Tricrystalline TiO2 with enhanced photocatalytic activity and durability for removing volatile organic compounds from indoor air

It is important to develop efficient and economic techniques for removing volatile organic compounds (VOCs) in indoor air. Heterogeneous TiO₂-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline TiO₂ with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO₃. The obtained samples were characterized by X-ray diffraction and N₂ adsorption–desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline TiO₂ exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline TiO₂, due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline TiO₂ prepared at R_HNO3 = 0.8, containing 80.7% anatase, 15.6% brookite and 3.7% rutile, exhibited the highest photocatalytic activity, about 3.85-fold higher than that of P25. The high activity did not significantly degrade even after five reuse cycles. In conclusion, it is expected that our study regarding gas-phase degradation of toluene over tricrystalline TiO₂ will enrich the chemistry of the TiO₂-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic.     

Acid-assisted hydrothermal synthesis of nanocrystalline TiO2 from titanate nanotubes: Influence of acids on the photodegradation of gaseous toluene

In order to efficiently remove volatile organic compounds (VOCs) from indoor air, onedimensional titanate nanotubes (TiNTs) were hydrothermally treated to prepare TiO₂ nanocrystals with different crystalline phases, shapes and sizes. The influences of various acids such as CH₃COOH, HNO₃, HCl, HF and H₂SO₄ used in the treatment were separately compared to optimize the performance of the TiO₂ nanocrystals. Comparedwith the strong and corrosive inorganic acids, CH₃COOH was not only safer andmore environmentally friendly, but also more efficient in promoting the photocatalytic activity of the obtained TiO₂. Itwasobserved that the anatase TiO₂ synthesized in 15 mol/L CH₃COOH solution exhibited the highest photodegradation rate of gaseous toluene (94%), exceeding that of P25 (44%) by a factor ofmore than two. The improved photocatalytic activity was attributed to the small crystallite size and surface modification by CH₃COOH. The influence of relative humidity (20%-80%) on the performance of TiO₂ nanocrystals was also studied. The anatase TiO₂ synthesized in 15 mol/L CH₃COOH solution was more tolerant tomoisture than the other TiO₂ nanocrystals and P25.     

Influence of environmental temperature and relative humidity on photocatalytic oxidation of toluene on activated carbon fibers coated TiO2

TiO₂ supported on active carbon fiber (TiO₂/ACF), an absorbable photocatalyst, is a new kind of material applied in air purification. In this paper, the influence of environmental temperature (T) and relative humidity (RH) on the gas-solid adsorption of toluene and the photocatalytic oxidation (PCO) efficiency of adsorbed toluene on TiO₂/ACF were studied, and then, the purification capability of TiO₂/ACF was estimated. PCO results showed that although the PCO efficiency increased under high RH and T levels, the amount of adsorption of toluene decreased. Moreover, quantitative analysis results of intermediates indicated that more environmental risk emerged when PCO of toluene was carried out at higher environmental T and RH levels because more toxic intermediates would be accumulated on the TiO₂/ACF. So, it is significant to control the environmental T and RH conditions in the application of the PCO technique. T = 25°C and RH530% is the optimal condition for purifying toluene in our experimental system. __________ Translated from Urban Environment & Urban Ecology, 2007, 20(5): 10–13 [译自: 城市环境与城市生态]     

Fabrication of Bi2O3/TiO2 nanocomposites and their applications to the degradation of pollutants in air and water under visible-light

A nanoheterojunction composite photocatalyst Bi2O3/TiO2working under visible-light(λ 420 nm) was prepared by combining two semiconductors Bi2O3 and TiO2 varying the Bi2O3/TiO2molar ratio. Maleic acid was employed as an organic binder to unite Bi2O3 and TiO2 nanoparticles. The SEM, TEM, XRD and diffuse reflectance spectra were utilized to characterize the prepared Bi2O3/TiO2nanoheterojunction. The nanocomposite exhibited unusual high photocatalytic activity in decomposing 2-propanol in gas phase and phenol in aqueous phase and, evolution of CO2 under visible light irradiation while the end members exhibited low photocatalytic activity. The composite was optimized to 5 mol% Bi2O3/TiO2. The remarkable high photocatalytic efficiency originates from the unique relative energy band position of Bi2O3 and TiO2 as well as the absorption of visible light by Bi2O3.     

TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应

以内分泌干扰物阿特拉津为模型污染物,研究了TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应.结果表明,在H2O2存在条件下,金红石TiO2经可见光激发可持续稳定地产生.OH自由基,在Fe3+协同作用下,.OH自由基生成量急剧增加;TiO2能可见光催化H2O2降解阿特拉津,金红石TiO2显示出较锐钛矿TiO2及混晶TiO2(TiO2P25)更高的催化活性,反应60 min,阿特拉津的降解率可达40%;以Fe3+协同TiO2可见光催化H2O2降解阿特拉津时,反应效率显著加快,反应5 min即对阿特拉津的降解率达到100%,而金红石TiO2显示出更为明显的协同效应.     

Visible light responsive N-F-codoped TiO2 photocatalysts for the degradation of 4-chlorophenol

Visible light responsive N-F-codoped TiO₂ photocatalysts exhibit a higher catalytic activity than N-doped TiO₂ for the degradation of 4-chlorophenol due to the synergistic effect of nonmetal elements.     

Enhanced photocatalytic activity of fish scale loaded TiO2 composites under solar light irradiation

Fish scale (FS) loaded TiO₂ composites were investigated as photocatalysts in degradation of Methyl Orange under solar light irradiation. Composites were prepared through sol-gel method by varying mass ratio of TiO₂/FS at 90:10, 70:30 and 50:50, respectively. The catalysts prepared in this study were characterized by using XRD, SEM, FT-IR and nitrogen sorption. The effects of solar irradiation, mass ratio of TiO₂/FS composites, irradiation time and catalyst loadings were studied. Synergistic effect was found in TiO₂/FS of 90:10 composite which performed higher photocatalytic degradation than synthesized TiO₂ under solar light irradiation. However, further increasing fish scale content in the composites reduced the photocatalytic activity drastically. Under solar light irradiation, all the catalysts in this study exhibited photocatalytic activity, except TiO₂/FS of 50:50 composite that only acted as a weak biosorbent without performing any photocatalytic property. Photocatalytic degradation increased with increasing catalyst loading and irradiation time but decreased with increased of initial dye concentration.     

Surface modification of polypropylene non-woven fibers with TiO2 nanoparticles via layer-by-layer self assembly method: Preparation and photocatalytic activity

Polypropylene (PP) meltblown fibers were coated with titanium dioxide (TiO₂) nanoparticles using layer-by-layer (LbL) deposition technique. The fibers were first modified with 3 layers of poly(4-styrenesulfonic acid) (PSS) and poly(diallyl-dimethylammonium chloride) (PDADMAC) to improve the anchoring of the TiO₂ nanoparticle clusters. PDADMAC, which is positively charged, was then used as counter polyelectrolyte in tandem with anionic TiO₂ nanoparticles to construct TiO₂/PDADMAC bilayer in the LbL fashion. The number of deposited TiO₂/PDADMAC layers was varied from 1 to 7 bilayer, and could be used to adjust TiO₂ loading. The LbL technique showed higher TiO₂ loading efficiency than the impregnation approach. The modified fibers were tested for their photocatalytic activity against a model dye, Methylene Blue (MB). Results showed that the TiO₂ modified fibers exhibited excellent photocatalytic activity efficiency similar to that of TiO₂ powder dispersed in solution. The deposition of TiO₂ 3 bilayer on the PP substrate was sufficient to produce nanocomposite fibers that could bleach the MB solution in less than 4 hr. TiO₂-LbL constructions also preserved TiO₂ adhesion on substrate surface after 1 cycle of photocatalytic test. Successive photocatalytic test showed decline in MB reduction rate with loss of TiO₂ particles from the substrate outer surface. However, even in the third cycle, the TiO₂ modified fibers are still moderately effective as it could remove more than 95% of MB after 8 hr of treatment.     

Simulated-sunlight-activated photocatalysis of Methylene Blue using cerium-doped SiO2/TiO2 nanostructured fibers

Cerium-doped SiO₂/TiO₂ nanostructured fibers were fabricated by electrospinning technology. The prepared fibers were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Using the fibers as catalysts, photocatalytic degradation of Methylene Blue (MB) aqueous solution was carried out under simulated sunlight. The 0.2% Ce doping proved to be the optimal concentration for the doping of TiO₂/SiO₂, compared to other Ce-doped molar concentrations. The 0.2% Ce-doped SiO₂/TiO₂ fibers exhibited higher photocatalytic activity than industrial Degussa P25 and the samples doped with only Ce or SiO₂. The reasons for improving the photocatalytic activity were also discussed. Several operational parameters were studied, which showed that the photocatalytic efficiency of MB was influenced by parameters such as the initial dye concentration, the initial pH, inorganic anions, and so on. In addition, the influences of an electron acceptor and a radical scavenger suggested that OH was the dominant photooxidant during the photocatalytic process. The reuse evaluation of the fibers indicated that their photocatalytic activity had good stability.     

WC/TiO2纳米复合界面光催化剂制备及其光催化降解酚类污染物研究

设计并制备了新型WC/TiO2纳米复合界面光催化剂应用于酚类污染物的光催化降解反应中.采用X射线衍射(XRD)和扫描电子显微镜(SEM)技术分析了WC/TiO2纳米复合界面光催化剂的晶型和表面形貌.结果显示锐钛矿型TiO2纳米颗粒均匀地分散在WC纳米球表面并很好地构筑了WC/TiO2界面.研究了不同WC负载比例的WC/TiO2光催化剂在模拟太阳光照射下降解苯酚的光催化性能.结果表明:WC/TiO2复合界面的形成可以有效地提高TiO2光催化降解性能;其中,3%WC/TiO2(质量分数)光催化降解苯酚的活性最高.利用紫外-可见光谱(UV-Vis)和高效液相色谱-质谱联用技术(HPLC-MS)分析了WC/TiO2纳米复合界面光催化剂降解苯酚的中间产物,提出了苯酚在WC/TiO2界面上可能的降解机理.     

Graphene TiO2 nanocomposites with high photocatalytic activity for the degradation of sodium pentachlorophenol

A series of graphene–TiO2photocatalysts was synthesized by doping TiO2 with graphene oxide via hydrothermal treatment. The photocatalytic capability of the catalysts under ultraviolet irradiation was evaluated in terms of sodium pentachlorophenol（PCP-Na） decomposition and mineralization. The structural and physicochemical properties of these nanocomposites were characterized by X-ray diffraction, N2adsorption–desorption, transmission electron microscopy, scanning electron microscopy, Ultraviolet–visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectra, and Fourier-transform infrared spectroscopy. The graphene–TiO2nanocomposites exhibited higher photocatalytic efficiency than commercial P25 for the degradation of PCP-Na, and 63.4% to 82.9% of the total organic carbon was fully mineralized. The improved photocatalytic activity may be attributed to the accelerated interfacial electron-transfer process and the significantly prolonged lifetime of electron-hole pairs imparted by graphene sheets in the nanocomposites. However,excessive graphene and the inhomogeneous aggregation of TiO2 nanoparticles may decrease photodegradation efficiency.     

BiOCl/TiO2的氯化改性及其新式光生自由基催化反应

采用溶胶凝胶法制备了BiOCl/TiO₂复合催化剂,透射电镜（TEM）照片显示,两种半导体分布均匀、相互连接,形成的异质结可以为电子传导提供有效通道.经过氯化处理的复合材料具备更强的光催化能力,在紫外光条件下对苯的降解率达到90%,是原BiOCl/TiO₂的2倍、纯TiO₂的10倍.本文利用X射线光电子能谱、红外光谱和电子顺磁共振,对表面氯化的机理进行研究.结果表明,氯元素以Ti—Cl的方式吸附在催化剂表面,在光照条件下光生空穴夺取一个电子,使其生成氯自由基,进而配合超氧、羟基,构成一种新型的三自由基光催化体系,使催化降解能力大幅提升.最后,利用实验方法得到了光生氯自由基的直接证据,并构建了该体系的光催化反应机理.     

RGO/TiO2光催化降解2,4-二氯苯氧乙酸研究

通过Hummers法及紫外光/热还原工艺制得还原氧化石墨烯(RGO),采用溶胶-凝胶-煅烧法,以RGO和钛酸酊脂为前驱体制备出RGO/TiO2光催化复合材料,并利用XRD、FT-IR等对其进行了表征.对RGO/TiO2光催化降解性能的研究发现,复合光催化剂RGO/TiO2对2,4-二氯苯氧乙酸(2,4-D)的光催化降解活性显著优于纯TiO2,并且发现负载量和pH值对光催化降解性能有较大的影响:RGO/TiO2投加量为1.2g·L~(-1)、RGO负载量2%、pH为3、初始浓度为50 mg·L~(-1)反应12 h,2,4-D去除率达到98.75%;2,4-D降解率随着RGO/TiO2投加量的增大先增大后减小;RGO/TiO2对2,4-D的降解为脱氯还原和催化氧化过程,产生氯酚、苯酚等中间产物.     

TiO2-石墨烯（Gn）复合材料光催化降解O3研究

通过改性Hummer法及溶胶凝胶法,制备出TiO2-石墨烯光催化复合材料.经吸附-光催化活性实验选出光催化活性最高的含C量为1.5%(质量分数)的TiO2-石墨烯复合材料,并在自行设计的模拟大型客机环境的气相光催化反应器中,进行O3光催化降解实验研究.结果表明,TiO2-石墨烯复合光催化材料在较短时间内对O3有较高的降解效率,且其光催化活性显著优于纯TiO2材料.初始O3浓度为(0.150～0.200)×10-6时,复合光催化剂受紫外光激发60 min的光催化降解率为66.12%,初始O3浓度为(0.950～1.000)×10-6时,其光催化降解率约为77%,较低浓度时((0.100～0.150)×10-6),O3去除率也能达到45.45%.此外,通过探讨光催化材料的重复使用性能,表明复合光催化剂重复使用4次以内,其对O3的光催化降解率保持基本稳定.     

Review of the progress in preparing nano TiO2: An important environmental engineering material

TiO2 nanomaterial is promising with its high potential and outstanding performance in photocatalytic environmental applications, such as CO2 conversion, water treatment, and air quality control. For many of these applications, the particle size, crystal structure and phase,porosity, and surface area influence the activity of TiO2 dramatically. TiO2 nanomaterials with special structures and morphologies, such as nanospheres, nanowires, nanotubes, nanorods,and nanoflowers are thus synthesized due to their desired characteristics. With an emphasis on the different morphologies of TiO2 and the influence factors in the synthesis, this review summarizes fourteen TiO2 preparation methods, such as the sol–gel method, solvothermal method, and reverse micelle method. The TiO2 formation mechanisms, the advantages and disadvantages of the preparation methods, and the photocatalytic environmental application examples are proposed as well.     

有机物多相光催化降解反应中催化剂固定化技术研究

以ＴｉＣｌ４和异丙醇为原料,通过化学反应将钛组分以键合方式引入载体多孔硅胶颗粒的表面,经高温处理提高活性,制备出的催化剂以甲基检溶液的脱色反应有很好的光催化活性,与相同量的粉末ＴｉＯ２作用相比,活性升高,经分析测定催化剂颗粒上有３１．０５％的钛成分且表面仍保持硅胶颗粒的骨架结构,具有大比表面和高分散性的优点,利用该方法即可以制备大颗粒载体型ＴｉＯ２催化剂,也可能进一步解决用于实际太阳光废水处理装置     

Photocatalytic activity of TiO2 containing anatase nanoparticles and rutile nanoflower structure consisting of nanorods

A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a futile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80：20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.     

Photocatalytic degradation of organochlorine compounds using TiO2 supported on fiberglass cloth

The feasibility of photocatalytic degradation of organochlorine compounds using TiO₂ supported on fiberglass cloth as a photocatalyst was studied. The results showed that 2.0×10^-4 mol/dm³ of dichloroethylene, trichloroethylene and tetrachloroethylene can be completely photocatalytically degraded within a short time under illumination with a 375W medium pressure mercury lamp. The effects of parameters such as illumination time, initial concentration of organochlorine compounds, amount of air flow and concentration of H₂O₂ on the photocatalytic degradation were investigated. The TiO₂ supported on the fiberglass was not easily detached and after 500h illumination there was no significant loss of photocatalytic activity of TiO₂. The passible mechanisms of photocatalytic degradation were discussed.     

Bi掺杂In2TiO5纳米带的制备及其光催化性能

以Bi(NO_3)_3、Ti(OC_4H_9)_4、In(NO_3)_3和聚乙烯吡咯烷酮(PVP-K30)为原料,采用静电纺丝法和沉淀法相结合,成功制备了Bi掺杂In_2TiO_5(Bi-In_2TiO_5)纳米带.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能量色散谱(EDS)、紫外-可见漫反射光谱(UV-vis DRS)和氮气吸附-脱附等温线(BET)等技术对样品进行表征.结果表明,Bi的掺杂未引入新的杂相,样品均为正交晶系结构,掺杂前后样品的形貌未发生明显变化.适量的Bi掺杂,在In2Ti O5晶格中形成杂质能级,降低了In_2TiO_5的带隙能.当掺杂量为2%时,制备的Bi-In_2TiO_5纳米带的光催化活性最高.在氙灯(150 W)辐照下,150 min,对罗丹明B的降解率达95.8%,且该催化剂对氟喹诺酮类抗生素左氧氟沙星(LEV)也表现出优良的光催化降解性能.     

Advances in photocatalytic disinfection of bacteria: Development of photocatalysts and mechanisms

Photocatalysis has attracted worldwide attention due to its potential in solar energy conversion. As a “green” advanced oxidation technology, it has been extensively used for water disinfection and wastewater treatment. This article provides a review of the recent progress in solar energy-induced photocatalytic disinfection of bacteria, focusing on the development of highly efficient photocatalysts and their underlying mechanisms in bacterial inactivation. The photocatalysts are classified into TiO₂-based and non-TiO₂-based systems, as TiO₂ is the most investigated photocatalyst. The synthesis methods, modification strategies, bacterial disinfection activities and mechanisms of different types of photocatalysts are reviewed in detail. Emphasis is given to the modified TiO₂, including noble metal deposition, non-metal doping, dye sensitization and composite TiO₂, along with typical non-TiO₂-based photocatalysts for bacterial disinfection, including metal oxides, sulfides, bismuth metallates, graphene-based photocatalysts, carbon nitride-based photocatalysts and natural photocatalysts. A simple and versatile methodology by using a partition system combined with scavenging study is introduced to study the photocatalytic disinfection mechanisms in different photocatalytic systems. This review summarizes the current state of the work on photocatalytic disinfection of bacteria, and is expected to offer useful insights for the future development in the field.