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1.
Lanthanum-modified TiO2 photocatalysts (0.2–1.5 wt% La) were investigated in the methanol decomposition in an aqueous solution. The photocatalysts were prepared by the common sol-gel method followed by calcination. The structural (X-ray diffraction, Raman, X-ray photoelectron spectroscopy), textural (N2 physisorption), and optical properties (diffuse reflectance spectroscopy, photoelectrochemical measurements) of all synthetized nanomaterials were correlated with photocatalytic activity. Both pure TiO2 and La-doped TiO2 photocatalysts proved higher yields of hydrogen in comparison to photolysis. The photocatalyst with optimal amount of lanthanum (0.2 wt% La) showed almost two times higher amount of hydrogen produced at the same time as in the presence of pure TiO2. The photocatalytic activity increased with both increasing photocurrent response and decreasing amount of lattice and surface O species. It has been shown that both direct and indirect mechanisms of methanol photocatalytic oxidation participate in the production of hydrogen. Both direct and indirect mechanisms take part in the formation of hydrogen.  相似文献   

2.
The photocatalytic reduction of CO2 with H2O was investigated using Cu/TiO2 photocatalysts in aqueous solution. For this purpose, Cu/TiO2 photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N2 physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO2 decreased in the presence of Cu/TiO2 in comparison to pure TiO2, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H2 production necessary for CO2 reduction more difficult.  相似文献   

3.
The study is aimed at evaluating the potential of immobilized TiO2-based zeolite composite for solar-driven photocatalytic water treatment. In that purpose, TiO2-iron-exchanged zeolite (FeZ) composite was prepared using commercial Aeroxide TiO2 P25 and iron-exchanged zeolite of ZSM5 type, FeZ. The activity of TiO2-FeZ, immobilized on glass support, was evaluated under solar irradiation for removal of diclofenac (DCF) in water. TiO2-FeZ immobilized in a form of thin film was characterized for its morphology, structure, and composition using scanning electron microscopy/energy-dispersive x-ray spectroscopy (SEM/EDX). Diffuse reflectance spectroscopy (DRS) was used to determine potential changes in band gaps of prepared TiO2-FeZ in comparison to pure TiO2. The influence of pH, concentration of hydrogen peroxide, FeZ wt% within the composite, and photocatalyst dosage on DCF removal and conversion efficiency by solar/TiO2-FeZ/H2O2 process was investigated. TiO2-FeZ demonstrated higher photocatalytic activity than pure TiO2 under solar irradiation in acidic conditions and presence of H2O2.  相似文献   

4.
TiO2:Nb nanopowders within a dopant concentration in the range of 0.1?C15?at.% were prepared by one-step flame spray synthesis. Effect of niobium doping on structural, optical and photocatalytic properties of titanium dioxide nanopowders was studied. Morphology and structure were investigated by means of Brunauer?CEmmett?CTeller isotherm, X-ray diffraction and transmission electron microscopy. Diffuse reflectance and the resulting band gap energy were determined by diffuse reflectance spectroscopy. Photocatalytic activity of the investigated nanopowders was revised for the photodecomposition of methylene blue (MB), methyl orange (MO) and 4-chlorophenol under UVA and VIS light irradiation. Commercial TiO2-P25 nanopowder was used as a reference. The specific surface area of the powders was ranging from 42.9?m2/g for TiO2:0.1?at.% Nb to 90.0?m2/g for TiO2:15?at.% Nb. TiO2:Nb particles were nanosized, spherically shaped and polycrystalline. Anatase was the predominant phase in all samples. The anatase-related transition was at 3.31?eV and rutile-related one at 3.14?eV. TiO2:Nb nanopowders exhibited additional absorption in the visible range. In comparison to TiO2-P25, improved photocatalytic activity of TiO2:Nb was observed for the degradation of MB and MO under both UVA and VIS irradiation, where low doping level (Nb?<?1?at.%) was the most effective. Niobium doping affected structural, optical and photocatalytic properties of TiO2. Low dopant level enhanced photocatalytic performance under UVA and VIS irradiation. Therefore, TiO2:Nb (Nb?<?1?at.%) can be proposed as an efficient selective solar light photocatalyst.  相似文献   

5.

Background

The photocatalytic degradation of pyrene under UV (125?W Hg-Arc, 10.4?mW/cm2) irradiation of TiO2 aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu2+, Fe3+, Ag+, and Au3+, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1?eV) of TiO2, the photoexcited electron transfer occurs more readily and reduces electron?Chole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO2 because of rapid Fermi energy equilibrium between the CB of TiO2 and its surface adsorbed metal ions.

Results and discussion

The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni2+ having more negative reduction potential (?0.25?eV) than the CB of TiO2 imparts negligible co-catalytic activity to TiO2 photoreaction. It also revealed that loading of Au3+ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe+3 and Au3+ ions gradually increases from 0.1 to 2?wt.%, the pyrene photodecomposition rate also become faster.  相似文献   

6.
The simultaneous photocatalytic removal of nitrate from aqueous environment in presence of organic hole scavenger using TiO2 has long been explored. However, the use of unmodified TiO2 in such reaction resulted in non-performance or release of significant amount of undesirable reaction products in the process, a problem that triggered surface modification of TiO2 for enhanced photocatalytic performance. Previous studies focused on decreasing rate of charge carrier recombination and absorption of light in the visible region. Yet, increasing active sites and adsorption capacity by combining TiO2 with a high surface area adsorbent such as activated carbon (AC) remains unexploited. This study reports the potential of such modification in simultaneous removal of nitrates and oxalic acid in aqueous environment. The adsorptive behaviour of nitrate and oxalic acid on TiO2 and TiO2/AC composites were studied. The Langmuir adsorption coefficient for nitrate was four times greater than that of oxalic acid. However, the amount of oxalic acid adsorbed was about 10 times greater than the amount of nitrate taken up. Despite this advantage, the materials did not appear to produce more active photocatalysts for the simultaneous degradation of nitrate and oxalic acid. The photocatalytic activity of TiO2 and its carbon-based composites was improved by combination with Cu2O particles. Consequently, 2.5 Cu2O/TiO2 exhibited the maximum photocatalytic performance with 57.6 and 99.8% removal of nitrate and oxalic acid, respectively, while selectivity stood at 45.7, 12.4 and 41.9% for NH4+, NO2? and N2, respectively. For the carbon based, 2.5 Cu2O/TiO2-20AC showed removal of 12.7% nitrate and 80.3% oxalic acid and achieved 21.6, 0 and 78.4% selectivity for NH4+, NO2? and N2, respectively. Using the optimal AC loading (20 wt%) resulted in significant decrease in the selectivity for NH4+ with no formation of NO2?, which unveils that selectivity for N2 and low/no selectivity for undesirable products can be manipulated by controlling the rate of consumption of oxalic acid. In contract, no nitrate reduction was observed with Cu2O promoted TiO2-T and its TiO2-(T)-20AC, which may be connected to amorphous nature of TiO2-T and perhaps served as charge carrier trapping sites that impeded activity.  相似文献   

7.

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO2 has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e cb) with electron holes (hvb+) on the irradiated TiO2 surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO42−) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO2 photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.  相似文献   

8.
We have successfully synthesized the composites of two-phase g-C3N4 heterojunction photocatalysts by one-step method. And the reduced graphene oxide/two-phase g-C3N4 heterojunction photocatalyst was fabricated via a facile hydrothermal reduction method. The characterization results indicated that the two-phase g-C3N4 was integrated closely, and the common phenomenon of agglomeration for g-C3N4 was significantly reduced. Moreover, the oxidized graphene was reduced successfully in the composites and the graphene was overlaid on the surface or the interlayers of g-C3N4 heterojunction composite uniformly. In addition, we have carried out the photocatalytic activity experiments by H2 evolution and rhodamine B removal, tetracycline removal under the visible light irradiation. The results revealed that the composite has improved the separation efficiency a lot than the pure photocatalyst. The photocurrent test demonstrated that the recombination of electrons and holes were efficiently inhibited as well as enhanced the photocatalytic activity. The 0.4% rGO loaded samples, 0.4% rGOCN2, own the best performance. Its rate of H2 evolution was 15 times as high as that of the pure g-C3N4.  相似文献   

9.
Li X  Zou X  Qu Z  Zhao Q  Wang L 《Chemosphere》2011,83(5):674-679
In this work, Ag-doping TiO2 nanotubes were prepared and employed as the photocatalyst for the degradation of toluene. The TiO2 nanotube powder was produced by the rapid-breakdown potentiostatic anodization of Ti foil in chloride-containing electrolytes, and then doped with Ag through an incipient wetness impregnation method. The samples were characterized by scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, surface photovoltage measurements, X-ray photoelectron spectroscopy and N2 adsorption. The nanotubular TiO2 photocatalysts showed an outer diameter of approximately 40 nm, fine mesoporous structure and high specific surface area. The photocatalytic activity of Ag-doping TiO2 nanotube powder was evaluated through photooxidation of gaseous toluene. The results indicated that the degradation efficiency of toluene could get 98% after 4 h reaction using the Ag-doping TiO2 nanotubes as the photocatalyst under UV light illumination, which was higher than that of the pure TiO2 nanotubes, Ag-doping P25 or P25. Benzaldehyde species could be observed during the photocatalytic oxidation monitored by in situ FTIR, and the formed benzaldehyde intermediate during reaction would be partially oxidized into CO2 and H2O.  相似文献   

10.
Annihilation of electrons–holes recombination process is the main remedy to enhance the photocatalytic activity of the semiconductors photocatalysts. Doping of this class of photocatalysts by foreign nanoparticles is usually utilized to create high Schottky barrier that facilitates electron capture. In the literature, because nonpolar nanoparticles (usually pristine metals, e.g., Ag, Pt, Au, etc.) were utilized in the doping process, the corresponding improvement was relatively low. In this study, CdSO4-doped TiO2 nanoparticles are introduced as a powerful and reusable photocatalyst for the photocatalytic degradation of methomyl pesticide in concentrated aqueous solutions. The utilized CdSO4 nanoparticles form polar grains in the TiO2 matrix due to the electrons leaving characteristic of the sulfate anion. The introduced nanoparticles could successfully eliminate the harmful pesticide under the sunlight radiation within a very short time (less than 1 h), with a removal capacity reaching 1,000 mg pesticide per gram of the introduced photocatalyst. Moreover, increase in the initial concentration of the methomyl did not affect the photocatalytic performance; typically 300, 500, 1,000, and 2,000 mg/l solutions were completely treated within 30, 30, 40, and 60 min, respectively, using 100 mg catalyst. Interestingly, the photocatalytic efficiency was not affected upon multiple use of the photocatalyst. Moreover, negative activation energy was obtained which reveals super activity of the introduced photocatalyst. The distinct photocatalytic activity indicates the complete annihilation of the electrons–holes recombination process and abundant existence of electrons on the catalyst surfaces due to strong electrons capturing the operation of the utilized polar CdSO4 nanoparticles. The introduced photocatalyst has been prepared using the sol–gel technique. Overall, the simplicity of the synthesizing procedure and the obtained featured photocatalytic activity strongly recommend the introduced nanoparticles to treat the methomyl-containing polluted water.  相似文献   

11.
This work aimed to optimize high-performance photocatalysts based on graphene oxide/titanium dioxide (GO/TiO2) nanocomposites for the effective degradation of aqueous pollutants. The catalytic activity was tested against the degradation of dichloroacetic acid (DCA), a by-product of disinfection processes that is present in many industrial wastewaters and effluents. GO/TiO2 photocatalysts were prepared using three different methods, hydrothermal, solvothermal, and mechanical, and varying the GO/TiO2 ratio in the range of 1 to 10%. Several techniques were applied to characterize the catalysts, and better coupling of GO and TiO2 was observed in the thermally synthesized composites. Although the results obtained for DCA degradation showed a coupled influence of the composite preparation method and its composition, promising results were obtained with the photocatalysts compared to the limited activity of conventional TiO2. In the best case, corresponding to the composite synthesized via hydrothermal method with 5% of GO/TiO2 weight ratio, an enhancement of 2.5 times of the photocatalytic degradation yield of DCA was obtained compared to bare TiO2, thus opening more efficient ways to promote the application of photocatalytic remediation technologies.  相似文献   

12.

Acetaminophen (ACT) is one of the most frequently detected pharmaceuticals in aqueous environments, and treatment of ACT were generally carried out by photocatalytic degradations under high energy UV irradiation. In this study, potassium ferricyanide was utilized as a quadruple-elemental dopant in a TiO2 photocatalyst in order to enhance its visible-light activity. Two critical parameters (amounts of dopants and durations of calcination) of the synthesis of the photocatalyst by a sol–gel method were systematically evaluated. Crystal structure of the doping TiO2 was examined by X-ray diffraction while the effects of the two parameters on the photocatalytic activity were elucidated by various characterizations. Increasing the amount of dopant or the duration of calcination red-shifted the UV–vis DRS of the doped TiO2. The estimated band gap energy of the doped TiO2 decreased slightly as the amount of dopant increased, but it increased as the duration of calcination increased. The FT-IR yielded characteristic peaks that revealed the effects of the two parameters, whereas the SEM images revealed the morphological evolutions of each effect. The photocatalyst, synthesized at optimum conditions was able to remove 99.1 % acetaminophen with rate constant of 7.9 × 10−3 min−1, which was 4.88 times greater than virgin TiO2. In general, this study not only optimized synthetic conditions of the new visible-light active photocatalyst for ACT degradation but also presented characterizations conducted by SEM, XRD, UV–vis DRS, and FTIR to elucidate the relationship between modified structure and the photocatalytic activity.

Effects of doping amounts of K3[Fe(CN)6] and calcunation duration on visible light absorbance of TiO2 photocatalysts

  相似文献   

13.
纳米TiO2/活性炭复合光催化剂的制备及其对甲醛气体降解   总被引:2,自引:2,他引:0  
研究了纳米TiO2/活性炭复合光催化剂对空气中典型污染气体甲醛的光催化降解特性。采用扫描电镜(SEM)表征复合催化剂的表面特征。结果显示,经改性后的纳米TiO2在复合催化剂表面分布均匀,呈球状。对甲醛气体的降解实验显示TiO2负载量为1%时对甲醛的去除效果最好,6 h去除率为61.7%。结果显示复合催化剂把甲醛气体分解成CO2,可以直接排空,无二次污染。  相似文献   

14.
Noble metal Ag-decorated, monodisperse TiO2 aggregates were successfully synthesized by an ionic strength-assisted, simple sol–gel method and were used for the photocatalytic degradation of the antibiotic oxytetracycline (OTC) under both UV and visible light (UV–visible light) irradiation. The synthesized samples were characterized by X-ray diffraction analysis (XRD); UV–vis diffuse reflectance spectroscopy; environmental scanning electron microscopy (ESEM); transmission electron microscopy (TEM); high-resolution TEM (HR-TEM); micro-Raman, energy-dispersive X-ray spectroscopy (EDS); and inductively coupled plasma optical emission spectrometry (ICP-OES). The results showed that the uniformity of TiO2 aggregates was finely tuned by the sol–gel method, and Ag was well decorated on the monodisperse TiO2 aggregates. The absorption of the samples in the visible light region increased with increasing Ag loading that was proportional to the amount of Ag precursor added in the solution over the tested concentration range. The Brunauer, Emmett, and Teller (The BET) surface area slightly decreased with increasing Ag loading on the TiO2 aggregates. Ag-decorated TiO2 samples demonstrated enhanced photocatalytic activity for the degradation of OTC under UV–visible light illumination compared to that of pure TiO2. The sample containing 1.9 wt% Ag showed the highest photocatalytic activity for the degradation of OTC under both UV–visible light and visible light illumination. During the experiments, the detected Ag leaching for the best TiO2-Ag photocatalyst was much lower than the National Secondary Drinking Water Regulation for Ag limit (0.1 mg L?1) issued by the US Environmental Protection Agency.  相似文献   

15.
Sr-doped CuBi2O4 micro-particles were successively synthesized via a solid-state technique and were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and UV–vis diffuse reflectance spectroscopy (UV–vis-DRS) techniques. Results show that Sr-doped CuBi2O4 was crystallized with a spinel-type structure and tetragonal crystal system, and the band gap energy was about 1.35 eV. The as-prepared Sr-doped CuBi2O4 treated at 573 °C for 12 h exhibited the highest efficiency, as a result of 97.22 % of CR degradation within 220 min, which is approximately 31 times greater than CR photodegradation when catalyzed by CuBi2O4 (3.13 %) and about 2.3 times superior than that catalyzed by the untreated Sr–doped CuBi2O4 sample (42.08 %). Pseudo-first-order kinetic model gave the best fit, with highest correlation coefficients (R 2?=?0.94–0.97). The Sr–doping and extending reaction time up to 12 h could be effective in producing Sr-doped CuBi2O4 materials that delay electron–hole recombination, thereby increasing the lifetime of the electron electron–hole separation and support the charge carrier transfer to the catalyst surface. On the basis of the calculated energy band positions, superoxide radical anions (O2 ?–) were the main oxidative species responsible for the photocatalytic degradation of CR dye solution.  相似文献   

16.

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO2 nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO2 system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir–Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm? 1 and 0.984 ppm min? 1, respectively. In this work, we also compared the reactivity between the commercial TiO2 Degussa P-25 and a rutile TiO2. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO2 for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO2 process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO2.  相似文献   

17.
Textile dye effluents are typically characterized by strong color and recalcitrance, even at very low concentration. The process of enrichment of anionic azo dye on the surface of TiO2 fibers followed by photosensitization degradation under ambient air conditions was extensively investigated. Adsorption isotherms and zeta potentials were used to describe the “dye/TiO2 surface” interface, taking into account the effects of pH on the nature and population of the surface groups on the TiO2 fibers. The extent of the photocatalytic degradation of dye on TiO2 surface was determined by FTIR. N2 adsorption isotherms and optical spectra were employed to investigate the effect of photosensitization. The adsorption of dyes on the TiO2 surface occurs via electrostatic attraction through the formation of single- or multidentate-coordinated surface complexes. Almost complete photobleaching of the absorption band at 534 nm is achieved in ~4 h. Dye-sensitized TiO2 fiber could absorb part of the visible light spectrum (λ?<?600 nm). Interfacial electron transfer can potentially alter the degradation efficiency. The regenerated TiO2 fiber could be reused for subsequent decolorization without a decline in adsorption efficiency compared with freshly prepared TiO2 samples, which may be attributed to preservation of the hierarchical pore structure and restoration of the original surface properties. In summary, we propose an efficient “adsorption–photoregeneration–reuse” process applying TiO2 fibers for the degradation of dyes in water.  相似文献   

18.
CdS-TiO_2/MWCNTs结构表征及其光催化性能   总被引:1,自引:1,他引:0  
采用溶胶-凝胶法,制备了多壁碳纳米管(MWCNTs)负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜(TEM)、比表面分析(BET)、X射线衍射(XRD)和紫外-可见吸收光谱(UV-vis)等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明:纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。  相似文献   

19.
Abstract

The photocatalytic oxidation of propoxur, a nitrogen‐containing pesticide, has been investigated using aqueous TiO2 suspensions as catalyst in this study. The operating variables considered in the study were initial pH, temperature, [H2O2] and TiO2 loading. Results showed that 1 g/l of TiO2 was the optimum dosage for oxidizing propoxur in this system. Hydrogen peroxide can increase the oxidation rate with increasing its initial concentration. There was no obvious difference in the rate of propoxur oxidation at the initial pH of 4, 6 and 9, and the final pHs of reaction solutions were around 5.5. However, propoxur degraded slower at initial pH 2, and the pH did not vary during the period of photocatalytic reaction. The photocatalytic oxidation of propoxur using TiO2 suspensions as the photocatalyst was reaction‐controlled as indicated by the activation energy.  相似文献   

20.
以水解法制备的锐钛矿型TiO2为载体,制备了CuO/TiO2型光催化剂.以亚甲基蓝为对象,在可见光照射下研究了H2O3加入量、pH值和催化剂投加量对脱色效果的影响,同时与改性前的TiO2催化剂进行了脱色效果的对比.结果表明亚甲基蓝在碱性条件下能较好脱色,H2O2用量和CuO/TiO2催化剂投加量分别为每1 000 mL反应液各加入10 mL和0.1 g时脱色最好;另外,TiO2催化剂也在碱性条件下能较好脱色,H2O2用量和催化剂投加量分别为每1 000 mL反应液各加入12.5 mL和0.1 g时脱色最好.最优条件下对比实验表明,CuO/TiO2型催化剂在可见光照射下具有很高的催化活性,亚甲基蓝2 h脱色率达到88%,远好于改性前的TiO2和Degussa P25催化剂.  相似文献   

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