铁酸镍负载TiO2的可磁分离光催化剂的制备及性能

A magnetically separable photocatalyst TiO2/SiO2/NiFe2O4 （TSN） with a typical ferromagnetic hysteresis was prepared by a liquid catalytic phase transfer method. When the intensity of applied magnetic field weakened to zero, the remnant magnetism of the prepared photocatalyst faded to zero. The photocatalytst can be separated from water when an external magnetic field is added and redispersed into aqueous solution after the external magnetic field is eliminated, that makes the photocatalysts promising for wastewater treatment. Transmission electron microscope （TEM） and X-ray diffractometer （XRD） were used to characterize the structure of the photocatalyst indicating that the magnetic SiOffNiFe204 （SN） particle was compactly enveloped by P-25 titania and Tit2 shell was formed. The magnetic composite showed high photocatalytic activity for the degradation of methyl orange in water. A thin SiO2 layer between NiFe2O4 and TiO2 shell prevented effectively the leakage of charges from TiO2 particles to NiFe2O4, which gave rise to the increase in photocatalytic activity. Moreover, the experiment on recycled use of TSN demonstrated a good repeatability of the photocatalytic activity.     

Synthesis and characterization of carbon-doped titania as a visible-light-sensitive photocatalyst

The synthesis and use of carbon-doped TiO₂ particles in photocatalysis under visible light are demonstrated. The carbon-doped titania with its mesoporous structure was prepared by chemical modification and characterized by several techniques including X-ray diffraction, transmission electron spectroscopy (TEM), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectra (EPR), and diffuse reflectance UV-Vis. absorption spectra, with emphasis on the effect of carbon as a doping compound to the titania. Based on EPR data, the photocatalytic activity by visible light can be ascribed to the trapping of electrons at interior sites of the carbon-doped titania between the valence and conduction bands in the titania band structure, and is able to activated by visible light of a wavelength of up to 550 nm. The photocatalytic activity of the carbon-doped TiO₂ nanoparticles was evaluated by examining the decomposition of phenol by irradiation with artificial solar light (>420 nm) and the results were compared with those using Degussa P25, a commercially available titania nanomaterial.     

Synergy effect on a suspended mixture of ceria and activated carbon for the photocatalytic degradation of phenol

Ceria, prepared by a precipitation method, was used as a new photocatalyst under UV light irradiation. The as-prepared sample was characterized by XRD and SEM. Results showed that the ceria was cubic fluorite structure and sized in nanometer range. The photocatalytic degradation of phenol was investigated in the presence of a suspended mixture of ceria and activated carbon. A synergy effect was observed with an enhancement of the apparent rate constant by a factor of 5.6 times. The apparent quantum yield of the ceria-AC system was also increased 2.9 times. The activated carbon with strong adsorption activity provided sites for the adsorption of phenol. Then, the adsorbed phenol would migrate continuously to the surface of ceria particles. Some phenol still remained adsorbing on the catalyst when no traces of phenol were detected in the solution. This adsorbed phenol could be degraded by maintaining UV-irradiation.     

Hydrothermal synthesis of titanium dioxides from peroxotitanate solution using different amine group-containing organics and their photocatalytic activity

Nanosized TiO₂ particles were prepared by hydrothermal method of the amorphous powders which were precipitated in an aqueous peroxotitanate solution using different amine group-containing organics. The physical properties of prepared nanosized TiO₂ particles were investigated. We also examined the activity of TiO₂ particles as a photocatalyst for the decomposition of orange II. The TiO₂ particles calcined at 400 °C were shown to have a stable anatase phase which has no organic compounds. The particles size of titania particles decreased from 15 to 10 nm as the carbon chain length increased. The titania nanoparticles were shown to have a polygonal shape prepared using NH₄OH and tetramethylammonium hydroxide (TMAOH) as additives, however, the micrographs showed the spherical and narrow size distribution prepared using tetraethyl-ammonium hydroxide (TEAOH) and tetrabutylammonium hydroxide (TBAOH). The titania particles prepared using TEAOH as an amine group-containing organic showed the highest activity on the photocatalytic decomposition of orange II. In addition, the titania particles calcined at 500 °C showed the highest activity on the photocatalytic decomposition of orange II.     

金属有机物化学气相沉积法制备负载型纳米TiO2光催化剂及性能评价

纳米粉末TiO2是有效的光催化剂，但存在回收困难、分散性差、颗粒易团聚等问题，极大地限制了其在废水处理中的实际应用。为解决上述问题，采用常压金属有机物化学气相沉积技术在活性炭表面沉积构成纳米TiO2固定化非均相光催化剂。XRD图谱表明煅烧温度为773K时负载的TiO2晶型结构为锐钛矿，873K时出现金红石相。TEM分析表明负载量为8％(wt)时负载的TiO2颗粒的粒径为10～20nm；载体负载前后BET面积减少仅为6％。以对氯苯酚(4-CP)为污染物进行了光催化降解实验，结果表明制备的负载型TiO2的光催化活性不仅接近商业粉末光催化剂P25，而且可以重复使用10次其光催化活性保持不变，显示了较好的废水处理应用前景。     

Visible light driven photooxidation of phenol on TiO2/Cu-loaded carbon catalysts

The photocatalytic performance of titania/Cu-carbon composites was investigated towards phenol degradation under visible light. The approach consisted on the incorporation of the transition metal on the carbon component of the hybrid composite via impregnation of the carbon precursor with a metal salt followed by activation. Data showed a homogeneous dispersion of copper particles within the carbonaceous matrix, predominantly as copper (II) species. The synthesized carbons displayed a well developed nanoporous texture, although comparatively the impregnation of copper caused a marked inhibition of the textural development of the carbon precursor. The phenol photooxidation tests carried out on 1:1 titania/carbon composites showed the outstanding role of copper under visible light, with an increased efficiency in terms of phenol conversion, mineralization degree and degradation rate. This is important, since similar overall conversions were obtained with half of the amount of the photoactive semiconductor (1:1 composites). The beneficial effect of copper loading was also observed in the marked regioselectivity towards the preferential formation of catechol. Furthermore, the copper-loaded photocatalyst was found to be stable with no lixiviation or photorreduction of the copper species after illumination.     

Fine Control of Nitrogen Content in N-doped Titania Photocatalysts Prepared from Layered Titania/Isostearate Nanocomposites for High Visible-Light Photocatalytic Activity

In this contribution, high photocatalytic activity under visible-light irradiation realized by means of the fine control of the nitrogen content in doped titania photocatalysts is reported. The photocatalyst samples were prepared from a layered titania/isostearate nanocomposite as precursor, and the fine control of nitrogen content was achieved by the adjustment of the amount of hybridized isostearate in the nanocomposite, preserving the crystallinity and specific surface area of the final samples. Photocatalytic activity under the UV-light irradiation (290 and 350 nm) decreases with nitrogen content. Under visible-light irradiation (470 nm), a maximum value of photocatalytic activity was observed at [N]/[Ti] = 0.0145, whereas the absorbance in the visible-light region increases with nitrogen content. Fine control of the doped-nitrogen content provides a possible route to achieving high visible-light photocatalytic activity where the maximum value of the apparent quantum yield under 470 nm light irradiation exceeds 2%.     

Enhanced photocatalytic activity of TiO2/SiO2 by the influence of Cu-doping under reducing calcination atmosphere

Cu-doped titania photocatalyst supported on silica beads (Cu-TiO₂/SiO₂) were prepared under different Cu-ion concentration and under different calcination atmosphere. The properties and performance of Cu-TiO₂/SiO₂ were compared with undoped TiO₂/SiO₂ photocatalyst. The effect of Cu-doping and calcination atmosphere on photocatalytic degradation of phenol under both black light and visible light irradiation were investigated, where in both cases the degradation rate of phenol by Cu-doped catalyst prepared under reducing calcination atmosphere was found to be higher than the undoped catalyst or Cu-doped catalyst prepared under air atmosphere. This may be attributed to increase in visible light absorption and lengthening of photogenerated electron–hole pair recombination time. The photocatalytic beads were characterized by X-ray diffraction (XRD), UV-Vis absorption spectroscopy and SEM/EDAX analysis.     

Efficient gas phase photodecomposition of acetone by Ru-doped Titania

Nanocrystalline titania particles doped with ruthenium oxide have been prepared by homogenous hydrolysis of TiOSO₄ in aqueous solutions in the presence of urea. The synthesized particles were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HRTEM), Selected Area Electron Diffraction (SAED) and surface area (BET) and porosity determination (BJH). The photocatalytic activity of Ru-doped titania samples was determined in the gas phase by decomposition of acetone during irradiation at 365 nm and 400 nm. The Ru-doped titania samples demonstrated enhanced photocatalytic activity under visible light. Ruthenium oxide causes the anatase to rutile transformation to occur at lower temperatures and decreasing of band-gap energy of Ru-doped samples.     

Synergy effect in the photocatalytic degradation of phenol on a suspended mixture of titania and activated carbon

The photocatalytic degradation of phenol, chosen as an aromatic model molecule, has been performed at room temperature (20°C) in contact with a suspended mixture of titania and of activated carbon (AC). Non-additive adsorption capacities were observed when the solids were mixed, and this was ascribed to a strong interaction, involving half of the surface of titania and ca. 14% of that of AC. A synergy effect was observed with an increase of the first order rate constant by a factor of 2.5. As for neat titania, the same main intermediate products (hydroquinone and benzoquinone) were found but in much smaller quantities and during a much smaller lifetime, suggesting that the same reaction mechanism occurred in the presence of photoinactive AC. The synergy effect was ascribed to an extended adsorption of phenol on AC followed by a transfer to titania where it is photocatalytically degraded. The synergy effect could not be improved by previous physical treatments of the solid mixture such as grinding and sonication. Some phenol remained adsorbed on AC when no traces of organic compounds were detected in the purified water. This adsorbed phenol could be destroyed by illuminated titania while maintaining UV-irradiation. This combined photocatalytic system may appear as a new performing one, more efficient with a shorter time necessary for decontaminating diluted used waters.     

Parameter effect on photocatalytic degradation of phenol using TiO2-P25/activated carbon (AC)

P25 powder embedded and TiO₂ immobilized on activated carbon (TiO₂-P25/AC) was prepared by P25 powder modified sol-gel and dip-coated method. The photocatalysts were characterized by XRD, BET, SEM and their photocatalytic activities were evaluated through phenol degradation in a fluidized bed photoreactor. The addition of P25 in the photocatalysts could significantly enhance the photocatalytic activity, and the optimum loading of P25 was 3 g L^?1. The operating parameter results indicated that the optimum pH for phenol degradation was 5.2; the effect of air flow rate gave an optimal value of 2 L min^?1; the increasing of UV light intensity led to an increase of degradation efficiency due to more photons absorbed on the surface of the photocatalyst. The kinetics of the phenol degradation fitted well with the Langmuir-Hinshelwood kinetics model. Finally, the photocatalytic ability of TiO₂-P25/AC was reduced only 10% after five cycles for phenol degradation.     

Photocatalysis by Composite Particles Containing Inert Domains

Titanium dioxide is a well-known photocatalyst for the treatment of air and water. The use of structures comprised of photocatalytic sites and high capacity adsorption sites may improve the TiO₂ photoefficiency, in cases where the contaminnants do not adsorb well onto the photocatalyst. In this work, composite particles composed of activated carbon, partially coated with sol-gel-made titanium dioxide, were prepared and characterized. It was found that chelating the titanium tetraiso-propoxide, used as a precursor, with acetylacetone is crucial for obtaining reasonable loading (up to 12–15% in weight). High content of water or humidity tends to form thick films that might bridge over the pores of the activated carbon, thus reducing the available surface area. The photocatalytic activity of the composite particles was tested by following the rate of production of carbon dioxide during the photodegradation of Rhodamine 6G in an aqueous solution. Enhanced mineralization rates relative to sol-gel-made titanium dioxide particles (by ˜30%) were observed. This enhancement is attributed to the adsorption of the contaminants in the vicinity of the photoactive sites. It was further found that the composite particles produced relatively less of the toxic by-product carbon monoxide, than sol-gel-made titanium dioxide or the commercially available Degussa P25. The reason for this effect is yet to be determined.     

Synthesizing and Comparing the Photocatalytic Properties of High Surface Area Rutile and Anatase Titania Nanoparticles

Rutile titania nanocrystalline particles with high specific surface areas were directly prepared by thermal hydrolysis of titanium tetrachloride aqueous solution. The as-prepared rutile titania powder was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area analysis, and Fourier transform Raman and IR spectroscopies. Neither anatase nor amorphous titania could be detected in this titania powder by XRD, Raman spectroscopy, and high-resolution TEM. In the phenol degradation reaction, the rutile titania powder with an initial crystalline size of 7 nm was found to have higher photocatalytic activity than that of anatase titania with the same specific surface area. The rutile titania powders calcined at 300° and 450°C also showed a relatively high photocatalytic property. The high activity of the as-prepared rutile titania was attributed to the abundance of hydroxy groups in the powder, as was proven by thermogravimetric analysis data, which provided more active sites for the degradation reaction.     

Preparations and photocatalytic properties of magnetically separable nitrogen-doped TiO2 supported on nickel ferrite

A magnetically separable nitrogen-doped photocatalyst TiO_2−xN_x/SiO₂/NiFe₂O₄ (TSN) with a typical ferromagnetic hysteresis was prepared by a simple process: the magnetic SiO₂/NiFe₂O₄ (SN) dispersion prepared by a liquid catalytic phase transformation method and the visible-light-active photocatalyst TiO_2−xN_x were mixed, sonificated, dried, and calcined at 400 °C. The prepared photocatalyst is photoactive under visible light irradiation and easy to be separated from a slurry-type photoreactor under the application of an external magnetic field, being one of promising photocatalysts for wastewater treatment. Transmission electron microscope (TEM) and X-ray diffractometer (XRD) were used to characterize the structure of the TSN photocatalyst. The results indicate that the magnetic SiO₂/NiFe₂O₄ (SN) nanoparticles adhere to the surface of TiO_2−xN_x congeries. The magnetic photocatalyst TSN shows high catalytic activity for the degradation of methyl orange in water under UV and visible light irradiation (λ > 400 nm). SiO₂ coating round the surface of NiFe₂O₄ nanoparticles prevents effectively the injection of charges from TiO₂ particles to NiFe₂O₄, which gives rise to the increase in photocatalytic activity. Moreover, the recycled TSN exhibits a good repeatability of the photocatalytic activity.     

TiCl4为原料掺碳二氧化钛的可见光催化活性

为拓展二氧化钛对可见光的响应,采用水解法和其它步骤制备了碳掺杂二氧化钛粉末。用X射线衍射和紫外-可见光漫反射吸收光谱以及X射线光电子能谱对制备的样品进行了表征,对可见光照射下的光催化活性进行了测试,并考察了光催化的重复性。结果表明：碳掺杂致使二氧化钛在可见光区的光吸收增强,在降解甲基橙的实验中表现出良好的可见光催化活性。     

Magnetically recyclable Ni1-xCdxCeyFe2-yO4-rGO nanocomposite photocatalyst for visible light driven photocatalysis

In this study, a magnetically recyclable Ni_1-xCd_xCe_yFe_2-yO₄-rGO (x, y = 0.05) (NCCF-rGO) nanocomposite photocatalyst has been prepared by following a facile in-situ co-precipitation method combined with ultra-sonication means. The as-synthesized magnetically separable NCCF-rGO nanocomposite photocatalyst efficiently degrades methylene blue (MB) dye in comparison to bare Ni_1-xCd_xCe_yFe_2-yO₄ (x, y = 0.05) (NCCF) nanoparticles (NPs) under visible light irradiation. The photo-degradation rate of MB with NCCF-rGO was ~9 times higher than NCCF nanoparticles (NPs). This enhanced photocatalytic performance of NCCF-rGO photocatalyst was due to the presence of reduced graphene oxide, which greatly help in production of photoactive species by reducing the rate of electro-hole pair recombination. The role of photoactive species that were responsible for the photocatalytic degradation of methylene blue has also been investigated. The as-synthesized NCCF-rGO photocatalyst expressed superb chemical stability and photocatalytic activity even after seven cycle runs. Moreover, the NCCF-rGO nanocomposite worked at all pH values and showed good acid resistance. In particular, the as-synthesized NCCF-rGO photocatalyst could be collected for the next cycle run by simply applying an external magnetic field. Hence, the NCCF-rGO nanocomposite could have potential use in organic dyes contained wastewater treatment.     

Improvement in photocatalytic activity of morphologically controlled Pd-supporting TiO2 particles via sol–gel process using inkjet nozzle

The purpose of the present study is to prepare palladium-supporting porous titania particles via a sol–gel process using an inkjet nozzle and to improve the photocatalytic activity of the particles. The morphology of titania particles produced by the sol–gel process using an inkjet nozzle was evaluated by scanning electron microscopy and nitrogen physisorption measurements. The photocatalytic activity of the obtained titania particles was evaluated using the changes in the concentration of a methylene blue solution under UVC light irradiation and the effect of palladium supported on the inner and outer surfaces of the titania particles on the photocatalytic activity was investigated.The titania particles prepared by inkjet processing exhibited spherical porous structures. The particle and pore size distributions of the obtained titania particles were more uniform than those of the titania particles prepared using the non-inkjet nozzle. The titania particles supporting palladium on the inner and outer surfaces exhibited a faster rate of photocatalytic degradation than the titania particles supporting palladium on only the outer surface, with anatase titania particles exhibiting the highest rate of photocatalytic degradation. Thus, we have successfully improved the photocatalytic activity of titania particles by supporting palladium on the inner and outer titania surfaces. This sol–gel process using an inkjet nozzle is an effective method for the preparation of porous titania particles supporting palladium on their inner and outer surfaces.     

TiO2掺杂粉体的溶胶-凝胶和水热合成及其光降解甲醛

为了研究不同掺杂对二氧化钛光化学活性的影响,采用溶胶-凝胶,水热法,由TiOCl2成功制备了掺杂氮原子的二氧化钛样品,并制备了掺杂0.5%(摩尔分数)Fe3 ,Gu2 ,V5 ,Pd2 等金属离子的可见光响应型介孔材料.样品经由X射线衍射,透射电镜,Brunauer-Emmett-Teller(BET)比表面积,Barrett-Joyner-Halenda孔径分布,紫外可见光谱,光电子能谱和荧光光谱等表征;以荧光灯为光源(入射光波长λ≥410 nm),光催化降解甲醛为模式,评价了样品的催化活性.结果表明:掺杂Fe3 ,Cu2 ,V5 ,Pd2 的二氧化钛和单一掺氮的二氧化钛样品的粒径均为10 nm左右,BET比表面积为130 m2/g左右,均为锐钛矿相二氧化钛;Fe/TiO2,Cu/TiO2,V/TiO2,Pd/TiO2和TiO2/N样品的带隙能依次为:2.99,2.93,2.36,2.92 eV和2.87 eV,其在可见光下的光催化降解速率常数分别为:0.006 3,0.008 6,0.004 9,0.003 l/min和0.003 3/min.Cu/TiO2较高的荧光强度和较大的比表面积,导致了其较高的可见光光解活性.     

Performance of activated carbons in consecutive phenol photooxidation cycles

The long term performance of semiconductor-free activated carbons showing photochemical activity was explored by monitoring the photodegradation of phenol from aqueous solution along 20 h of illumination in consecutive photocatalytic cycles. The efficiency of the process was evaluated in terms of phenol conversion, mineralization degree and evaluation of degradation intermediates upon cycling. Data showed a strong dependence of the photooxidation efficiency on the hydrophobic/hydrophilic nature of the carbons. The outstanding role of dissolved oxygen as a promoter of phenol photodegradation through the formation of O-radicals upon illumination of the carbons was also demonstrated. The excess of oxygen not only improved phenol conversion and mineralization, but delayed the clogging of the carbon’s porosity upon cycling. This is important since a fraction of the photooxidation reaction also takes place inside the porous network of the carbon materials. Overall, the performance of the activated carbons, especially in conditions of excess of oxygen, is comparable to that of commercial titania.     

光催化再生型活性炭的研制

光催化再生型活性炭的研制是实现吸附饱和活性炭原位再生的重要环节。本文采用溶胶凝胶——再活化法在商品活性炭表面合成TiO2光催化剂，制得新型炭吸附材料一光催化再生型活性炭。以苯酚为模型化合物，考察了该材料的吸附性能和紫外光照射条件下的光催化再生性能。以扫描电子显微镜、低温液氮吸附研究光催化再生型活性炭的表面结构、孔径结构和TiO2的分布状况。结果表明，光催化再生型活性炭保留了原料活性炭的吸附性能，在紫外光照射下即可逐渐恢复其吸附性能。其吸附性能随担载量的增加而降低，再生率随担载量的增加而升高，催化剂担载量为2．0wt％活性炭具有适宜的吸附性能和光催化再生性能。其再生率随再生次数增加而下降。光催化再生型活性炭具有原料炭相似的表面结构和孔径结构。TiO2在活性炭基材料表面呈不均匀分布，主要集中在活性炭的大孔和表面凹陷处。