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1.
A transparent, thin-film TiO2 layer prepared by sol-gel deposition is shown to be more active for photocatalytic oxidation (PCO) of acetaldehyde, acetic acid, and toluene than Degussa P25 thin films. The sol-gel TiO2 adsorbs 30-70% less organic, but the PCO activity per adsorbed molecule is 3.5-8.5 times higher on the sol-gel TiO2 than on Degussa P25. In addition, less-reactive intermediates do not appear to form as readily on the sol-gel catalyst as they do on Degussa P25, and thus the sol-gel catalyst deactivates slower during toluene PCO. Rates were measured in transient experiments for a monolayer of adsorbed organic, and transient experiments are shown to be an effective way to measure rates, selectivities, surface coverages, and formation of less-reactive intermediates in the same set of experiments.  相似文献   

2.
The photocatalytic degradation of various organics such as phenol, p-nitrophenol, and salicylic acid was carried out with combustion-synthesized nano-TiO2 under UV and solar exposure. Under identical conditions of UV exposure, the initial degradation rate of phenol with combustion-synthesized TiO2 is 2 times higher than the initial degradation rate of phenol with commercial Degussa P-25 TiO2. The intermediates such as catechol (CC) and hydroquinone (HQ) were not detected during the degradation of phenol with combustion-synthesized TiO2, while both the intermediates were detected when phenol was degraded over Degussa P-25. This indicates that the rates of secondary photolysis of CC and HQ occur extremely faster than the rates at which they are formed from phenol and further implies that the primary hydroxylation step is rate limiting for the combustion-synthesized TiO2 aided photodegradation of phenol. The degradation rates of salicylic acid and p-nitrophenol were also investigated, and the rates were higher for combustion-synthesized titania compared to Degussa P-25 TiO2. Superior activity of combustion-synthesized TiO2 toward photodegradation of organic compounds can be attributed to crystallinity, higher surface area, more surface hydroxyl groups, and optical absorption at higher wavelength.  相似文献   

3.
Oxidation of arsenite, As(III), to arsenate, As(V), is required for the efficient removal of arsenic by many water treatment technologies. The photocatalyzed oxidation of As(III) on titanium dioxide, TiO2, offers an environmentally benign method for this unit operation. In this study, we explore the efficacy and mechanism of TiO2-photocatalyzed As(III) oxidation at circumneutral pH and over a range of As(III) concentrations approaching those typically encountered in water treatment systems. We focus on the effect of As adsorption on observed rates of photooxidation. Adsorption (in the dark) of both As(III) and As(V) on Degussa P25 TiO2 was examined at pH 6.3 over a range in dissolved arsenic concentrations, [As]diss, of 0.10-89 microM and 0.2 or 0.05 g L(-1) TiO2 for As(III) and As(V), respectively. Adsorption isotherms generally followed the Langmuir-Hinshelwood model with As(III) exhibiting an adsorption maxima of 32 micromol g(-1). As(V) adsorption did not reach a plateau under the experimental conditions examined; the maximum adsorbed concentration observed was 130 micromol g(-1). The extent of As(III) and As(V) adsorption observed at the beginning and end of the kinetic studies was consistent with that observed in the adsorption isotherms. Kinetic studies were performed in batch systems at pH 6.3 with 0.8-42 microM As(III) and 0.05 g L(-1) TiO2; complete oxidation of As(III) was observed within 10-60 min of irradiation at 365 nm. The observed effect of As(III) concentration on reaction kinetics was consistent with surface saturation at higher concentrations. Addition of phosphate at 0.5-10 microM had little effect on either As(III) sorption or its photooxidation rate but did inhibit adsorption of the product As(V). The selective use of hydroxyl radical quenchers and superoxide dismutase demonstrated that superoxide, O2-, plays a major role in the oxidation of As(III) to As(V).  相似文献   

4.
The simultaneous photocatalytic degradation of phenol and 4-nitrophenol and reduction of metal ions like copper (Cu2+) and chromium (Cr6+) was studied with solution combustion synthesized nanoanatase TiO2 (CS TiO2) and commercial titania, Degussa P-25. The presence of metal ion reduces the rate of degradation of phenol and 4-nitrophenol. It was found that Cu2+ reduction to Cu+ is accelerated in the presence of phenol. In the case of Cr6+, CS TiO2 enhances the initial adsorption of Cr6+ and complete reduction is achieved within the first 10 min of UV irradiation. The presence of phenol or 4-nitrophenol also enhances the initial adsorption of Cr6+ and its reduction. The metal ion reduction in the presence of CS TiO2 is compared with that of Degussa P-25. The rate of reduction of metal ions in presence of Degussa P-25 is twice as slow as that of CS TiO2 in presence of both phenol and 4-nitrophenol. The presence of Cu2+ and Cr6+ also induces the formation of the intermediates which were not observed for the phenol-CS TiO2 system. The formation and consumption of the intermediates are modeled with a simple series reaction mechanism. A detailed dual-cycle, multistep reaction mechanism of TiO2 photocatalysis for the simultaneous degradation and reduction is proposed and the model is developed following the network reduction technique. The kinetic rate constants in the model are evaluated for the systems studied.  相似文献   

5.
Here we report the simultaneous Cr(VI) reduction and 4-chlorophenol (4-CP) oxidation in water under visible light (wavelength > 400 nm) using commercial Degussa P25 TiO2. This remarkable observation was attributed to a synergistic effect among TiO2, Cr(VI), and 4-CP. It is well known that TiO2 alone cannot remove either 4-CP or Cr(VI) efficiently under visible light. Moreover, the interaction between Cr(VI) and 4-CP is minimal if not negligible. However, we found that the combination of TiO2, Cr(VI), and 4-CP together can enable efficient Cr(VI) reduction and 4-CP oxidation under visible light. The specific roles of the three ingredients in the synergistic system were studied parametrically. It was found that optimal concentrations of Cr(VI) and TiO2 exist for the Cr(VI) reduction and 4-CP oxidation. Cr(VI) was compared experimentally with other metals such as Cu(ll), Fe(lll), Mn(IV), Ce(IV), and V(V). Among all these metal ions, only Cr(VI) promotes the photocatalytic oxidation of 4-CP. The amount of 4-CP removed was directly related to the initial concentration of Cr(VI). The system was also tested with four other chemicals (aniline, salicylic acid, formic acid, and diethyl phosphoramidate). We found that the same phenomenon occurred for organics containing acid and/or phenolic groups. Cr(VI) was reduced at the same time as the organic chemicals being oxidized during photoreaction under visible light. The synergistic effect was also found with pure anatase TiO2 and rutile TiO2. This study demonstrates a possible economical way for environmental cleanup under visible light.  相似文献   

6.
The photocatalytic degradation of a herbicide derivative, chlorotoluron [3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 1], has been investigated in aqueous suspensions of titanium dioxide (TiO2) under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics of the model compound was investigated under different conditions such as type of TiO2, pH, catalyst concentration, substrate concentration, temperature, and in the presence of different electron acceptors such as hydrogen peroxide (H2O2), potassium persulfate (K2S2O8), and potassium bromate (KBrO3) besides molecular oxygen. TiO2 Degussa P25 was found to be a more efficient photocatalyst for the degradation of the model compound as compared with other photocatalysts. The degradation products were analyzed using GC/MS analysis technique and probable pathways for the formation of different products have been proposed.  相似文献   

7.
Photocatalytic activity of both commercial and homemade samples was tested for the degradation of toluene in the gas phase by using two different irradiation sources, UV and solar. The role played by humidity in affecting the final toluene degradation was discussed. Catalyst deactivation (due to the high toluene level, 1000 ppm) and subsequent regeneration, by washing with water, were analyzed. Highest degradations and corresponding kinetic constants were achieved in the case of the anatase/brookite composite samples, while the commercial ones (including P25 Degussa) showed lower efficiency. Various adsorbed aromatic species (benzoic acid, the major surface product hydroquinone, benzylic alcohol, benzaldehyde, and cresols) obtained by washing the exhaust catalysts were analyzed by HPLC. Parallel results were achieved by Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy. The presence of different photodegradation surface species for the various photocatalysts suggests the occurrence of different reaction pathways, depending on the fine physicochemical features of the specific TiO2 adopted in the reaction.  相似文献   

8.
Photocatalytic oxidation of arsenic(III): evidence of hydroxyl radicals   总被引:1,自引:0,他引:1  
Arsenic contamination has been found in the groundwater of several countries. Photocatalysis can rapidly oxidize arsenite (As(III)) to less labile and less toxic arsenate (As(V)), which then can be removed by adsorption onto photocatalyst surfaces. This study investigates the photocatalytic oxidation of As(III) to As(V) as a function of As(III) concentration, pH, catalyst loading, light intensity, dissolved oxygen concentration, type of TiO2 surfaces, and ferric ions to understand the kinetics and the mechanism of As(III) oxidation in the UV/TiO2 system. Photocatalytic oxidation of As(III) to As(V) takes place in minutes and follows zero-order kinetics. Benzoic acid (BA) was used as a hydroxyl radical (.OH) scavenger to provide evidence for the .OH as the main oxidant for oxidation of As(III). The .OH radical was independently generated by nitrate photolysis, and kinetics of As(III) oxidation by the .OH radical was determined. Formation of salicylic acid (SA) from the oxidation of BA by .OH also demonstrates the involvement of .OH in the mechanism of As(III) oxidation. The effect of Fe(III) on As(III) oxidation at different pH values with and without TiO2 under UV light was examined. The results suggest that .OH is the dominant oxidant for As(III) oxidation. Two commercially available TiO2 suspensions, Degussa P25 and Hombikat UV100, were tested for the removal of arsenic through oxidation of As(III) to As(V) followed by adsorption of As(V) onto TiO2 surfaces. Results showed that complete removal of arsenic below the World Health Organization drinking water limit of 10 microg/L could be achieved.  相似文献   

9.
Highly crystalline metastable bismuth titanate (Bi??TiO??) nanosheets are prepared via a simple green wet chemical route for the first time. The Bi??TiO??)photocatalysts were characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy dispersive spectrum analysis (EDS), X-ray diffraction (XRD), N? adsorption-desorption (BET), and UV-vis diffuse reflectance spectroscopy (DRS). Inspiringly, Bi??TiO?? nanosheets showed high photocatalytic activity for the degradation of nonbiodegradable azo dye under simulated sunlight and visible-light irradiation. The experimental results showed that the photocatalytic activity of the Bi??TiO?? nanosheets was superior to the commercial Degussa P25 TiO?, and demonstrated that the morphology and crystal structure have a distinct effect on the photocatalytic activity. The reasons for the high photocatalytic activity and the formation mechanism of Bi??TiO?? nanosheets are also discussed.  相似文献   

10.
Photocatalytic technologies were utilized to develop an environment-friendly system that is capable of removing and oxidizing organic pollutants from an air stream. A series of long-afterglow phosphors emitting long lifetime fluorescence was adapted to prepared TiO(2)-based composite photocatalysts for the photodegradation of gas-phase acetaldehyde. Although the photocatalytic reaction by an undoped titania (Degussa P25) was stopped immediately after turning off the irradiation light, the long-afterglow phosphor/nitorogen-doped TiO(2) (TiO(2-x)N(y)) composites maintained the acetaldehyde photodegradation ability even after turning off the light for a long time. This novel photocatalytic property may be attributed to the presence of the long-afterglow phosphor, which can reserve the light energy and generate the persistent fluorescence afterward as the light source for the photocatalytic reaction with the visible-light responsive TiO(2-x)N(y). The substitution of the undoped TiO(2) with TiO(2-x)N(y) was essential to use the fluorescence as a light source for photocatalysis. Such a self-fluorescence-assisted system could enhance the performance of photocatalysts for environmental cleanup.  相似文献   

11.
High-throughput screening was employed to evaluate bactericidal activities of hybrid Ag-TiO? nanoparticles comprising variations in TiO? crystalline phase, Ag content, and synthesis method. Hybrid Ag-TiO? nanoparticles were prepared by either wet-impregnation or UV photo deposition onto both Degussa P25 and DuPont R902 TiO? nanoparticles. The presence of Ag was confirmed by ICP, TEM, and XRD analysis. The size of Ag nanoparticles formed on anatase/rutile P25 TiO? nanoparticles was smaller than those formed on pure rutile R902. When activated by UV light, all hybrid Ag-TiO? nanoparticles exhibited stronger bactericidal activity than UV alone, Ag/UV, or UV/TiO?. For experiments conducted in the dark, bactericidal activity of Ag-TiO? nanoparticles was greater than either bare TiO? (inert) or pure Ag nanoparticles, suggesting that the hybrid materials produced a synergistic antibacterial effect unrelated to photoactivity. Moreover, less Ag(+) dissolved from Ag-TiO? nanoparticles than from Ag nanoparticles, indicating the antibacterial activities of Ag-TiO? was not only caused by releasing of toxic metal ions. It is clear that nanotechnology can produce more effective bactericides; however, the challenge remains to identify practical ways to take advantage of these exciting new material properties.  相似文献   

12.
冯晨  于洋 《食品工业科技》2021,42(3):304-309,319
为探究枸杞多糖(Lycium barbarum polysaccharide,LBP)对脂多糖(lipopolysaccharide,LPS)诱导的BV2小胶质细胞的保护作用。本研究利用MTT法检测细胞活性,ELISA检测炎症因子的分泌,Western Blot检测蛋白表达情况。结果显示,单独LPS处理BV2小胶质细胞后,细胞的活性无显著变化而细胞上清液中的炎症因子PGE2、IL-1β、IL-6及TNF-α释放显著增多;将枸杞多糖梯度与LPS诱导的BV2小胶质细胞共孵育24 h后,有效地提升了LPS诱导的BV2小胶质细胞的活性,同时显著抑制了LPS激活的BV2小胶质细胞炎症因子的释放(P<0.05);流式结果表明,LPS组小胶质细胞可产生大量ROS,小胶质细胞经不同浓度LBP处理12 h后,ROS含量显著降低(P<0.05);Western Blot检测结果显示,与对照组相比,LPS组和LBP组中NF-κB信号通路相关蛋白表达及细胞核内p65蛋白表达水平均显著上调(P<0.05),且与LBP浓度成反比,而细胞质内p65蛋白表达显著降低(P<0.05),且随着LBP浓度增加而降低。本研究表明,枸杞多糖对LPS激活的BV2小胶质细胞有显著的保护作用,对于LPS激活的BV2小胶质细胞引起的炎症反应具有抑制作用,同时能抑制小胶质细胞中ROS的含量以发挥抗氧化应激作用,同时有效地抑制LPS刺激后细胞内p-TAK1、iκB、p-iκB及p-p65的表达。  相似文献   

13.
Prostephanus truncatus (Horn) adults were treated in the laboratory with permethrin (25:75), deltamethrin, (1R)-phenothrin (20:80), lindane, pirimiphos-methyl, malathion, fenvalerate, and chlorpyrifos-methyl, by topical application, by exposure to treated filter papers, and by exposure to maize grain treated with dilute dust formations. Field trials were also carried out in Tanzania in a large wire mesh crib to compare the protection afforded to maize grain stored in small hessian bags (7.5 kg), with that of cobs wihout husks stored in wire mesh compartments. The superiority of the synthetic pyrethroids over the organophosphorus compounds was clearly demonstrated in all the experiments except that in which insects were exposed to treated filter papers, when the observations were not conclusive. In the field trial, loose grain was protected more effectively than cobs; permethrin dust applied at 2.5 ppm resulted in only 4% damage to loose grain in a storage period of 10 months.  相似文献   

14.
Joo-Shin  Kim 《Journal of food science》2005,70(3):C208-C213
ABSTRACT: Radical scavenging capacity and antioxidant activity of an E vitamer fraction from rice bran were investigated. The E vitamer fraction was prepared by a liquid-liquid extraction method. The free radical scavenging capacity of the E vitamer fraction was measured by the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) method at the concentration range of 2.5 to 640 ppm, whereas the antioxidant activities were measured by both the reducing power and ferric thiocyanate (FTC) methods at different concentrations (0, 2.5, 10, 40, and 160 ppm). Radical scavenging capacity of the fraction was effective up to 160 ppm, then remained stable. Also, at a concentration of 160 ppm, it was highly effective in inhibiting linoleic acid peroxidation. Similarly, superoxide scavenging and antioxidant activities of the E vitamer fraction were compared with those of the synthetic phenol compounds. Results showed that with a concentration of the E vitamer fraction at 160 ppm, the antioxidant activity was comparable to both butylated hydroxytoluene (BHT, 160 ppm) and butylated hydroxyanisole (BHA, 160 ppm). No significant differences (P > 0.05) were found among them. The E vitamer fraction may be a good substitute for the synthetic phenol antioxidants currently used in industry because the former is more natural and comparatively effective in its radical scavenging capacity and antioxidant activity.  相似文献   

15.
The spectroscopic and redox properties of iron(lll) protoporphyrin chloride (hemin) and cobalt(lll) meso-tetra-(4-carboxyphenyl) porphyrin chloride (CoTCP) were quantified in fluid solution and when anchored to mesoporous nanocrystalline TiO2 thin films. Surface binding was well-described by the Langmuir adsorption isotherm model from which adduct formation constants of 10(5) M(-1) and limiting surface coverages of 10(-8) mol/cm2 were abstracted. In acetonitrile and dimethyl sulfoxide electrolytes, TiO2 binding was found to induce a substantial negative shift in the M(III/II) formal reduction potentials. In DMSO electrolyte, the Co(III/II) and Fe(III/II) potentials were -559 and -727 mV versus ferrocenium/ferrocene (Fc+/Fc) and shifted to -782 and -1063 mV, respectively, after surface binding. The Bronsted acidity of the TiO2 surface was found to correlate with the measured reduction potentials. For TiO2 pretreated with aqueous solutions from pH 4-9, the Co(III/II) potential showed a -66 mV/pH unit change, while the Fe(llI/II) potential of hemin changed by -40 mV/pH from pH 1 to 14. Spectroelectrochemical data gave isosbestic, reversible spectral changes in the visible region assigned to M(III/II) redox chemistry with lambda(iso) = 410, 460, 530, 545, 568, and 593 nm for CoTCP/TiO2 and lambda(iso) = 408, 441, 500, 576, and 643 nm for hemin/TiO2. In aqueous solution, the CoTCP reduction potentials were also found to be pH dependent upon surface binding, with CoTCP = -583 mV and CoTCP/TiO2 = -685 mV versus Fc+/Fc at pH 6. For CoTCP/TiO2, the aqueous pH dependence of the potentials was -52 mV/pH. The rate constant for heme/TiO2 reduction of CCl4 increased from 3.9 +/- 0.7 x 10(-4) to 2.0 +/- 0.1 x 10(-3) s(-1) when the pH was raised from 4 to 8.  相似文献   

16.
Food safety issues and increases in food borne illnesses have promulgated the development of new sanitation methods to eliminate pathogenic organisms on foods and surfaces in food service areas. Electrolyzed oxidizing water (EO water) shows promise as an environmentally friendly broad spectrum microbial decontamination agent. EO water is generated by the passage of a dilute salt solution ( approximately 1% NaCl) through an electrochemical cell. This electrolytic process converts chloride ions and water molecules into chlorine oxidants (Cl(2), HOCl/ClO(-)). At a near-neutral pH (pH 6.3-6.5), the predominant chemical species is the highly biocidal hypochlorous acid species (HOCl) with the oxidation reduction potential (ORP) of the solution ranging from 800 to 900mV. The biocidal activity of near-neutral EO water was evaluated at 25 degrees C using pure cultures of Escherichia coli, Salmonella typhimurium, Staphylococcus aureus, Listeria monocytogenes, and Enterococcus faecalis. Treatment of these organisms, in pure culture, with EO water at concentrations of 20, 50, 100, and 120ppm total residual chlorine (TRC) and 10min of contact time resulted in 100% inactivation of all five organisms (reduction of 6.1-6.7log(10)CFU/mL). Spray treatment of surfaces in food service areas with EO water containing 278-310ppm TRC (pH 6.38) resulted in a 79-100% reduction of microbial growth. Dip (10min) treatment of spinach at 100 and 120ppm TRC resulted in a 4.0-5.0log(10)CFU/mL reduction of bacterial counts for all organisms tested. Dipping (10min) of lettuce at 100 and 120ppm TRC reduced bacterial counts of E. coli by 0.24-0.25log(10)CFU/mL and reduced all other organisms by 2.43-3.81log(10)CFU/mL.  相似文献   

17.
Laboratory selection experiments were undertaken in order for the resistance development of Tribolium confusum adults to diatomaceous earth (DE) to be assessed. Adults from an initial laboratory reared population (P) were selected by exposure on hard wheat treated with 800 ppm of DE for 4 days at 25 °C and 65% r.h. The surviving adults and their progeny were maintained on flour and 5% brewer's yeast until the emergence of the next generation of adults. The emerged (F1) adults were again exposed on treated hard wheat, as described above, and the whole procedure was repeated for 10 consecutive generations. Mortality of the emerged adults was assessed through bioassays that were undertaken in each generation at 25 °C and 65% r.h. In each bioassay, five dose levels of DE (250, 500, 800, 1000 and 1500 ppm) and four exposure intervals (24, 48 h, 7 and 14 days) were tested. Mortality of confused flour beetles generally declined at each dose rate and exposure interval with each generation, and significant differences were observed between the initial population (P) and after five or more (F5+) generations of selection.  相似文献   

18.
为改善蛋清液的起泡性,采用不同超声功率(120,240 W)和超声时间(1,5,10,20,30 min)的高场强超声(20 kHz)对蛋清蛋白进行改性.结果表明,在功率120 W下超声处理20 min,蛋清蛋白的起泡性最佳(266.7%),是未处理蛋清的6.9倍.超声处理显著降低了蛋清液的表观黏度、表面张力和粒径大小...  相似文献   

19.
The fathead minnow is a useful species for evaluating the toxicity of wastewater effluents. While this fish is widely used for "survival" studies of metal toxicity, little or no work has been done on the tissue distribution of metals in fathead minnows. To determine the distribution of tissue lead, aquarium studies were conducted for several weeks with fish maintained in soft synthetic freshwater. Lead- (II) nitrate was added to three aquaria attaining concentrations of 20-30 ppb (aquarium B), 100-140 ppb (aquarium C), and roughly 200 ppb (aquarium D). Results were compared to controls (aquarium A). During the initial week, the majority of aquarium D fish died, whereas few deaths occurred in the other groups. Lead accumulation was dose- and tissue-dependent, with highest uptake by the gills. Gill concentrations of aquarium D fish averaged about 4-fold higherthan in skeleton or skin and muscle. In vitro, lead (2.5-25 ppm) caused dose-dependent reductions in the ratio of reduced glutathione/oxidized glutathione (GSH/GSSG) in gills incubated in physiological buffer. These findings demonstrate that fathead minnow gills bind and accumulate waterborne lead rapidly and preferentially and raise the possibility that gill lipid peroxidation contributes to lead toxicity at low water hardness.  相似文献   

20.
A porous beta-Ga2O3 photocatalyst has been successfully prepared. The photocatalyst was characterized by XRD, N2 adsorption-desorption, TEM, UV/vis, and FTIR techniques. The photocatalytic activity of the sample was evaluated by the decomposition of benzene in air under UV light illumination and was compared with that of the commercial titania (Degussa P25) and Pt/P25. Results revealed that the synthesized Ga2O3 was porous beta-Ga2O3 and was highly photoactive for mineralizing benzene and its derivatives (e.g., toluene and ethylbenzene) to CO2 under ambient conditions. The photocatalytic conversion of benzene over beta-Ga2O3 was about 1 order of magnitude higher than that over P25, and no obvious deactivation of beta-Ga2O3 was observed during the prolonged operation of 80 h. The high activity and long-term stability of the Ga2O3 have been ascribed to its stronger oxidative capability and higher specific surface area in comparison with P25.  相似文献   

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