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1.
以TiO2为载体,采用等体积浸渍法制备了负载型CuxMn1-xCe0.75Zr0.25/TiO2(x=1.0、0.75、0.5、0.25、0)负载型催化剂,采用XRD、H2-TPR、O2-TPD和XPS等方法对催化剂进行了表征,并通过低温等离子体协同催化剂对大流量的甲苯模拟废气进行了催化降解反应研究。结果表明,Cu和Mn单主金属催化剂的活性优于Cu-Mn双主金属催化剂,其原因是双金属催化剂中Mn的添加减弱了Cu与助剂Ce之间的相互作用,使得催化剂的晶格氧减少,低温还原性能降低。在反应初期,甲苯降解主要依赖于催化剂的活性,具有较好的低温还原性以及丰富的氧空穴和晶格氧含量的CuCe0.75Zr0.25/TiO2的活性最好;Mn具有较强的O3分解能力,当等离子体比能密度(SED)增加到一定值后,等离子体与催化剂的协同作用增强,从而使得MnCe0.75Zr0.25/TiO2催化剂活性高于CuCe0.75Zr0.25/TiO2,强化了甲苯的脱除。  相似文献   

2.
The present study focused on the different acute toxicity of TiO2 nanoparticles(TiO2 NPs) towards the bacteria in suspension culture and adherent culture under the dark conditions. The study investigated the bacteria toxicity with TiO2 NPs at different concentrations(1—2000 mg/L), sizes(10 nm, 35 nm) and specific surface areas in unit volume solution(0—224 m2/L) characterized by the cell viability, extracellular polymeric substances(EPS) release and biofilm formation. The bacteria in adherent culture was found to be more resistant against the toxicity of TiO2 NPs compared to that in suspension culture. An NP dose and surface area dependent(rather than the size) bacterial viability was observed in suspension culture, specifically the surface area positively correlated with the toxicity of TiO2 NPs. The size of TiO2 NPs, however, played a more critical role in toxicity of TiO2 NPs in adherent culture. Therefore, the surface area dependent toxicity of TiO2 NPs is a comprehensive parameter describing the dose and size dependent toxicity of TiO2 NPs. The electron microscopic(SEM, TEM, EDX) observations suggested the EPS release and biofilm formation, during aggregation of TiO2 NPs on the bacteria after 12 h cultivation in adherent culture under the dark condition. A possible toxic mechanism could be that “effective surface areas” that directly contact with the bacterial membrane greatly contributed to the toxicity of TiO2 NPs in both suspension culture and adherent culture. Therefore, as for the possible resistance mechanism, EPS secretion and subsequent biofilm formation may protect the bacteria against the toxicity of TiO2 NPs.  相似文献   

3.
Application of atmospheric pressure plasma as an alternative technology for the destruction of toluene is demonstrated in this study. Used TiO2 colloidal solution was obtained by an improved sol–gel method, and coated on glass beads to prepare decomposition of toluene. The physical property of synthesized TiO2 catalyst film was analyzed by XRD and SEM spectroscopy. From these results, it was identified that the catalyst film exhibited anatase structure with particle size of about 50–100 nm after calcination at 500 °C for 1 h. The decomposition of toluene in TiO2/O2 plasma system was investigated. Amounts of the catalyst and toluene concentration were fixed as 3 wt.% and 1000 ppm, respectively. The analyses for performance of toluene decomposition and intermediates in reaction were done by the in situ method using the mass spectroscopy and gas chromatography. The toluene of 40% was decomposed at pulse voltage of 13 kV in the only O2 plasma condition without TiO2 catalyst. Furthermore, the conversion enhanced remarkably in the TiO2/O2 plasma system, and it reached 70% at pulse voltage of 13 kV after 120 min. This result was very notable compared with that in photocatalytic system, with below 40% after 120 min reaction.  相似文献   

4.
Nanosized pure TiO2 particles with high crystallinity and large surface area were prepared by hydrolysis of tetrabutyl titanate in water/Triton X-100/isooctane reverse micelle solutions as reaction media followed by hydrothermal treatment to improve crystallinity. The prepared TiO2 nanoparticles were characterized by XRD, BET, TGA, FT-IR and TEM. The size of ultrafine particles was controlled by changing the water content of the reverse micelle solution. The TiO2 particles showed monodispersity, large surface area and high degrees of crystallinity and thermostability. The photocatalytic activity of the TiO2 particles was evaluated by decomposition of toluene in the gas phase. The activity of the TiO2 nanoparticles was higher than that of commercially available anatase fine particles, such as ST-01, which is one of the most active photocatalysts for degradation of organic compounds in the gas phase.  相似文献   

5.
采用共沉淀法制备TiO2-CeO2光催化吸附脱硫材料,通过低温N2吸附脱附和X射线衍射等技术对TiO2-CeO2的物理化学性质进行了表征。结果表明,紫外光辐射显著提高了TiO2-CeO2的吸附脱硫性能;柴油中有机硫在TiO2-CeO2表面发生了光催化氧化转化为极性较强的砜类,可选择性地吸附在材料表面而被脱除。当TiO2-CeO2材料中钛铈物质的量比为9:1、煅烧温度为500℃时,其光催化吸附协同脱硫效果最好;在紫外光辐射下反应5 h,油品中DBT的脱除率高达99.6%。TiO2-CeO2光催化吸附协同脱硫工艺可有效解决吸附脱硫工艺中芳烃竞争吸附导致吸附脱硫选择性低的问题;在模拟油品中添加质量分数为25%的甲苯,反应7 h后油品脱硫率仍高达96.6%。TiO2-CeO2对不同硫化物的光催化吸附协同脱硫效果顺序为:4,6-DMDBT> DBT> BT。TiO2-CeO2经四次再生循环使用后,脱硫率没有明显降低。  相似文献   

6.
基于微波水热法和微乳液法合成SnO2/TiO2纳米管复合光催化剂.通过X射线衍射(XRD)、配有能量色散X射线光谱仪(EDX)的透射电镜(TEM)和电化学手段对光催化剂进行表征.以甲苯为模型污染物,考察光催化剂在紫外光(UV)和真空远紫外光(VUV)下的性能及失活再生.结果表明,SnO2/TiO2纳米管复合光催化剂形成三元异质结(锐钛矿相TiO2(A-TiO2)/金红石相TiO2(R-TiO2)、A-TiO2/SnO2和R-TiO2/SnO2异质结),促使光生电子-空穴对的有效分离,提高光催化活性.SnO2/TiO2表现出最佳的光催化性能,UV和VUV条件下的甲苯降解率均达100%,CO2生成速率(k2)均为P25的3倍左右.但由于UV光照矿化能力不足,中间产物易在催化剂表面累积.随着UV光照时间的增加,SnO2/TiO2逐渐失活,20 h后k2由138.5 mg·m-3·h-1下降到76.1 mg·m-3·h-1.利用VUV再生失活的SnO2/TiO2,过程中产生的·OH、O2-·、O(1D)、O(3P)、O3等活性物质可氧化吸附于催化剂活性位的难降解中间产物,使催化剂得以再生,12 h后k2恢复到143.6 mg·m-3·h-1.UV和VUV的协同效应使UV降解耦合VUV再生成为一种可持续的光催化降解污染物模式.  相似文献   

7.
The degradation of 2-chlorophenol (2-CP) was investigated by a combination of TiO2-based photocatalysis and adsorption. Three combined systems were compared: (i) TiO2 was intercalated into the interlamellar space of a hydrophilic montmorillonite by means of a heterocoagulation process (TiO2 pillared montmorillonite, TPM); (ii) TiO2 was hydrothermally crystallized on hexadecylpyridinium chloride-treated montmorillonite (HDPM-T); (iii) hexadecylpyridinium chloride-treated montmorillonite (HDPM) was used as adsorbent and Degussa P25 TiO2 as photocatalyst (HDPM/TiO2).

The process of mineralization of the organic substrate was characterized by measuring the total organic carbon (TOC) and total inorganic chloride contents, while the degradation of 2-CP and the formation of intermediates were followed by HPLC. The adsorbent-photocatalyst systems were characterized by X-ray diffraction measurements. In all the investigated systems, the degradation of 2-CP was accompanied by a continuous decrease in TOC content. The most advantageous situation was found with HDPM/TiO2, for which the highest rate of oxidation of 2-CP was observed. In this case the photocatalytically recovered adsorbent may be re-used without further regeneration. A significantly lower 2-CP degradation rate was observed when TiO2 was fixed on layer silicates. When TPM was applied, only a rather low decrease in TOC content was observed during 10 h of irradiation, i.e. only slight mineralization of the organic pollutant occurred, which is probably due to the low crystallinity and small size of the TiO2 particles. In the case of HDPM-T, the observed quite high reduction in TOC content shows that the hydrothermally processed TiO2 sample may compete with the Degussa P25, but the degradation of the organic pollutant is accompanied by a continuous destruction of the adsorbent.  相似文献   


8.
用浸渍、烧结方法制备了不锈钢网(3×15cm)负载催化剂:由溶胶-凝胶法制备含(400目)电气石粉的二氧化钛催化剂,并与直接混合电气石粉、P-25 TiO2的复合负载催化剂进行对照;利用X射线衍射、扫描电镜、透射电镜等表征催化剂结构;研究了催化剂在反应器(14L)中由20W紫外杀菌灯照射下光催化氧化去除气相甲苯污染物的效果.结果表明,在制溶胶过程中添加微米级电气石粉,得到催化剂粒径较小,其负载量和催化活性均有提高,平均催化比活性达到1.90mg·m-2·min-1或0.11mg·g-1·min-1,该催化剂在静态条件下反应4h,对初始浓度为180mg·m-3和70mg·m-3的甲苯去除率分别达到87%和82%;而同样的高初始浓度下,负载P-25仅可去除21%甲苯,复合负载P-25、电气石可去除58%甲苯,其催化比活性达到1.35mg·m-2·min-1或0.18mg·g-1·min-1.  相似文献   

9.
通过在锐钛矿TiO_2载体表面上负载Cu-BTC(BTC,1,3,5-苯甲酸)前驱体,还原处理制备光催化剂CuO-Ti~(3+)/TiO_2(Cu-TiMB),对其在可见光条件下气相甲苯净化催化性能进行了研究。结果表明,该改良方法制备的CuO-Ti~(3+)/TiO_2(CuTiM B)催化剂的活性是浸渍法所得催化剂CuO-TiO_2(Cu-TiD)的2.68倍。CuO-Ti~(3+)/TiO_2(Cu-TiMB)具有更大的比表面积(147 m2/g)和较小的颗粒粒径(0.45μm),呈现多孔状,CuO的分散度较高;催化剂表面Ti~(3+)提供了大量的氧缺位,在400-800 nm波段的光响应能力显著增强。CuO-Ti~(3+)/TiO_2(Cu-TiMB)催化剂中Cu~(2+)、Cu~+与Ti~(3+)形成的异质结构进一步增多了氧缺位数量,延缓e--h+的复合时间;氧缺陷增强了捕获吸附氧能力,通过金属氧化物价态变化增强化学吸附能力,提高了光催化性能。  相似文献   

10.
Surface modified titania dioxide composite nanoparticles prepared by hydrogen reduction reaction and a mesoporous TiO2 foam made from a surface modifier and a long chain organic surfactant were characterized by diffractive, spectroscopic and microscopic techniques and studied for their catalytic activity towards the decomposition of an industrial water pollutant, methyl orange. The surface deposition of ruthenium and silicon particles improved the photocatalytic activity of the composite particles resulting in a faster decomposition of the methyl orange compared to commercial TiO2 alone. Modification of TiO2 with RuO2 only offered a marginal benefit over TiO2 while the incorporation of RuO2 and SiO2 into TiO2 resulted in a marked increase in the rate constant and catalytic activity. These results are consistent with the enhanced surface properties of the composite materials resulting from the modification of TiO2 with RuO2 and SiO2. This surface enhancement effects appear synergetic to the charge separation process and hence the photocatalytic results are explained on the basis of a mechanism involving efficient charge transfer across the interfaces of the composites involving photogenerated electron–hole pairs. Results obtained in this study show that the percentage degradation after 1 h of illumination was 47.15% for TiO2 foam, 75.5 and 106.4%, respectively, for TiO2/RuO2 (SiO2 5%, w/w) and TiO2/RuO2(SiO2 10%, w/w) and 34.15% for commercial TiO2.  相似文献   

11.
The dispersion stability of rutile TiO2 powder with a unique nano-structure synthesized by homogeneous precipitation process at low temperatures (HPPLT) has been investigated with adding the various electrolytes in both pure aqueous and organic media. Zeta potential measurements have shown that the addition of electrolytes such as CsCl, CaCl2, FeCl3, and ZrCl4 to aqueous and pure organic dispersion media leads to generally a charge reversal from negative to positive on the surface of TiO2 particle. The electrostatic repulsive force acting on between TiO2 particles dispersed in pure organic media was found to be significantly greater than that in aqueous media, which is closely related to the physical properties of the organic solvents, such as viscosities and dielectric constant. The surface potentials of TiO2 particles have been greatly modified by the particulate properties, pH, dispersion medium, and valence of the ionic species, which governs the colloidal behavior of TiO2 particles virtually.  相似文献   

12.
The photocatalytic reaction in an aqueous TiO2 suspension has been found to be enhanced by the additiona of some metal powders such as copper, silver, nickel and cobalt into the suspension. Just mixing a metal powder into the suspension gave nearly the same efficiency as metal-loading on the semiconductor particles. The effect is attributed to the rapid transfer of the photogenerated electrons from the TiO2 to the metal particles, resulting in the effective separation of the electrons and holes.

The photo-current measurements were performed using inert collecting electrodes in the suspensions of TiO2, where formate was added as a hole scavenger, with and without a metal powder. Higher anodic photocurrent was obtained in the presence of a metal than in its absence, indicating that the metal-mediated electron transfer reaction occurs more effectively from the electron-rich TiO2 particles to the collecting electrode than the direct discharge of the electron-rich TiO2 on the collecting electrode.  相似文献   


13.
Vacuum ultraviolet irradiation coupled with photocatalytic oxidation (VUV-PCO) is an efficient and promising method for eliminating pollutants at room temperature; it involves three processes: vacuum ultraviolet (VUV) photolysis, photocatalytic oxidation (PCO), and ozone catalytic oxidation. Herein, toluene was chosen as the representative volatile organic compound (VOC), which is one of the most important precursors to form fine particulate matter and photochemical smog, because of its high toxicity and extensive existence in industries. All experiments were performed in a fixed-bed continuous-flow reactor that contained units for VUV photolysis and PCO. Mesoporous P-Mn-TiO2 was prepared by one-step hydrolysis and used as a catalyst for the oxidation of gaseous toluene under VUV irradiation through the VUV-PCO process. The as-prepared P-Mn-TiO2 samples were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), ultraviolet-visible light (UV-Vis) spectroscopy, and X-ray diffraction (XRD) analysis to determine the physicochemical properties of the catalysts and to determine the mechanisms of Mn doping and phosphoric acid modification and the effects of these processes on photocatalytic activity, ozone catalytic activity, and adsorption performance. The results indicated that the synergistic effect of phosphoric acid modification and Mn doping can improve the ozone catalytic activity and photocatalytic performance by increasing the number of oxygen active sites, completely eliminating the outlet ozone, and simultaneously promoting the efficient degradation of toluene. Moreover, doping TiO2 with Mn3+ significantly enhanced light harvesting, and numerous oxygen vacancies can be generated on the catalyst surface because of the presence of doped Mn3+ in the lattice, which adsorbs and transforms the oxygen species for toluene degradation. In addition, modification with an appropriate amount of phosphate groups can facilitate O2 and O3 adsorption on the TiO2 surface that can favor photo-induced charge carrier separation, thereby significantly improving the photocatalytic and ozone catalytic activities. The excellent catalytic performance of mesoporous P-Mn-TiO2 for toluene degradation and outlet ozone elimination was ascribed to the formation of highly reactive oxidizing species such as O(1D), O(3P), and ·OH via the catalytic decomposition of O3 adsorbed on the oxygen vacancy sites containing Mn and phosphate groups on the catalyst surface. In the VUV-PCO process, toluene was first destructed via VUV photolysis and oxidized by residual O3 generated from VUV photolysis and the active oxygen species formed in the presence of the catalyst. Finally, toluene and the generated intermediate products were oxidized and degraded to CO2 and H2O through VUV-PCO. In addition, the outlet ozone byproduct was simultaneously eliminated by the multifunctional catalyst.   相似文献   

14.
EPR measurements reveal remarkable differences on the type of radicals produced after UV illumination of TiO2, CeO2 and 0.8% CeO2/TiO2 photocatalysts. Photoactivation of the TiO2 sample in vacuum results in the formation of Ti4+–O species and a small amount of Ti3+ centers. In the presence of adsorbed oxygen, irradiation of this material also generates Ti4+–O3 radicals. In the case of the CeO2/TiO2 catalyst, the ceria component is present in a highly dispersed state, as indicated by XRD and UV–Vis diffuse reflectance spectra (DRS) results. Accordingly, the only type of Ce4+–O2 adducts generated on the CeO2/TiO2 sample are indicative of the presence of two-dimensional patches of ceria on the anatase surface. On the other hand, photoactivation of the CeO2/TiO2 sample in the presence of oxygen also leads to the formation of some Ti4+–O and Ti3+ centers. In the case of the CeO2 sample, superoxide radicals are observed upon irradiation in vacuum and subsequent oxygen adsorption. Further irradiation of this material in the presence of oxygen increases the amount of Ce4+–O2 radicals and simultaneously generates new species, which are tentatively assigned to Ce4+–O2H radicals. Photocatalytic activity was tested for toluene oxidation, and the results obtained show that the photodegradation rate is slightly lower for CeO2/TiO2 than for the TiO2 sample. However, the selectivity towards benzaldehyde (6–13%) is comparable for both materials. In the case of CeO2, the photo-oxidation rate is an order of magnitude lower than for TiO2, although mineralization of toluene is almost complete. Photoactivity results are discussed in connection with the characteristics of the radicals observed.  相似文献   

15.
宋华  徐晓伟  代敏  宋华林 《燃料化学学报》2014,42(11):1400-1408
以两种类型的TiO2(锐钛矿anatase、晶须载体whiskers)为载体,分别采用程序升温还原(H2-TPR)法和溶剂热法制备Ni2P/TiO2催化剂,并用X射线衍射(XRD)、N2吸附比表面积(BET)测定、N2等温吸附脱附、CO吸附表征、X射线光电子能谱(XPS)技术、扫描电镜(SEM)对催化剂的结构和性质进行了表征。考察了不同的制备方法及不同类型TiO2载体对Ni2P/TiO2催化剂二苯并噻吩(DBT)加氢脱硫(HDS)性能的影响。结果表明,溶剂热法制备催化剂过程中,保持了TiO2晶体结构,抑制了TiPO4的形成,HDS活性高于H2-TPR法制备的催化剂;与锐钛矿TiO2为载体的催化剂相比,以晶须TiO2为载体的催化剂具有更优良的表面性质,能生成较多晶体颗粒粒径较小、分散性好的Ni2P活性相,具有更高的HDS活性。以晶须TiO2为载体,采用溶剂热法制备的Ni2P/TiO2催化剂,具有最好的加氢脱硫活性,在340℃、3.0MPa、氢油体积比为500、质量空速(WHSV)2.0h-1的条件下,二苯并噻吩转化率达到为98.2%。  相似文献   

16.
采用共沉淀法和原位溶胶-凝胶法制备了TiO2-Al2O3复合载体,其负载的磷化镍催化剂采用等体积浸渍法和H2原位还原法制备.通过N2吸附(BET)、X射线衍射(XRD)、透射电镜(TEM)、程序升温还原(TPR),X射线光电子能谱(XPS)和等离子体发射光谱(ICP-AES)表征技术对催化剂进行了表征,并通过喹啉的加氢脱氮反应评价了催化剂的加氢脱氮性能.结果表明,原位溶胶-凝胶法制成的复合载体基本保留了原有的γ-Al2O3的孔特征,具有较大的比表面积和较宽的孔分布,TiO2主要以表面富集的形式分散在管状的γ-Al2O3表面,其负载的磷化镍催化剂还原后所形成的活性相为Ni2P和Ni12P5;而共沉淀法制成的复合载体比表面积较小,孔径分布更加集中,TiO2趋于在块状的Al2O3表面均匀分散,其负载的磷化镍催化剂具有更好的可还原性,还原后所形成的活性相为Ni2P.不同的载体制备方法和不同的钛铝比对催化剂加氢脱氮性能影响较大,当n(Ti)/n(Al)=1/8时,共沉淀法载体负载的催化剂表现出最佳的加氢脱氮性能,在340℃,3 MPa,氢油体积比500,液时空速3 h-1的反应条件下,喹啉的脱氮率可以达到91.3%.  相似文献   

17.
A facile approach was developed to prepare highly dispersed TiO2 nanoparticles with selected phase. The crystallization phase of the nanoparticles can be easily tuned from anatase to rutile by the dosage of hydrochloric acid in the reaction system. The crystallite size of the as-prepared anatase TiO2 nanoparticles was ca. 3.2 nm with high dispersion. A transparent TiO2 colloid was obtained by dispersing the as-prepared anatase TiO2 nanoparticles in deionized water without any organic additives added. The concentration of TiO2-H2O colloid can be as high as 1600 g/L. The optical transmittance of TiO2-H2O colloid with a low concentration was nearly 100% in the visible region. Furthermore, anatase TiO2 nanoparticles(TiO2-NPs) showed superior photocatalytic performance compared to rutile TiO2-NPs.  相似文献   

18.
The repetitive discoloration kinetics of the azo-dye Methyl Orange (taken as a model organic compound) was followed under solar simulated radiation (90 mW/cm2) to assess the performance of the TiO2/Tedlar® composite photocatalyst. The influence of solution parameters on the photo-discoloration process: pH, dye concentration, applied light intensity and concentration of H2O2 were systematically investigated. During the photocatalysis a modification occurs in the TiO2/Tedlar® composite due to the TiO2 interaction with the Tedlar® film. Physical insight is given for the stabilization mechanism of the TiO2 particles in the Tedlar matrix based on the data obtained by X-ray photoelectron spectroscopy (XPS). The F 1s peak of the Tedlar film indicates that the TiO2 is loaded on the Tedlar fluoro-groups. The loading of TiO2 on the 75 μm thick Tedlar® film was 0.9% (w/w) as determined by atomic absorption spectrophotometry (AAS). Attenuated total reflection infrared spectroscopy (ATRIR) shows no formation of additional bands within the photodiscoloration reaction. This shows that an efficient catalysis taking place on the TiO2/Tedlar® surface. The rugosity (mean square roughness, rms) of the TiO2/Tedlar® film was determined by atomic force microscopy (AFM) to be 19.7 nm. This value remained constant during long-term operation. Transmission electron microscopy (TEM) reports the thickness and coverage of TiO2 Degussa P-25 on the Tedlar® surface before and after photocatalysis.  相似文献   

19.
首先采用相分离的水解-溶剂热法制备了Bi2O3纳米粒子,然后利用简单的湿化学法在Bi2O3表面负载不同比例的TiO2纳米颗粒,进而得到TiO2/Bi2O3纳米复合体。通过气氛调控的表面光电压谱(SPS)等测试表明,表面负载适量的TiO2后能够提高Bi2O3光生电荷分离。可见光催化产氢和降解污染物测试结果进一步证明,表面负载适量的TiO2后可显著提高其可见光催化活性,其中Ti/Bi摩尔比为7%时具有最高的光催化活性。这主要归因于TiO2具有较为合适的导带能级位置,可以接收Bi2O3在可见光激发下所产生的高能级电子,从而抑制光生电子-空穴对复合,并且维持了高能级电子较高的还原能力。  相似文献   

20.
以二氧化钛纳米管阵列(TiO_2NTs)为基体,利用脉冲电沉积的方法将Pr掺杂的PbO_2修饰到TiO_2NTs管中,制备出新型电极材料Ti/TiO_2NTs/nanoPbO_2-Pr用来降解有机废水。通过循环伏安测试(CV)和线性伏安法(LSV)等手段对电极性能进行评估,研究表明,新型电极材料Ti/TiO_2NTs/nanoPbO_2-Pr具有高的电催化活性。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、X射线光电子能谱(XPS)等对其进行表面形貌、晶形结构和元素组成进行研究。结果表明,通过脉冲电沉积成功将Pr-PbO_2沉积到TiO_2纳米管中,其中元素Pr是以Pr_2O_3形式存在。亚甲基蓝降解实验证明,Ti/TiO_2NTs/nanoPbO_2-Pr电极降解120min后亚甲基蓝的去除率高达99.8%。  相似文献   

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