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.     

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.     

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 Ti O_2-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline Ti O_2 with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO_3.The obtained samples were characterized by X-ray diffraction and N_2 adsorption–desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline Ti O_2 exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline Ti O_2,due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline Ti O_2 prepared at R HNO_3= 0.8, containing80.7% 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 Ti O_2 will enrich the chemistry of the Ti O_2-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic.     

Graphitic carbon nitride-based photocatalysts in the applications of environmental catalysis

Semiconductor photocatalytic technology has shown great prospects in converting solar energy into chemical energy to mitigate energy crisis and solve environmental pollution problems. The key issue is the development of high-efficiency photocatalysts. Various strategies in the state-of-the-art advancements, such as heterostructure construction, heteroatom doping, metal/single atom loading, and defect engineering, have been presented for the graphitic carbon nitride (g-C₃N₄)-based nanocomposite catalysts to design their surface chemical environments and internal electronic structures to make them more suitable for different photocatalytic applications. In this review, nanoarchitecture design, synthesis methods, photochemical properties, potential photocatalytic applications, and related reaction mechanisms of the modified high-efficiency carbon nitride-based photocatalysts were briefly summarized. The superior photocatalytic performance was identified to be associated with the enhanced visible-light response, fast photoinduced electron-hole separation, efficient charge migration, and increased unsaturated active sites. Moreover, the further advance of the visible-light harvesting and solar-to-energy conversions are proposed.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

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.     

Synthesis of TiO2 visible light catalysts with controllable crystalline phase and morphology from Ti-bearing electric arc furnace molten slag

TiO₂ visible light catalysts with different crystalline phases and morphologies were synthesized from titanium-bearing electric arc furnace molten slag (Ti-bearing EAF slag) by using a simple acidolysis process. The effects of the pH of the HCl solution, liquid to solid ratio (R_L/S, HCl solution to the residue ratio, mL/g) and acidolysis time on the micro-morphology and crystalline phase of as-prepared TiO₂ photocatalysts were systematically investigated. The results indicated that with decreasing pH in the HCl solution and increasing R_L/S, the crystalline phase and micro-morphology of the obtained TiO₂ nanostructures tended to transform from anatase type TiO₂ with spherical nanoparticle structures to rutile type TiO₂ with needle-like nanorod structures. The acidolysis time had little influence on the crystalline phase but great impact on the size of the obtained TiO₂. The growth mechanism of TiO₂ from Ti-bearing EAF slag during the acidolysis process was also discussed. In addition, the influence of R_L/S on the photocatalytic properties of the synthesized nanostructured TiO₂ was studied. The results showed that the photodegradation efficiency for Rhodamine B solution could reach 91.00% in 120 min when the R_L/S was controlled at 50:1.     

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.     

Fe2O3/TiO2负载膨胀珍珠岩光催化降解罗丹明B

为获得高效催化活性的光催化材料,研究不同煅烧氛围对材料在可见光下催化性能的影响,以膨胀珍珠岩（EP）为载体,采用溶胶-凝胶法,在不同煅烧氛围（O₂和/或NH₃）下制备Fe₂O₃/TiO₂负载EP的光催化复合材料〔Fe₂O₃-TEP（O₂）、Fe₂O₃-TEP（NH₃）、Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）〕,采用EDS（X-射线色散能谱）、BET（比表面积及孔径分析）、XRD（X射线衍射）、SEM（扫描电子显微镜）、XPS（X射线光电子能谱）等对复合材料进行表征,并研究了其在可见光下对罗丹明B的光催化降解效果.结果表明:①复合材料成功负载了Ti、Fe元素,负载的TiO₂以锐钛矿型存在,Fe₂O₃的掺杂增强了TiO₂对可见光的响应能力;②不同的煅烧氛围明显影响复合材料的晶粒尺寸、比表面积和光催化性能,其中,Fe₂O₃-TEP（O₂,NH₃）的光催化性能最好,4 h后罗丹明B降解率达到87.59%,Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）4 h后对罗丹明B的降解率则分别为65.02%、62.48%和47.48%;③在试验条件下,复合材料的光催化反应符合一阶反应动力学方程,Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）相应的降解速率常数分别为0.008 3、0.004 3、0.004 3和0.002 7 min-1.研究显示,通过溶胶-凝胶法所制备的复合材料（Fe₂O₃-TEP）经煅烧后所得矿相均一;Fe₂O₃掺杂TiO₂可形成Ti—O—Fe键,减小TiO₂固有的禁带宽度;复合材料光催化性能也受到煅烧氛围的影响,先O₂后NH₃煅烧条件下所得材料的光催化性能最佳.      

Effect of transition metal doping under reducing calcination atmosphere on photocatalytic property of TiO2 immobilized on SiO2 beads

TiO₂ immobilized on SiO₂ (TiO₂/SiO₂) have been prepared by sol-gel method and various ions of transition metals (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) were doped on the photocatalyst using wet impregnation method under reducing calcination atmosphere. The photocatalytic activity of metal doped TiO₂/SiO₂ towards phenol degradation under black light irradiation were investigated and compared with undoped TiO₂/SiO₂. The results showed that the photoresponse of Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂ were larger than undoped TiO₂/SiO₂, indicating that the photogenerated carriers were separated more efficiently in Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂. The reactivity was in the order of Cu²⁺ > Zn²⁺ > Ni²⁺ > Cr³⁺ > Co²⁺. The different photoreactivity was ascribed to combine effect of the different ionic radii and photocorrison tendency of the dopants. The sample was also characterized by surface analytical methods such as X-ray diffraction, scanning electron micrograph/electron dispersive X-ray analyzer and UV-Vis absorption spectrum.     

Strategies for improving the photocatalytic performance of metal-organic frameworks for CO2 reduction: A review

Photocatalytic CO₂ reduction is an appealing strategy for mitigating the environmental effects of greenhouse gases while simultaneously producing valuable carbon-neutral fuels. Numerous attempts have been made to produce effective and efficient photocatalysts for CO₂ reduction. In contrast, the selection of competitive catalysts continues to be a substantial hindrance and a considerable difficulty in the development of photocatalytic CO₂ reduction. It is vital to emphasize different techniques for building effective photocatalysts to improve CO₂ reduction performance in order to achieve a long-term sustainability. Metal-organic frameworks (MOFs) are recently emerging as a new type of photocatalysts for CO₂ reduction due to their excellent CO₂ adsorption capability and unique structural characteristics. This review examines the most recent breakthroughs in various techniques for modifying MOFs in order to improve their efficiency of photocatalytic CO₂ reduction. The advantages of MOFs using as photocatalysts are summarized, followed by different methods for enhancing their effectiveness for photocatalytic CO₂ reduction via partial ion exchange of metal clusters, design of bimetal clusters, the modification of organic linkers, and the embedding of metal complexes. For integrating MOFs with semiconductors, metallic nanoparticles (NPs), and other materials, a number of different approaches have been also reviewed. The final section of this review discusses the existing challenges and future prospects of MOFs as photocatalysts for CO₂ reduction. Hopefully, this review can stimulate intensive research on the rational design and development of more effective MOF-based photocatalysts for visible-light driven CO₂ conversion.     

Combined effects of adsorption and photocatalysis by hybrid TiO2/ZnO-calcium alginate beads for the removal of copper

The use of nanosized titanium dioxide(TiO_2) and zinc oxide(ZnO) in the suspension form during treatment makes the recovering and recycling of photocatalysts difficult.Hence,supported photocatalysts are preferred for practical water treatment applications.This study was conducted to investigate the efficiency of calcium alginate(CaAlg) beads that were immobilized with hybrid photocatalysts,TiO_2/ZnO to form TiO_2/ZnO-CaAlg.These immobilized beads,with three different mass ratios of TiO_2:ZnO(1:1,1:2,and 2:1) were used to remove Cu(Ⅱ) in aqueous solutions in the presence of ultraviolet light.These beads were subjected to three cycles of photocatalytic treatment with different initial Cu(Ⅱ) concentrations(10-80 ppm).EDX spectra have confirmed the inclusion of Ti and Zn on the surface of the CaAlg beads.Meanwhile,the surface morphology of the beads as determined using SEM,has indicated differences of before and after the photocatalytic treatment of Cu(Ⅱ).Among all three,the equivalent mass ratio TiO_2/ZnO-CaAlg beads have shown the best performance in removing Cu(Ⅱ) during all three recycling experiments.Those TiO_2/ZnO-CaAlg beads have also shown consistent removal of Cu,ranging from 7.14-52.0 ppm(first cycle) for initial concentrations of10-80 ppm.In comparison,bare CaAlg was only able to remove 6.9-48 ppm of similar initial Cu concentrations.Thus,the potential use of TiO_2/ZnO-CaAlg beads as environmentally friendly composite material can be further extended for heavy metal removal from contaminated water.     

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.     

钯掺TiO2光催化降解全氟辛酸

全氟辛酸(perfluorooctanoic acid,PFOA)以其分布广泛性、生物蓄积性、生物毒性强而成为全球关注的一种新型持久性有机污染物.采用化学还原法制备钯掺二氧化钛(Pd-Ti O2)催化剂,利用XRD、FESEM、UV-vis DRS对催化剂进行表征,并考察其在365 nm紫外光照射下对PFOA的光催化降解效果.结果表明,化学还原的制备方法使Ti O2粒径减小、比表面积增大且对紫外光的吸收性能增大,但并不引起PFOA光催化效果的改变.而Pd掺杂后大大增强了PFOA的降解效果,反应7 h后溶液中氟离子浓度为6.62 mg·L-1,是Ti O2(P25)的7.3倍.投加俘获剂与通入氮气的实验证明,在PFOA的降解过程中·OH起重要作用,氧气的存在可促进PFOA的降解.采用UPLC-QTOF-MS对产物进行鉴定分析,PFOA的可能降解过程是经h+氧化后发生脱羧基反应,产生的全氟烷烃自由基(·CnF2n+1)被·OH氧化,脱氟生成短链全氟羧酸.Pd能作为电子(e-)捕获剂、加速e-向O2等电子受体的转移,从而缓解e-累积,提高对PFOA的降解效果.     

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 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.     

C3N4/BiOBr复合可见光催化剂的性能及其作用机制

利用水热合成法制备了C_3N_4/BiOBr复合可见光催化剂,通过XRD、FT-IR、SEM、DRS、PL等手段对催化剂的物相组成和光化学性能进行了系统表征,利用对罗丹明B(RhB)的降解实验评价了催化剂在可见光照下的光催化降解活性和稳定性并通过ESR分析和自由基捕获实验探究了RhB的光催化降解机制.结果表明,水热合成法可成功制备结晶性能良好的C_3N_4/BiOBr复合可见光催化剂;C_3N_4的复合降低了BiOBr光催化剂的电子-空穴的复合,提高了光催化降解活性,其中15%C_3N_4/BiOBr的活性最佳,可见光照18 min后RhB的脱色率达100%,较纯BiOBr提高了1.5倍,且重复使用5次后仍具有较高的光催化降解活性;复合催化剂光催化降解RhB过程中参与降解的主要活性物种为空穴(h~+)和超氧自由基(·O_2~-),其中h~+影响更为显著.     

Ce/TiO2/g-C3N4异质结的制备及光催化降解PFOA反应机制

采用溶胶凝胶-超声混合法制备了铈/二氧化钛/石墨相氮化碳（Ce/TiO₂/g-C₃N₄）异质结催化剂，通过透射电子显微镜（TEM）、X-射线粉末衍射仪（XRD）、傅里叶变换红外光谱仪（FTIR）和紫外-可见分光光度计（UV-Vis）等表征了复合材料的结构、晶相、活性基团和光吸收性能，并考察了可见光下该催化剂对模拟全氟辛酸（PFOA）废水的降解效果.结果表明，Ce/TiO₂/g-C₃N₄分散性好，粒径小于20 nm，金属Ce的掺入及TiO₂/g-C₃N₄异质结的生成，有效抑制了光生电子和空穴对的复合，使复合光催化剂禁带宽度减小，光吸收范围增大，光催化性能得到明显提升.在pH值为2，PFOA浓度为4 mg·L^-1，催化剂投加量为1 g·L^-1的条件下，可见光照射180 min后，可降解94.4%的PFOA，脱氟率为38.6%.降解过程符合准一级反应动力学，速率常数为0.522 h^-1.通过HPLC-MS分析降解产物，同时结合氟元素物料平衡的计算结果，认为降解机制主要是以阴离子形式存在的PFOA吸附至表面带有大量正电荷的催化剂表面后，在光生空穴和活性自由基的作用下，以自由基机理逐步脱去CF₂生成短链的PFCAs，同时生成氟离子.     

FeTiO3/TiO2纳米异质结的制备和可见光催化性能

采用水热法和溶胶凝胶法制备了新型FeTiO3/TiO2纳米异质结复合材料,并明确了最优的掺杂比例(0.5%).随后利用X射线衍射能谱(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、扫描电镜(SEM)和透射电镜(TEM)等手段对该复合材料进行表征,证实了其结晶度、吸光度随掺杂量的规律性变化.电镜照片显示,该复合材料具有蓬松多孔的微观结构,且晶格条纹清晰、分散度高,有利于光电子的传导.对苯的降解实验表明,相比于纯TiO2,该催化剂的气相可见光催化能力大幅提高,降解率提升了3倍,达到40%,而CO2生成量提升了5倍,超过300 ppm.同时,电化学测试和电子顺磁共振谱(ESR)等均证实,FeTiO3的窄能带能够提高TiO2的光响应,实现可见光激发;而二者的能带相互匹配,有助于转移光生载流子,实现电子-空穴的高效分离,进而其光生电子和自由基生成能力大幅增强,因此,表现出了较强、较稳定的光催化活性.     

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.