Characterization of Pd/TiO2 embedded in multi-walled carbon nanotube catalyst with a high photocatalytic activity

Pd particles loading on TiO₂-embedded multi-walled carbon nanotubes (MWCNTs), MWCNTs, and TiO₂ particles were prepared via an impregnation method with palladium(II) chlorate solution followed by heat treatment at high temperature. To characterize the catalysts, BET surface area, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray, Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy were employed. The prepared catalysts were tested in degradation of methyl orange under visible light. Pd/TiO₂-MWCNTs catalyst demonstrates the highest photocatalytic activity, and the phase transformation from PdO to Pd0 phase takes place at heat treatment of embedded TiO₂. The nanoparticles size of TiO₂ can be decreased by introduction of MWCNTs species. Combining structural characterization with kinetic study results we could conclude that the superior catalytic performance could arise due to the Pd/TiO₂-MWCNTs catalyst’s structure.     

PdO nanoparticles decorated TiO2 film with enhanced photocatalytic and self-cleaning properties

Magnetron sputtering and gas aggregation source (GAS) approaches were combined for the preparation of columnar TiO₂ structures decorated with PdO nanoparticles (NPs). The totally solvent-free synthesis approach provides good control of surface coverage, size, morphology, and stoichiometry of PdO NPs in comparison to wet chemical synthesis methods. X-ray photoelectron spectroscopy (XPS) analysis showed that the heat treatment led to the formation of a mixed oxide state PdO/PdO₂ on the TiO₂ layer. A steady equilibrium between PdO (oxidation by free and adsorbed ?OH) and PdO₂ (reduced by trapped photogenerated electrons) phases under UV irradiation seems to provide an efficient electron-hole pair separation. Such robust PdO–TiO₂ thin films have a strong potential for use as photocatalytic and self-cleaning windows or similar out-door technical surfaces.     

Template‐free Fabrication of Hierarchical Macro‐/mesoporous N‐doped TiO2/graphene Oxide Composites with Enhanced Visible‐light Photocatalytic Activity

Hierarchical macro‐/mesoporous N‐doped TiO₂/graphene oxide (N‐TiO₂/GO) composites were prepared without using templates by the simple dropwise addition mixed solution of tetrabutyl titanate and ethanol containg graphene oxide (GO) to the ammonia solution, and then calcined at 350 °C. The as‐prepared samples were characterized by scanning electron microscopy (SEM), Brunauer‐Emmett‐Teller (BET) surface area, X‐ray diffraction (XRD), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and UV‐Vis absorption spectroscopy. The photocatalytic activity was evaluated by the photocatalytic degradation of methyl orange in an aqueous solution under visible‐light irradiation. The results show that N‐TiO₂/GO composites exhibited enhanced photocatalytic activity. GO content exhibited an obvious influence on photocatalytic performance, and the optimal GO addition content was 1 wt%. The enhanced photocatalytic activity could be attributed to the synergetic effects of three factors including the improved visible light absorption, the hierarchical macro‐mesoporous structure, and the efficient charge separation by GO.     

低温静电自组装法制备贵金属修饰TiO_2纳米结构薄膜及其增强的光催化性能(英文)

以碱-水热法在金属Ti片上原位生长了TiO2纳米结构(纳米花和纳米线)薄膜,并采用低温静电自组装方法将超细贵金属(金、铂、钯)纳米颗粒均匀沉积于多孔TiO2薄膜上.负载于Ti片上的贵金属/TiO2纳米结构薄膜具有一体化结构、多孔架构和高光催化活性.超高分辨率场发射扫描电子显微镜(FESEM)直接观察表明贵金属纳米颗粒在TiO2表面分布均匀,且颗粒之间相互分离,金、铂、钯纳米颗粒的平均粒径分别约为4.0、2.0和10.0nm.俄歇电子能谱(AES)纵深成分分析表明贵金属不仅沉积于薄膜表面,且大量分布于TiO2纳米结构薄膜内部,其深度超过580 nm.X射线光电子能谱(XPS)分析表明,经300°C下在空气中热处理后,纳米金仍保持金属态,纳米铂部分被氧化成PtOabs,而钯粒子则完全被氧化成氧化钯(PdO).以低温静电自组装法沉积贵金属,贵金属负载量可通过调节组装时间与溶胶pH值来控制.光催化降解甲基橙的结果表明,沉积的纳米金和铂能显著增加TiO2纳米结构薄膜的光催化活性,说明金和铂粒子可促进光生载流子的分离;但负载的PdO对TiO2薄膜的光催化性能增强几乎无作用.     

Doping of TiO2–GO and TiO2–rGO with Noble Metals: Synthesis,Characterization and Photocatalytic Performance for Azo Dye Discoloration

The nanocomposites of titania coupled with graphene oxide (GO) and reduced graphene oxide (rGO), respectively, were prepared by homogeneous hydrolysis with urea. Graphene was obtained by effect of high‐intensity cavitation field on natural graphite in the presence of strong aprotic solvents in pressurized ultrasonic reactor. The morphology of TiO₂–GO and TiO₂–rGO composites was assessed by scanning electron microscopy and atomic force microscopy. The nitrogen adsorption–desorption was used for determination of surface area (BET) and porosity. Raman and IR spectroscopy were used for qualitative analysis and diffuse reflectance spectroscopy was employed to estimate band‐gap energies. Further enhancement of the photocatalytic activity was attained by codoping of composites with noble metals—Au, Pd and Pt. The photocatalytic activity of TiO₂–GO and TiO₂–rGO were assessed by photocatalytic decomposition of Orange II dye in an aqueous slurry under UV and visible light irradiation. The photocatalytic activity of noble metals codoped samples was determined with decomposition of Reactive Black 5 azo dye.     

Template‐free Fabrication of ZnS/TiO2 Photocatalyst with Macrochannels

Constructing a porous structure in photocatalysts is an effective strategy for improving the photocatalytic activity because of its enhanced molecule transfer capability and light capturing efficiency. In this work, a hierarchical macro‐/mesoporous ZnS/TiO₂ composite with macrochannels was successfully synthesized without using templates by the simple dropwise addition of an ethanol solution of tetrabutyl titanate and zinc acetate into a sodium sulfide aqueous solution, which was then calcined at 450°C. Compared with pure TiO₂, the ordered porous ZnS/TiO₂ composite exhibited an enhanced photocatalytic activity on methylene blue removal under UV‐light irradiation. The results indicate that the macro‐/mesoporous structure, the large specific surface area, and the heterostructure combination between ZnS and TiO₂ play a synergistic effect on the enhanced photocatalytic activity via improving the light absorption and the diffusion of organic molecules, providing more reactive sites for the photocatalytic reaction and improving the separation of photogenerated electron–hole pairs, respectively. Radical trapping experiments demonstrated that holes (h⁺) and superoxide anion radicals (O₂⁻) play an important role in the photocatalytic oxidation process.     

Microwave‐Hydrothermal Preparation and Visible‐Light Photoactivity of Plasmonic Photocatalyst Ag‐TiO2 Nanocomposite Hollow Spheres

Visible‐light‐driven plasmonic photocatalyst Ag‐TiO₂ nanocomposite hollow spheres are prepared by a template‐free chemically‐induced self‐transformation strategy under microwave‐hydrothermal conditions, followed by a photochemical reduction process under xenon lamp irradiation. The prepared samples are characterized by using scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N₂ adsorption‐desorption isotherms, X‐ray photoelectron spectroscopy, UV/Vis and Raman spectroscopy. Production of ?OH radicals on the surface of visible‐light illuminated TiO₂ was detected by using a photoluminescence method with terephthalic acid as the probe molecule. The photocatalytic activity of as‐prepared samples was evaluated by photocatalytic decolorization of Rhodamine B (RhB) aqueous solution at ambient temperature under visible‐light irradiation. The results show that the surface plasmon absorption band of the silver nanoparticles supported on the TiO₂ hollow spheres was red shifted, and a strong surface enhanced Raman scattering effect for the Ag‐TiO₂ nanocomposite sample was observed. The prepared nanocomposite hollow spheres exhibits a highly visible‐light photocatalytic activity for photocatalytic degradation of RhB in water, and their photocatalytic activity is higher than that of pure TiO₂ and commercial Degussa P25 (P25) powders. Especially, the as‐prepared Ag‐TiO₂ nanocomposite hollow spheres at the nominal atomic ratio of silver to titanium ( R ) of 2 showed the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2.     

High ethanol sensitivity of Palladium/TiO2 nanobelt surface heterostructures dominated by enlarged surface area and nano-Schottky junctions

TiO₂ nanobelts were prepared by the hydrothermal growth method. The surface of the nanobelts was coarsened by selective acid corrosion and functionalized with Pd catalyst particles. Three nanobelt samples (TiO₂ nanobelts, surface-coarsened TiO₂ nanobelts and Pd nanoparticle/TiO₂ nanobelt surface heterostructures) were configured as gas sensors and their sensing ability was measured. Both the surface-coarsened nanobelts and the Pd nanoparticle-decorated TiO₂ nanobelts exhibited dramatically improved sensitivity to ethanol vapor. Pd nanoparticle-decorated TiO₂ nanobelts with surface heterostructures exhibited the best sensitivity, selectivity, working temperature, response/recovery time, and reproducibility. The excellent ethanol sensing performance is attributed to the large surface area and enhancement by Schottky barrier-type junctions between the Pd nanoparticles and TiO₂ nanobelts.     

Improved solar-driven photocatalytic performance of BiOI decorated TiO2 benefiting from the separation properties of photo-induced charge carriers

In this work, BiOI decorated TiO₂ photocatalysts were prepared in-situ by a facile hydrothermal method and characterized by X-ray diffraction (XRD), UV/Vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and surface photovoltage (SPV) spectroscopy. The reactive radicals during the photocatalytic reaction were detected by scavenger experiments. BiOI/TiO₂ composites exhibit higher performance than the pure TiO₂ towards photocatalytic decolorization of methyl orange (MO) aqueous solution, when the molar ratio of Bi/Ti is 2%, the sample has the highest photocatalytic activity. The enhanced photocatalytic performance of BiOI/TiO₂ could be ascribed to the separation properties of photo-induced charge carriers and strong interaction between BiOI and TiO₂. Based on the observations, a Z-scheme charge separation mechanism was proposed.     

Preparation of SnO2–TiO2/Fly Ash Cenospheres and its Application in Phenol Degradation

SnO₂–TiO₂/fly ash cenospheres (FAC) were prepared via hydrothermal method and used as an active photocatalyst in a photocatalytic system. Scanning electron microscopy, X‐ray diffraction analysis, UV–Vis diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy and N₂ adsorption–desorption measurements were used to determine the structure and optical property of SnO₂–TiO₂/FAC. Phenol was selected as the model substance for photocatalytic reactions to evaluate catalytic ability. Results showed that the degradation efficiency of phenol by SnO₂–TiO₂/FAC was 90.7% higher than that decomposed by TiO₂/FAC. Increased efficiency could be due to the enhanced synergistic effect of semiconductors and FAC could provide more adsorption sites for the pollutant in the photocatalytic reaction. Furthermore, SnO₂–TiO₂/FAC composites exhibited excellent photocatalytic stability in four reuse cycles. Radical‐trapping experiments further revealed the dominating functions of holes in the photocatalytic reaction.     

Photodegradation of Rhodamine B on Sulfur Doped ZnO/TiO2 Nanocomposite Photocatalyst under Visible-light Irradiation

Sulfur doped ZnO/TiO₂ nanocomposite photocatalysts were synthesized by a facile sol‐gel method. The structure and properties of catalysts were characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), UV‐vis diffusive reflectance spectroscopy (DRS) and N₂ desorption‐adsorption isotherm. The XRD study showed that TiO₂ was anatase phase and there was no obvious difference in crystal composition of various S‐ZnO/TiO₂. The XPS study showed that the Zn element exists as ZnO and S atoms form SO^2?₄. The prepared samples had mesoporosity revealed by N₂ desorption‐adsorption isotherm result. The degradation of Rhodamine B dye under visible light irradiation was chosen as probe reaction to evaluate the photocatalytic activity of the ZnO/TiO₂ nanocomposite. The commercial TiO₂ photocatalyst (Degussa P25) was taken as standard photocatalyst to contrast the prepared different photocatalyst in current work. The improvement of the photocatalytic activity of S‐ZnO/TiO₂ composite photocatalyst can be attributed to the suitable energetic positions between ZnO and TiO₂, the acidity site caused by sulfur doping and the enlargement of the specific area. S‐3.0ZnO/TiO₂ exhibited the highest photocatalytic activity under visible light irradiation after Zn amount was optimized, which was 2.6 times higher than P25.     

Electrospun Mesoporous InVO4/TiO2 Nanobelts with Enhanced Photocatalytic Properties

In the present paper, mesoporous InVO₄/TiO₂ nanobelts with diameter about 400 nm have been synthesized by elaborately designed electrospinning process. The microstructures of InVO₄/TiO₂ nanobelts are characterized in detail, and their photoelectrocatalytic properties are comprehensively investigated by the photocatalytic degradation tests with tetracycline (TTC) and rhodamine B (RhB) waste water. Furthermore, the energy bandgap and density of states of orthorhombic InVO₄ and anatase TiO₂ are modeled and analyzed by density functional theory. Compared with single InVO₄ nanobelts and TiO₂ nanofibers, mesoporous InVO₄/TiO₂ nanobelts possess the extraordinary photocatalytic efficiencies and exceptional cycle performances, which may be ascribed to the successful construction of heterostructures between InVO₄ and TiO₂ and unique one‐dimensional belt structures.     

Synthesis,characterization and photocatalytic application of TiO2/magnetic graphene for efficient photodegradation of crystal violet

A magnetized nano‐photocatalyst based on TiO₂/magnetic graphene was developed for efficient photodegradation of crystal violet (CV). Scanning electron microscopy, X‐ray diffraction, energy‐dispersive X‐ray spectroscopy and elemental mapping were used to characterize the prepared magnetic nano‐photocatalyst. The photocatalytic activity of the synthesized magnetic nano‐photocatalyst was evaluated using the decomposition of CV as a model organic pollutant under UV light irradiation. The obtained results showed that TiO₂/magnetic graphene exhibited much higher photocatalytic performance than bare TiO₂. Incorporation of graphene enhanced the activity of the prepared magnetic nano‐photocatalyst. TiO₂/magnetic graphene can be easily separated from an aqueous solution by applying an external magnetic field. Effects of pH, magnetized nano‐photocatalyst dosage, UV light irradiation time, H₂O₂ amount and initial concentration of dye on the photodegradation efficiency were evaluated and optimized. Efficient photodegradation (>98%) of the selected dye under optimized conditions using the synthesized nano‐photocatalyst under UV light irradiation was achieved in 25 min. The prepared magnetic nano‐photocatalyst can be used in a wide pH range (4–10) for degradation of CV. The effects of scavengers, namely methanol (OH^? scavenger), p‐benzoquinone (O₂^?? scavenger) and disodium ethylenediaminetetraacetate (hole scavenger), on CV photodegradation were investigated.     

The Synthesis and Photocatalytic Properties of TiO2 Nanotube Array by Starch‐Modified Anodic Oxidation

In this study, the characterization and photocatalytic activity of TiO₂ nanotube arrays prepared by anodization process with starch addition were investigated in detail. The results suggested that the optimum mass fraction of starch added in anodization process was 0.1%, with which TiO₂ nanotube arrays owning good tubular structure were synthesized. The tube length and average inner diameter of nanotubes were approximately 4 μm and 30 nm, respectively. Through the characterization of TiO₂ nanotube arrays by energy dispersive spectrometer, scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, Fourier Transform Infrared (FTIR) spectroscopy, it was found that the as‐prepared nanotubes possessed well uniformed and higher photodegradation responsive than the pure TiO₂. Moreover, it was expected that the as‐prepared nanotubes exhibited good photocatalytic activity for the degradation of RhB under UV‐light irradiation, which could be ascribed to their good morphology, enhanced UV‐light absorption property and electron transmission ability during the photocatalytic reaction. In addition, the nanotubes were not significantly regenerated during the cycling runs experiment. Overall, this study could provide a principle method to synthesize TiO₂ nanotube arrays with enhanced photocatalytic activity by anodization process with starch addition for environmental purification.     

Effect of Erbium on the Photocatalytic Activity of TiO2/Ag Nanocomposites under Visible Light Irradiation

Erbium co‐doped TiO₂/Ag catalysts are synthesized by using a simple, one‐step solvothermal method and characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, Raman analysis, X‐ray photoelectron spectroscopy, and diffuse reflectance spectroscopy. The catalysts exhibit anatase crystal structures with increased visible light absorption compared with pure TiO₂. Enhanced photocatalytic activity is observed with Er co‐doped TiO₂/Ag nanocomposites for Rhodamine B degradation under visible light irradiation. The photocatalytic activity of 1 % Er co‐doped TiO₂/Ag is much higher than that of TiO₂/Ag, TiO₂/Er, pure TiO₂, and commercial Degussa P25. The kinetics of the degradation process are studied and the pseudo‐first‐order rate constant (k) and half‐life time (t_1/2) of the reaction are calculated. The enhanced activity might be accredited to the efficient separation of electron–hole pairs by silver and higher visible light absorption of TiO₂ induced by Er.     

Synthesis of 3D hierarchical porous TiO2/InVO4 nanocomposites with enhanced visible-light photocatalytic properties

Three-dimensional (3D) hierarchical porous TiO₂/InVO₄ nanocomposites were fabricated by loading TiO₂ nanoparticles on the surface of porous InVO₄ microspheres. X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis spectroscopy and photoluminescence spectroscopy (PL) were adopted to analyze the structure–property relationship of samples. The results show that the surface of as-prepared TiO₂/InVO₄ nanocomposites are composed of uniformly interconnected bi-phase nanocrystals, forming a close interface between these two components, which is favorable for the highly efficient interparticle electron transfer to achieve enhanced photocatalytic properties. However, the adsorption ability is decreased due to the loading of TiO₂ nanoparticles on the surface of InVO₄. Therefore, under the joint action of these factors, the TiO₂/InVO₄ nanocomposites achieve the best photocatalytic activity when the mole ratio of In:Ti reaches 4:1, and the visible-light photocatalytic activity is about as 3.3 times high as that of pure InVO₄ without modification.     

Plasmon-resonance-enhanced visible-light photocatalytic activity of Ag quantum dots/TiO2 microspheres for methyl orange degradation

We successfully prepared Ag quantum dots modified TiO₂ microspheres by facile solvothermal and calcination method. The as-prepared Ag quantum dots/TiO₂ microspheres were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The Ag quantum dots/TiO₂ photocatalyst showed excellent visible light absorption and efficient photocatalytic activity for methyl orange degradation. And the sample with the molar ratio of 0.05 (Ag to Ti) showed the best visible light photocatalytic activity for methyl orange degradation, mainly because of the surface plasmon resonance (SPR) effects of Ag quantum dots to generate electron and hole pairs for enhanced visible light photocatalysis. Finally, possible visible light photocatalytic mechanism of Ag quantum dots/TiO₂ microspheres for methyl orange degradation was proposed in detail.     

溶剂热法制备Ag/TiO_2纳米材料及其光催化性能

以乙醇为溶剂,钛酸四丁酯为前驱体,用溶剂热法制备了Ag表面修饰的负载型纳米二氧化钛光催化剂.利用X射线衍射(XRD)、N2吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外-可见(UV-Vis)光谱等技术对其进行了系统的表征,以亚甲基蓝(MB)溶液的脱色降解为模型反应,考察了不同Ag含量样品的光催化性能.结果表明:用溶剂热法制备的样品中TiO2皆为锐钛矿相,金属Ag颗粒沉积在TiO2表面,粒径为2nm左右,比表面积较溶胶凝胶法制备的样品大大增加,最高可达151.44m2·g-1;UV-Vis光谱和光催化实验表明:Ag修饰使TiO2对光的吸收能力大大增强,吸收带边红移至可见光区,亚甲基蓝在该复合材料上的光催化降解反应遵循一级反应动力学模型;溶剂热法制备样品的光催化性能明显好于溶胶凝胶法制备的样品,在紫外光和可见光下,Ag摩尔分数为5%的样品表现出最佳的光催化活性.     

Preparation of Ce‐doped TiO2 Hollow Fibers and Their Photocatalytic Degradation Properties for Dye Compound

Cerium‐doped titanium dioxide (TiO₂) with a hollow fiber structure was successfully prepared using ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fiber as the template. The effects of cerium (Ce)‐doping on the crystallite sizes, crystal pattern, and optical property of the prepared catalysts were investigated by means of techniques such as scanning electron microscopy (SEM), X‐ray diffraction (XRD), BET surface area, and UV‐vis diffuse absorption spectroscopy. SEM observation showed that the prepared TiO₂ fibers possessed fibrous shape inherited from the cotton fiber and had a hollow structure. As confirmed by XRD and UV‐vis diffuse absorption spectroscopy examinations, Ce‐doping restrained the growth of grain size and extended the photoabsorption edge of TiO₂ hollow fiber into the visible light region. The present photocatalyst showed higher photocatalytic reactivity in photodegradation of highly concentrated methylene blue (MB) solutions than pure TiO₂ under UV and visible light, and the amount of Ce‐doped significantly affected the catalytic property. In the experiment condition, the photocatalytic activity of 0.5 mol% Ce‐doped TiO₂ fiber was optimal of all the prepared samples. In addition, the possibility of cyclic usage of the photocatalyst was also confirmed. The material was easily removed by centrifugal separation. Therefore, using the template method and by doping with cerium, TiO₂ may hopefully become a low‐energy consuming, high activity and green environmentally friendly catalytic material.     

Synthesis of Three‐dimensionally Ordered Macroporous TiO2 and TiO2/WO3 Composites and Their Photocatalytic Performance

This work presents the characterization and preparation of three‐dimensionally ordered macroporous TiO₂ and TiO₂/WO₃ composite nanoparticles with enhanced visible‐light‐responsive properties for rhodamine B (Rh B) photodegradation. The 3DOM TiO₂ and TiO₂/WO₃ composites were prepared through a dip‐infiltrating sol‐gel process using a polystyrene (PS) colloidal crystal template. The materials were characterized by SEM, TEM, XRD, BET, XPS and UV/Vis. The 3DOM TiO₂/WO₃ composite structures ranged from well‐defined 3DOM structures, which are highly ordered and interconnected via small pore windows, to collapsed three‐dimensional structures as the WO₃ content increased. The photoresponse range and specific surface area of the composite increased with less than 0.025 g of WCl₆. The 3DOM TiO₂/WO₃ composite with less than 0.025 g of WCl₆ exhibited a higher catalytic activity than 3DOM TiO₂ for the photocatalytic degradation of Rh B under simulated sunlight illumination.