNT), CN-incorporated TNT (CN/TNT), TNT, and TiO2, in that order. The order of their photocatalytic activities agrees with that of the electron‒hole separation rates determined from their photoluminescence emission spectra. The mitigation efficiency of the CN/Cu/TNT catalyst increased as the CN-to-Cu/TNT percentage was increased from 1% to 10%, but subsequently decreased as the CN-to-Cu/TNT percentage increased to 20%. The mitigation efficiencies of the CN/Cu/TNT catalyst decreased with increasing relative humidity, feed pollutant concentrations, and airstream flow rates. However, in most cases, the reaction rates of the target compounds increased when the feed concentration was increased from 1 to 5 ppm. The mineralization rates of all target pollutants were lower than the corresponding photocatalytic mitigation rates, which could be ascribed to the production of CO and organic intermediates observed during the photocatalysis of the target pollutants. Nevertheless, the intermediates formed during the photocatalytic mitigation process would not cause significant adverse health effects to building occupants, because their concentrations were far below their exposure or threshold limit values. A probable mechanism for the photocatalytic mitigation of the organic vapors by the CN/Cu/TNT catalyst under daylight illumination was also proposed.


Asunto(s)
Contaminantes Atmosféricos/aislamiento & purificación , Contaminación del Aire Interior/prevención & control , Cobre/química , Nanotubos/química , Nitrilos/química , Titanio/química , Compuestos Orgánicos Volátiles/aislamiento & purificación , Catálisis , Humanos , Nanocompuestos/química
7.
Ultrason Sonochem ; 42: 517-525, 2018 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-29429698

RESUMEN

Herein, nanosheets of g-C3N4 (CN), prepared using a green ultrasonication process under various conditions, were combined with Ag/black TiO2 nanocomposites (AgBT) to create two-dimensional (2D) CN/Ag/black TiO2 tri-composites (CNAgBT). The thickness of the CN sheets varied with the ultrasonication conditions. The CNAgBT sample prepared using ultrasound-treated CN exhibited the highest average photocatalytic efficiencies for the degradation of two model pollutants, followed in decreasing order by AgBT, black TiO2 (BT), sheet CN, bulk CN, and TiO2. The order of pollutant degradation efficiencies by the photocatalysts was consistent with that of the charge carrier separation efficiencies. The degradation efficiency of the CNAgBT increased as the CN-to-AgBT ratio increased from 0.05 to 0.1, but decreased gradually for higher ratios between 0.15 and 0.20, indicating a lower optimal CN-to-AgBT ratio. A plausible photocatalytic degradation mechanism for the CNAgBT nanocomposites was proposed. Additionally, CNAgBT with a CN-to-AgBT ratio of 0.1 displayed a higher hydrogen generation rate with a maximum value of 21.5 mmol g-1 over 5 h than those of the AgBT and BT. Overall, the CNAgBT prepared using ultrasonication-treated CNs showed enhanced photocatalytic performance for both pollutant degradation and hydrogen generation.

8.
Ultrason Sonochem ; 35(Pt A): 440-448, 2017 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-28340948

RESUMEN

In this study, an ultrasound-aided hydrothermal-impregnation method was used to synthesize three-dimensional (3D) urchin-like CdS-TiO2 nanostructures (UCTs) with variable CdS content. The photocatalytic efficiencies (for degrading limonene and toluene vapor) of UCTs synthesized using the ultrasound-aided process were greater than those of UCTs fabricated without ultrasound treatment. In addition, the photocatalytic efficiencies of ultrasound-treated UCTs were greater than those of zero-dimensional ultrasound-treated CdS-TiO2 particles, which, in turn, were greater than those of untreated 3D TiO2. These results indicate that ultrasonication is an amicable process for the synthesis of UCTs with high photocatalytic activity. The enhanced activity of ultrasound-treated photocatalysts is ascribed to the greater charge carrier efficiency, adsorption capacity, and light absorption efficiency of these materials. The photocatalytic efficiencies of ultrasound-treated UCTs increased as the CdS loading was increased from 0.1% to 0.3%, gradually dropping as the loading was further increased to 3.0%, which indicated the existence of an optimum CdS loading. UCT photocatalytic efficiencies depended on the input concentration of target pollutants, relative humidity, and air flow rate. The photocatalytic efficiency for the decomposition of limonene mixed with 2-propanol was lower than that for limonene alone, likely due to the radical scavenging properties of 2-propanol. However, the photocatalytic degradation efficiency of the latter alcohol was not changed upon admixture. Toluene exhibited the same behavior. The mineralization ratios of both target compounds were lower than their decomposition ratios, indicating formation of byproducts due to incomplete oxidation. In addition to CO, three organic compounds were observed as photocatalytic decomposition byproducts of limonene (acetic acid, limonene oxide, and methacrolein) and toluene (benzene, benzaldehyde, and p-xylene). UCTs synthesized by the ultrasound-aided hydrothermal-impregnation method could be used to decompose organic vapors with an efficiency of up to 98%, depending on operating conditions.

9.
J Nanosci Nanotechnol ; 16(5): 4544-53, 2016 May.
Artículo en Inglés | MEDLINE | ID: mdl-27483788

RESUMEN

In this study, a N-, C-, and S-doped titania (NCS-TiO2) composite was prepared by combining the titanium precursor with a single dopant source, and the photocatalytic activity of this system for the decomposition of volatile organic compounds (VOCs) at indoor-concentration levels, under exposure to visible light, was examined. The NCS-TiO2 composite and the pure TiO2 photocatalyst, used as a reference, were characterized via X-ray diffraction, scanning electron microscopy, ultraviolet-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The average efficiencies of benzene, toluene, ethyl benzene, and o-xylene decomposition using NCS-TiO2 for were 70, 87, -100, and -100%, respectively, whereas the values obtained using the pure TiO2 powder were -0, 18, 49, and 51%, respectively. These results suggested that, for the photocatalytic decomposition of toxic VOCs under visible-light exposure conditions, NCS-TiO2 was superior to the reference photocatalyst. The decomposition efficiencies of the target VOCs were inversely related to the initial concentration and relative humidity as well as to the air-flow rate. The decomposition efficiencies of the target chemicals achieved with a conventional lamp/NCS-TiO2 system were higher than those achieved with a light emitting diode/NCS-TiO2 system. Overall, NCS-TiO2 can be used for the efficient decomposition of VOCs under visible-light exposure, if the operational conditions are optimized.

10.
J Colloid Interface Sci ; 482: 58-72, 2016 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-27491002

RESUMEN

Novel ZnIn2S4-g-C3N4/BiVO4 nanorod-based ternary nanocomposite photocatalysts with enhanced visible light absorption were synthesized and systematically characterized to confirm the formation of ZnIn2S4 marigold flowers, the layered structure of the g-C3N4, BiVO4 nanorods, and the formation of binary and ternary nanocomposites. The visible light absorption of BiVO4 was significantly improved after coupling with g-C3N4 and ZnIn2S4, which was confirmed by UV-visible diffuse reflectance spectroscopic analysis. Ternary ZnIn2S4-g-C3N4/BiVO4 nanocomposites exhibited excellent visible light photocatalytic decomposition efficiency (VL-PDE) when used for the degradation of congo red (CR) dye and metronidazole (MTZ) pharmaceutical, as well as excellent stability and reusability. The ternary 5%ZnIn2S4-50%-g-C3N4/BiVO4 nanocomposite showed higher VL-PDE for CR (81.5%) and MTZ (59%) degradation than the binary composites, g-C3N4 and BiVO4. Radical quenching experiments showed that h(+), OH, and O2(-) were the reactive radicals, validating that the Z-scheme charge carrier transfer mechanism was responsible for the enhanced VL-PDE of the ternary ZnIn2S4-g-C3N4/BiVO4 nanocomposites, which was further confirmed by photoluminescence analysis. Furthermore, kinetic studies showed that the degradation followed pseudo-first-order kinetics, and that the ternary photocatalysts could be reused up to three times with good stability. The enhanced visible light absorption, high surface area, high adsorption capacity, Z-scheme charge carrier transfer, and increased lifetime of photo-produced electron-hole pairs were responsible for the increased visible light photocatalytic decomposition efficiency.

11.
J Hazard Mater ; 314: 22-31, 2016 08 15.
Artículo en Inglés | MEDLINE | ID: mdl-27107232

RESUMEN

Two-dimensional nanosheet structures of N-doped TiO2/WO3 composites (WO3-N-TNSs) with varying WO3 loadings were synthesized by incorporating WO3 and N sources into sonochemically prepared TiO2 nanosheets (TNSs). These nanostructures were employed as photocatalysts, and their efficacy in the decomposition of hazardous hexane vapor was investigated. The photocatalytic efficiencies of the WO3-N-TNS composites were higher than those of N-doped TNS (N-TNS), which in turn were higher than the corresponding values for un-doped TNS. These variations were ascribed to the different light absorbance efficiencies, adsorption abilities, and charge carrier separations between the samples. An optimal WO3 loading for the performance of WO3-N-TNS was determined. Interestingly, the photocatalytic efficiency for hexane mixed with isopropyl alcohol (IPA) was lower than that for pure hexane, whereas the degradation efficiency for IPA did not vary with the feed method. Also investigated were the hexane conversion into CO2 over a representative WO3-N-TNS sample, the durability of the photocatalyst, and potential byproduct formation. Based on measurements of the hydroxyl radical population, a heterojunction-type mechanism was considered more plausible than a direct Z-scheme-type mechanism for the photocatalytic decomposition of hexane over the WO3-N-TNS photocatalysts.

12.
Ultrason Sonochem ; 28: 250-256, 2016 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-26384905

RESUMEN

Titania (TiO2) photocatalysts, each embedded with one of six metals (Ag, Ce, Co, Fe, Mg, and Mn), were prepared using a simplified ultrasonic process. The characteristics of the prepared metal-embedded TiO2 (metal-TiO2) were determined using transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, photoluminescence emission spectroscopy, UV-visible spectroscopy, and nitrogen adsorption-desorption. Except for Co-TiO2, the metal-TiO2 photocatalysts showed improved performance for the decomposition of gaseous benzene and toluene, which are two of the most problematic indoor air pollutants that can cause a variety of adverse health symptoms, under daylight lamp irradiation. Photocatalytic activity was greatest for the Mg-TiO2 sample, followed by, in order, the Ag-TiO2, Ce-TiO2, Fe-TiO2, Mn-TiO2, unmodified TiO2, and Co-TiO2 samples. Although Mg-TiO2 showed the least redshift in its light absorption and the highest electron-hole recombination rate among the metal-TiO2 photocatalysts, it yielded the highest photocatalytic activity, likely because of its increased adsorption capacity and anatase composition. The degradation of benzene and toluene over Mg-TiO2 improved as ultrasound treatment amplitude increased from 20 to 37 µm, then decreased gradually as amplitude was further increased to 49 µm. Degradation efficiency also improved as ultrasound operation time increased from 30 to 60 min, then decreased gradually as amplitude was further increased to 90 min. Overall, this process could be utilized to prepare metal-TiO2 photocatalysts with improved performance for the decomposition of gas phase pollutants under daylight lamp irradiation.

13.
Phys Chem Chem Phys ; 18(2): 1000-16, 2016 Jan 14.
Artículo en Inglés | MEDLINE | ID: mdl-26661565

RESUMEN

Novel, hierarchically nanostructured, redox-mediator-free, direct Z-scheme nanocomposite photocatalysts were synthesized via a facile hydrothermal method followed by wet-impregnation. The photocatalysts had a ZnIn2S4 marigold flower/Bi2WO6 flower-like (ZIS/BW) composition, which led to superior visible-light photocatalytic efficiency with excellent stability and reusability. The hierarchical marigold flower and flower-like morphologies of ZIS and BW were confirmed by FE-SEM and TEM analyses and further revealed that formation of the hierarchical marigold flower-like ZIS structure followed the formation of nanoparticles, growth of the ZIS petals, and self-assembly of these species. Powder X-ray diffraction and UV-visible diffuse reflectance spectroscopy analyses as well as the enhancement in the surface area and pore volume of the composite provide evidence of strong coupling between hierarchical BW and the ZIS nanostructures. The efficiency of the hierarchical direct Z-scheme photocatalysts for photocatalytic decomposition of metronidazole (MTZ) under visible-light irradiation was evaluated. The hierarchically nanostructured ZIS/BW nanocomposites with 50% loading of ZIS exhibited superior visible-light photocatalytic decomposition efficiency (PDE) compared to the composites with other percentages of ZIS and pristine BW. A probable mechanism for the enhanced photocatalytic efficiency of the ZIS/BW composite in MTZ degradation under visible irradiation was proposed. Radical quenching studies demonstrated that h(+), ˙OH, and O2˙(-) are the primary reactive radicals involved, which confirms that the Z-scheme mechanism of transfer of charge carriers accounts for the higher photocatalytic activity. Kinetic analysis revealed that MTZ degradation follows pseudo-first-order kinetics and the reusability of the composite catalyst for up to four cycles confirms the excellent stability of the hierarchical structure. It is concluded that the hierarchical structure of the ZIS/BW photocatalyst, synergic effect, Z-scheme transfer of the charge carrier, high concentration of (˙OH) radical formation and the significant reduction in the charge carrier recombination account for the enhanced efficiency of the catalyst for photocatalytic decomposition of metronidazole by visible light under the present reaction conditions.

14.
Dalton Trans ; 44(36): 16024-35, 2015 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-26286295

RESUMEN

This article reports novel ternary composites consisting of Fe2O3 nanorods, TiO2 nanoparticles, and graphene oxide (GO) flakes that provide enhanced photocatalytic performance and stability. Fe2O3 nanorods grow evenly and embed themselves on the agglomerated TiO2/GO surface, which facilitate the formation of heterojunctions for effective migration of charge carriers at the interface of Fe2O3/TiO2 in the ternary composites. The formation of heterostructured Fe2O3-TiO2/GO composites and the effect of GO addition on the photophysical properties of the composites were systematically investigated using various spectroscopic techniques. The photocatalytic performance of Fe2O3 was improved by coupling with TiO2 in the presence of GO, suggesting uncommon electron transfer from the conduction band of Fe2O3 to that of TiO2via GO under visible-light irradiation. An improved charge separation in the composite materials compared with that in bare Fe2O3 was confirmed by drastic fluorescence quenching and stronger absorption in the visible range. The optimum content of GO in the ternary composite was 1.0 wt%, which exhibited enhanced photocatalytic activity. The synergistic effect, heterostructured composite and role of GO, as an electron transporter, in the ternary composites account for the enhanced photocatalytic activity.

15.
J Hazard Mater ; 299: 462-70, 2015 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-26241772

RESUMEN

This article reports a novel ternary nanocomposite consisting of ZnO, g-C3N4, and graphene oxide (GO) that provides enhanced photocatalytic performance and stability. The ZnO nanospheres disperse evenly and embed themselves in the porous g-C3N4. Composites with various g-C3N4 and GO to ZnO weight ratios were synthesized and characterized systematically. The results indicated that the absorption of binary g-C3N4/ZnO nanocomposites shifted to a lower energy compared to pure ZnO in a fashion consistent with the loading content of g-C3N4. Notably, the loading content of GO in the ZnO-g-C3N4 composite resulted in increased absorption in the visible range and improved charge separation efficiency, thereby drastically improving photocatalytic activity. Successful hybridization of ternary nanocomposite was confirmed by drastic quenching of fluorescence and broader visible light absorption. The optimal content of g-C3N4 in the ZnO-g-C3N4 composite was 50%, which exhibited the effective hybridization between ZnO and g-C3N4, and high photocatalytic efficiency. However, the photocatalytic degradation of the ternary nanocomposite showed performance that was two times greater than ZnO-g-C3N4, exhibiting 99.5% degradation efficiency after just 15 min of light irradiation. The combined heterojunction and synergistic effects of this composite account for the improved photocatalytic activity.

16.
ACS Appl Mater Interfaces ; 7(31): 17138-54, 2015 Aug 12.
Artículo en Inglés | MEDLINE | ID: mdl-26186618

RESUMEN

Novel redox-mediator-free direct Z-scheme CaIn2S4 marigold-flower-like/TiO2 (CIS/TNP) photocatalysts with different CaIn2S4 weight percentages were synthesized using a facile wet-impregnation method. Uniform hierarchical marigold-flower-like CaIn2S4 (CIS) microspheres were synthesized using a hydrothermal method. Field-emission scanning electron microscopy and transmission electron microscopy analyses suggested that the formation and aggregation of nanoparticles, followed by the growth of petals or sheets and their subsequent self-assembly, led to the formation of the uniform hierarchical marigold-flower-like CIS structures. The photocatalytic degradation efficiency of the direct Z-scheme CIS/TNP photocatalysts was evaluated through the degradation of the pharmaceutical compounds isoniazid (ISN) and metronidazole (MTZ). The direct Z-scheme CaIn2S4 marigold-flower-like/TiO2 (1%-CIS/TNP) photocatalyst showed enhanced performance in the ISN (71.9%) and MTZ (86.5%) photocatalytic degradations as compared to composites with different CaIn2S4 contents or the individual TiO2 and CaIn2S4. A possible enhancement mechanism based on the Z-scheme formed between the CIS and TNP for the improved photocatalytic efficiency was also proposed. The recombination rate of the photoinduced charge carriers was significantly suppressed for the direct Z-scheme CIS/TNP photocatalyst, which was confirmed by photoluminescence analysis. Radical-trapping studies revealed that photogenerated holes (h+), •OH, and O2•- are the primary active species, and suggested that the enhanced photocatalytic efficiency of the 1%-CIS/TNP follows the Z-scheme mechanism for transferring the charge carriers. It was further confirmed by hydroxyl (•OH) radical determination via fluorescence techniques revealed that higher concentration of •OH radical were formed over 1%-CIS/TNP than over bare CIS and TNP. The separation of the charge carriers was further confirmed using photocurrent and electron spin resonance measurements. Kinetic and chemical oxygen demand analyses were performed to confirm the ISN and MTZ degradation. The results demonstrated that the direct Z-scheme CIS/TNP photocatalyst shows superior decomposition efficiency for the degradation of these pharmaceuticals under the given reaction conditions.

17.
J Air Waste Manag Assoc ; 65(3): 365-73, 2015 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-25947132

RESUMEN

UNLABELLED: Iron-functionalized titanium dioxide (TiO2) composites with various Fe-to-Ti ratios were prepared on flexible glass fibers (GF-Fe-TiO2) via a sol-gel method, followed by a dip-coating process. The photocatalytic ability of these composites in degrading selected volatile organic compounds (VOCs; benzene, toluene, ethylbenzene, and o-xylene [BTEX]) at indoor concentration levels was examined. The GF-Fe-TiO2 composites were characterized using scanning electron microscopy, energy-dispersive X-ray elemental analysis, ultraviolet (UV)-visible spectroscopy, and X-ray diffraction. The GF-Fe-TiO2 composites showed superior photocatalytic performance to that of a reference glass fiber-supported TiO2 photocatalyst for the treatment of BTEX under visible light. However, this trend was reversed under UV irradiation. Specifically, the average BTEX photocatalytic efficiencies of the 0.01-GF-Fe-TiO2 composite in a 3-hr visible-light photocatalytic process were 4%, 33%, 51%, and 74%, respectively. Conversely, the average BTEX photocatalytic efficiencies obtained for GF-TiO2 were close to 0%, 5%, 16%, and 29%, respectively. These findings demonstrated that the GF-Fe-TiO2 composites could be applied to photocatalytically purify BTEX, especially under visible-light exposure. Moreover, the GF-Fe-TiO2 composites prepared with different Fe-to-Ti ratios displayed different BTEX photocatalytic decomposition efficiencies under visible or UV light, allowing for optimization of the Fe-to-Ti ratio (which was found to be 0.01). IMPLICATIONS: The application of nanomaterials for air purification necessitates a supporting material to stabilize them while in contact with the treated air in the photocatalytic chamber. Glass fibers have an obvious advantage over other supporting materials mainly because of its flexibility, which makes it much easier to handle. However, the applications of glass fiber-supported, visible light-activated photocatalysts to the treatment of air pollutants are rarely reported in literature. Accordingly, this study aimed to investigate the applicability of glass fiber-supported Fe-TiO2 for the purification of VOCs under visible- as well as UV-light exposure.


Asunto(s)
Derivados del Benceno/química , Benceno/química , Fotólisis , Tolueno/química , Xilenos/química , Contaminantes Atmosféricos/química , Catálisis , Vidrio , Hierro/química , Luz , Titanio/química
18.
J Hazard Mater ; 283: 680-8, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-25464310

RESUMEN

This study was conducted under visible-light exposure to investigate the photocatalytic characteristics of a multiwalled carbon nanotube/titania (TiO2) composite nanofiber (MTCN) using a continuous-flow tubular reactor. The MTCN was prepared by a sol-gel process, followed by an electrospinning technique. The photocatalytic decomposition efficiency for limonene on the MTCN was higher than those obtained from reference TiO2 nanofibers or P25 TiO2, and the experimental results agreed well with the Langmuir-Hinshelwood model. The CO concentrations generated during the photocatalysis did not reach levels toxic to humans. The mineralization efficiency for limonene on the MTCN was also higher than that for P25 TiO2. Moreover, the mineralization efficiency obtained using the MTCN increased steeply from 8.3 to 91.1% as the residence time increased from 7.8 to 78.0s, compared to the increase in the decomposition efficiencies for limonene from 90.1 to 99.9%. Three gas-phase intermediates (methacrolein, acetic acid, and limonene oxide) were quantitatively determined for the photocatalysis for limonene over the MTCN, whereas only two intermediates (acetic acid and limonene oxide) were quantitatively determined over P25 TiO2. Other provisional gas-phase intermediates included cyclopropyl methyl ketone and 2-ethylbutanal.


Asunto(s)
Contaminantes Atmosféricos/química , Ciclohexenos/química , Luz , Nanofibras/química , Nanotubos de Carbono/química , Fotólisis , Terpenos/química , Titanio/química , Dióxido de Carbono/química , Monóxido de Carbono/química , Limoneno
19.
Environ Technol ; 35(17-20): 2132-9, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-25145164

RESUMEN

In this study, one-dimensional rod-shaped titania (RST) and nitrogen-doped RST (N-RST) with different ratios of N to Ti were prepared using a hydrothermal method and their applications for purification of indoor toxic organic contaminants in a plug-flow reactor were examined under visible or ultraviolet (UV) irradiation. The surface characteristics of as-prepared photocatalysts were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), and UV-visible spectroscopy. The TEM images revealed that both pure RSTs and N-RSTs displayed uniform and nanorod-shaped structures. XRD revealed that the photocatalysts had crystalline TiO2. The UV-visible spectra demonstrated that the N-RSTs could be activated in the visible region. In most cases, N-RSTs showed higher degradation efficiencies than pure RSTs under visible-light and UV irradiation. N-RSTs with a N-to-Ti ratio of 0.5 exhibited the highest degradation efficiencies of benzene, toluene, ethyl benzene, and o-xylene (BTEX), suggesting the presence of an optimal N-to-Ti ratio for preparation of N-RSTs. In addition, the average degradation efficiencies of BTEX determined for the N-RSTs with a N-to-Ti ratio of 0.5 under visible-light irradiation for the lowest initial concentration (IC, 0.1 ppm) were 19%, 53%, 85%, and 92%, respectively, while the degradation efficiencies for the highest IC (2.0 ppm) were 2%, 8%, 17%, and 33%. These values decreased as the stream flow rate increased. Overall, the as-prepared N-RSTs could be effectively applied for degradation of toxic gas-phase organic contaminants under visible-light as well as UV irradiation.


Asunto(s)
Contaminantes Atmosféricos/análisis , Restauración y Remediación Ambiental/instrumentación , Gases/análisis , Compuestos Orgánicos/análisis , Contaminantes Atmosféricos/química , Gases/química , Nitrógeno/química , Compuestos Orgánicos/química , Procesos Fotoquímicos , Titanio/química
20.
J Environ Qual ; 43(5): 1519-26, 2014 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-25603237

RESUMEN

Although analysis of long-term data is necessary to obtain reliable information on characteristics of atmospheric visibility and its relationship with air pollution, it has rarely been performed. Therefore, a long-term evaluation of atmospheric visibility in characteristically different Korean cities, as well as a remote island, during 2001 to 2009, was performed in this study. In general, visibility decreased in the studied areas during the 9-yr study period. In addition, all areas displayed a distinct seasonal trend, with high visibility in the cold season relative to the warm season. Weekday visibility, however, did not significantly differ from weekend visibility. Similarly, the number of days per year for both low (<10 km) and high visibility (>19 km) fluctuated during the study period. Busan (a coastal city) exhibited the highest visibility, with an overall average of 17.6 km, followed by Daegu (a basin city), Ulsan (with concentrated petrochemical industries), Ullungdo (a remote island), and Seoul (the capital of Korea). Visibility was found to be significantly correlated with target air pollutants, except for ozone, for all metropolitan cities, whereas it was significantly correlated only with particulate matter with an aerodynamic diameter <10 µm (PM10) and ozone on the remote island (Ullungdo). Among the metropolitan cities, Seoul exhibited the lowest visibility for both the PM10 standard exceedance and non-exceedance days, followed by Ulsan, Daegu, and Busan. The results of this study can be used to establish effective strategies for improving urban visibility and air quality.

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