Photocatalytic activity of TiO2 supported on multi-walled carbon nanotubes under simulated solar irradiation

TiO₂ particles supported on multi-walled carbon nanotubes (MWCNTs) were prepared using a sol–gel method to investigate their photocatalytic activity under simulated solar irradiation for the degradation of methyl orange (MO) in aqueous solution. The prepared composites were analyzed using XRD, SEM, EDS and UV–vis absorption spectroscopy. The results of this study indicated that there was little difference in the shape and structure of MWCNTs/TiO₂ composite and pure TiO₂ particles. The composite exhibited enhanced absorption properties in the visible light range compared to pure TiO₂. The degradation of MO by MWCNTs/TiO₂ composite photocatalysts was investigated under irradiation with simulated solar light. The results of this study indicated that MWCNTs played a significant role in improving photocatalytic performance. Different amounts of MWCNTs had different effects on photodegradation efficiency, and the most efficient MO photodegradation was observed for a 2% MWCNT/TiO₂ mass ratio. Photocatalytic reaction kinetics were described using the Langmuir–Hinshelwood (L–H) model. The photocatalyst was reused for eight cycles, and it retained over 95.2% photocatalytic degradation efficiency. Possible decomposition mechanisms were also discussed. The results of this study indicated that photocatalytic reactions with TiO₂ particles supported on MWCNTs under simulated solar light irradiation are feasible and effective for degrading organic dye pollutants.     

Fabrication of plasmonic Au/TiO2 nanotube arrays with enhanced photoelectrocatalytic activities

Uniformly dispersed Au nanoparticles (NPs) deposited on the surface of highly ordered TiO₂ nanotube arrays (Au/TiO₂ NTs) were synthesized through a two-step process including anodization method and microwave-assisted chemical reduction route. The investigation indicated that Au NPs grew uniformly on the walls of TiO₂ NTs. Au/TiO₂ NTs exhibited excellent visible light absorption due to the LSPR effect of Au NPs. Au/TiO₂ NTs exhibited much higher photocurrent density and the photoconversion efficiency of Au decorated TiO₂ NTs was about 2.05 times greater than that of bare TiO₂ NTs. Besides, the PL intensity of Au/TiO₂ NTs was much lower than that of TiO₂ NTs, revealing a decrease in charge carrier recombination. The prepared Au/TiO₂ NTs exhibited superior photoelectrocatalytic activity and stability in the degradation of MB under simulated solar light irradiation. The synergy effect between nanotubular structures of TiO₂ and uniformly dispersed Au nanoparticles, as well as the small bias potential and strong interaction between Au and TiO₂, facilitated the Au plasmon-induced charge separation and transfer, which lead to highly efficient and stable photoelectrocatalytic activity.     

Aerosol processing of Ag/TiO2 composite nanoparticles for enhanced photocatalytic water treatment under UV and visible light irradiation

In this study, we investigated the effect of Ag addition on the photocatalytic reactivity of TiO₂ nanoparticles (NPs). Controlled amounts of Ag were incorporated in TiO₂ NPs using aerosol spray pyrolysis and subsequent calcination. Ag/TiO₂ composite NPs containing different amounts of Ag (e.g., 0, 0.5, 1, 2, and 5 wt%) were successfully fabricated. The photodegradation performances of the as-prepared Ag/TiO₂ composite NPs were tested using methylene blue (MB) solution under UV and visible light irradiation. Upon increasing the Ag content to 1 wt%, the resulting Ag/TiO₂ composite NPs exhibited increased photocatalytic reactivity due to lowered bandgap energy, which promoted both charge generation and separation. However, when the Ag content exceeded 1 wt%, the photocatalytic reactivity of the resulting Ag/TiO₂ composite NPs was considerably deteriorated due to the masking effect of the excess Ag on the reactive sites of TiO₂. Hence, the incorporation of an optimized amount of Ag in the TiO₂ matrix promotes the photocatalytic reactivity of Ag/TiO₂ composite NPs by controlling their bandgap energy and charge generation and separation processes. These results could lead to the development of photodegradation active substances for water treatment in organic solutions.     

Degradation of chlorophenol by photocatalysts with various transition metals

In this research, the photocatalytic degradation of 4-chlorophenol (4-CP) in TiO₂ aqueous suspension was studied. TiO₂ photocatalysts were prepared by sol-gel method. The dominant anatase-structure on TiO₂ particles was observed after calcining the TiO₂ gel at 500 °C for 1 hr. Photocatalysts with various transition metals (Fe, Cu, Nd, Pd and Pt) loading were tested to evaluate the effect of transition metal impurities on photodegradation. The photocatalytic degradation in most cases follows first-order kinetics. The maximum photodegradation efficiency was obtained with TiO₂ dosage of 0.4 g/L, retention time of 1 min and air flow rate of 2,500 cc/min. The photodegradation efficiency with Pt-TiO₂ or Pd-TiO₂ is higher than pure TiO₂ powder. The optimal content value of Pt and Pd is 2 wt%. However, the photodegradation efficiency with Fe(1.0 wt%)-TiO₂ and Cu(1.0 wt%)-TiO₂ is lower than pure TiO₂ powder. This paper was prepared at the 2004 Korea/Japan/Taiwan Chemical Engineering Conference held at Busan, Korea between November 3 and 4, 2004.     

Surface Functionalization of Electrospun TiO2 Nanofibers by Au Sputter Coating for Photocatalytic Applications

Au-doped titania (TiO₂:Au) nanofibers were prepared by a combination of the electrospinning method and sputtering technology. The results show that the morphologies of Au-deposited TiO₂ nanofibers can be well controlled by the sputtering time. The photocatalytic decomposition of acetaldehyde on the TiO₂:Au nanofibers was investigated at room temperature. Compared with pure TiO₂ nanofibers, the TiO₂:Au nanofibers exhibited higher photocatalytic activities.     

Hydrothermal growth of TiO2 nanowire membranes sensitized with CdS quantum dots for the enhancement of photocatalytic performance

In this paper, TiO₂ nanowires (NWs) on Ti foils were prepared using a simple hydrothermal approach and annealing treatment. CdS quantum dots (QDs) were assembled onto the crystallized TiO₂ NWs by sequential chemical bath deposition. Ultraviolet-visible absorption spectra showed that CdS adds bands in the visible to the TiO₂ absorption and exhibited a broad absorption band in the visible region, which extended the scope of absorption spectrum and helped improve the photocatalytic degradation efficiency. The results of photocatalytic experiment revealed that CdS-TiO₂ NWs possessed higher photocatalytic activities toward methyl orange than pure TiO₂ nanowires. The degradation efficiency of 96.32% after ten cycles indicated that the as-prepared CdS-TiO₂ composite exhibited excellent long-time recyclable ability and can be reused for the degradation of contaminants.     

Cu2O-based binary and ternary photocatalysts for the degradation of organic dyes under visible light

As competitive photocatalysts, Cu₂O nanoparticles meet with severe photogenerated carries recombination and insufficient light absorption, leading to the poor photocatalytic performance. Herein, the truncated Cu₂O-Au (CA) binary and Cu₂O-Au-TiO₂ (CAT) ternary octahedra with Au nanoparticles (Au NPs), preferentially supported on the (110) and (100) planes of Cu₂O, are synthesized for efficient photocatalytic degradation reactions. The photodegradation rates of MO of CA1 (Cu₂O-Au containing 1 wt % Au) and CAT are as high as 95.61% and 96.5% under 60 min of visible light irradiation, respectively. On the one hand, the synergistic function of localized surface plasmon resonance (LSPR) of Au NPs and Schottky barrier accelerate the separation and transfer of photogenerated carriers. On the other hand, a Z-scheme electron transfer system is constructed in CAT to promote the photodegradation performance. According to the finite-difference-time-domain (FDTD) simulation result, there is a strong electric field enhancement at the contact sites between Au, Cu₂O and TiO₂, which accelerates the electron transfer to a large extent and separates the electron-hole pairs. Therefore, this work may provide an approach for the synthesis and applications of multiple heterostructure catalyst.     

Au nanoparticles-doped g-C3N4 nanocomposites for enhanced photocatalytic performance under visible light illumination

Surface and bandgap engineering of graphitic carbon nitride (g-C₃N₄) could be vital in enhancing photocatalytic performance by suppressing the recombination rate of photogenerated electron-hole pairs. The present report investigated the doping effects of various wt.% (0.2–5.0%) of gold nanoparticles (Au NPs) to g-C₃N₄ (Au/g-C₃N₄) for the enhancement of the photocatalytic efficiency of g-C₃N₄ nanocomposites. A straightforward and cost-effective synthesis methodology has been applied for the desired nanocomposites. Relevant characterization tools such as XRD, XPS, TEM, FTIR, and UV–Vis were utilized to analyze various physicochemical properties. The TEM images clearly show that spherical Au NPs were homogeneously distributed into the thin carbon nitride graphitic layers, confirming the successful doping of Au. The higher-magnification TEM image confirms that the sizes of the Au NPs varied from 15 to 25 nm. The photoactivity of the newly designed Au/g-C₃N₄ nanocomposites has been evaluated for the degradation of both methylene blue dye and the drug gemifloxacin mesylate, and their efficiencies were compared with that of bare g-C₃N₄. Our findings revealed that Au/g-C₃N₄ nanocomposites with various Au contents had superior photocatalytic activity compared to bare g-C₃N₄. However, the 1%Au/g-C₃N₄ nanocomposite could be considered the optimum photocatalyst, producing 95.13% destruction of the target dye molecule in 90 min, in contrast to the 69% achieved with bare g-C3N4, under the clean energy of visible light illumination. Additionally, the photodegradation rate of the 1%Au/g-C₃N₄ nanocomposite is 2.69 times higher than the rate of bare g-C₃N₄. This report might open a new gateway towards a straightforward and cost-effective synthesis approach for Au/g-C₃N₄ nanocomposites and provides a smooth and robust platform for the utilization of this new nanocomposite for environmental remediation processes.     

Au掺杂水热均匀沉淀高温制备TiO_2的光催化性能

向水热均匀沉淀、800℃焙烧制得的高活性、易分离TiO2(TiO2-800)中掺杂金(Au),以光催化降解活性艳红染料X-3B作为模型反应,考察了掺Au量、制备条件、Au的价态等对Au/TiO2-800光催化性能的影响。结果表明,氨水作为沉淀剂,200℃焙烧的0.5%Au/TiO2-800的光催活性较TiO2-800有较大提高,染料X-3B的降解率由93%提高到了100%。还原实验显示,0.5%Au/TiO2-800表面存在的离子态Au能有效提高TiO2-800光催化活性。     

A unique Cu2O/TiO2 nanocomposite with enhanced photocatalytic performance under visible light irradiation

A unique Cu₂O/TiO₂ nanocomposite with high photocatalytic activity was synthesized via a two-step chemical solution method and used for the photocatalytic degradation of organic dye. The structure, morphology, composition, optical and photocatalytic properties of the as-prepared samples were investigated in detail. The results suggested that the Cu₂O/TiO₂ nanocomposite is composed of hierarchical TiO₂ hollow microstructure coated by a great many Cu₂O nanoparticles. The photocatalytic performance of Cu₂O/TiO₂ nanocomposite was evaluated by the photodegradation of methylene blue (MB) under visible light, and compared with those of the pure TiO₂ and Cu₂O photocatalysts synthesized by the identical synthetic route. Within 120 min of reaction time, nearly 100% decolorization efficiency of MB was achieved by Cu₂O/TiO₂ photocatalyst, which is much higher than that of pure TiO₂ (26%) or Cu₂O (32%). The outstanding photocatalytic efficiency was mainly ascribed to the unique architecture, the extended photoresponse range and efficient separation of the electron-hole pairs in the Cu₂O/TiO₂ heterojunction. In addition, the Cu₂O/TiO₂ nanocomposite also retains good cycling stability in the photodegradation of MB.     

Preparation, Characterization and Photocatalytic Activities of F-doped TiO2 Nanotubes

F-doped TiO₂ nanotubes were prepared by impregnation method. The prepared catalysts were characterized by XRD, TEM, and XPS. The photocatalytic activity of F-doped TiO₂ nanotubes was evaluated through the photodegradation of aqueous methyl orange. The experiments demonstrated that the F-doped TiO₂ nanotubes calcined at 300 °C possessed the best photocatalytic activity. Compared with pure TiO₂ nanotubes, the doping with F⁻ significantly enhanced the photocatalytic efficiency. The high photocatalytic activity was ascribed to several beneficial effects produced by F-doping: creation of oxygen vacancies, presence of Ti³⁺, and so on. An erratum to this article can be found at     

Preparation of renewable porous TiO<Subscript>2</Subscript>/PVA composite sphere as photocatalyst for methyl orange degradation

Firstly, preparation of porous polyvinyl alcohol (PVA) spheres were investigated in detail by phase inversion method using N,N-dimethylacetamide (DMAc) and polyvinylpyrrolidone (PVP) as pore-forming additives. The morphology and pore structure of PVA spheres were characterized by SEM and BET measurements. It was found that the addition of DMAc and PVP increased the pore volume and the surface pore size of PVA sphere respectively. The maximum surface area of the porous PVA sphere reached 220 m²/g. Secondly; the synthesis of photoactive TiO₂ NPs (anatase type) at the low temperature was developed by controlling the aging process of the TiO₂ precursors. The crystallinity and photoactivity of TiO₂ NPs increased with the aging time. Finally, TiO₂ NPs/PVA composite spheres were prepared by immersing PVA sphere into TiO₂ precursor solution. Their structures were characterized by XRD pattern, TEM and TGA measurement. It was found that TiO₂ NPs were successfully immobilized into PVA spheres. The photodegradation of methyl orange (MO) under UV light by TiO₂/PVA spheres showed a good photocatalytic efficiency. Moreover, TiO₂/PVA spheres can be easily regenerated by the repeated immersion process. Overall, the porous TiO₂/PVA sphere displays a good photoactive property and an advantage of easier recovery, which facilitates its application in large-scale wastewater treatment.     

Effect of Carbon Nanotubes and Carbon Nanotubes/Gold Nanoparticles Composite on the Photocatalytic Activity of TiO2 and TiO2‐SiO2

A carbon nanotube (CNT)/gold nanoparticle (NP) nanocomposite was synthesized by simultaneously reducing the Au ions and depositing Au NPs on the surface of a CNT. The functional groups were investigated with Fourier transform infrared spectra. From the Raman spectra, the D‐band and G‐band of the CNT were identified. The deposition of nanometer‐sized Au NPs on the CNT sites was observed by transmission electron microscopy. The photodegradation of methylene blue (MB) in aqueous solutions was studied using various photocatalysts, including TiO₂, TiO₂‐SiO₂, CNT/TiO₂, CNT/TiO₂‐SiO₂, Au/TiO₂, CNT‐Au/TiO₂, and CNT‐Au/TiO₂‐SiO₂ composites. CNT addition leads to a synergic effect, improving the photoactivity of the catalysts. A possible physically based mechanism was proposed involving the reduction of electron‐hole recombination and fast electron‐transfer possibility.     

Synthesis and Photocatalytic Activity of Anatase TiO2 Nanoparticles-coated Carbon Nanotubes

A simple and straightforward approach to prepare TiO₂-coated carbon nanotubes (CNTs) is presented. Anatase TiO₂ nanoparticles (NPs) with the average size ~8 nm were coated on CNTs from peroxo titanic acid (PTA) precursor even at low temperature of 100 °C. We demonstrate the effects of CNTs/TiO₂ molar ratio on the adsorption capability and photocatalytic efficiency under UV–visible irradiation. The samples showed not only good optical absorption in visible range, but also great adsorption capacity for methyl orange (MO) dye molecules. These properties facilitated the great enhancement of photocatalytic activity of TiO₂ NPs-coated CNTs photocatalysts. The TiO₂ NPs-coated CNTs exhibited 2.45 times higher photocatalytic activity for MO degradation than that of pure TiO₂.     

Ir promotion of TiO2 supported Au catalysts for selective hydrogenation of cinnamaldehyde

We synthesized Ir-on-Au (Au–Ir) nanoparticles (NPs) using 8–9 nm Au NPs, which had a partial coverage of Ir. Both the studied systems allowed the obtainment of cinnamyl alcohol with high selectivities (> 83%). However, Au–Ir/TiO₂ delivered a hydrogenation rate 5 times higher than that of Au/TiO₂. The deposition of Ir onto the surface of Au and the presence of surface Au–Ir alloy were confirmed by UV–vis and HRTEM respectively. Moreover. Moreover, the strongly shifted XPS binding energy implyed the electron transfer from Ir to Au, which was believed to be responsible for the enhanced H₂ activation capacity of Au.     

Improved Photocatalytic Activity Using Ternary Au-ZnO/rGO Nanocomposite

In the present study, ternary Au-ZnO/rGO nanocomposite was prepared using a modified polyol protocol. The ternary structure was attained by deposition of both gold nanoparticles (AuNPs) and ZnO NPs on the rGO surface. No surfactants or ligands are used in this chemical process. On the other hand, 1,3-propanediol was used as solvent, reducing agent and surfactant to ensure the formation of NPs and inhibit particles accumulation. The XRD data confirm the successful formation of the three materials and the high crystallinity of the as-prepared sample. Moreover, the XPS measurements confirmed the high purity of the nanocomposite. TEM images show the formation of ternary Au/ZnO/rGO nanostructure. However, Au and ZnO NPs exhibited spherical shape with an average size of 20 nm and homogeneously distribution onto the rGO surface. The ternary Au-ZnO/rGO nanocomposite exhibited optical response in both UV and visible region due to the plasmonic properties of AuNPs. The BET data revealed an increase of the surface area of Au-ZnO/rGO nanocomposite compared to bare ZnO and hybrid Au-ZnO NPs which render it a promising system for high photocatalytic activity. The preliminary photodegradation measurements against MB molecules prove the high performance of the ternary Au-ZnO/rGO nanocomposite to decompose pollutant molecules compared to bare ZnO. The observed photocatalytic activity enhancement could be attributed to the apport given by both plasmonic properties of AuNPs and the high surface area of rGO.

     

Influence of Metal (Au, Ag) Micro-Grid on the Photocatalytic Activity of TiO2 Film

In this paper, we prepared TiO₂ thin film with the surface modified by a connected Au micro-grid via a microsphere lithography strategy, and the modified films show higher photocatalytic activity than the pure TiO₂ film. The photocatalytic activity improved as Au loading increased, obtaining the best performance at a certain loading amount, and then decreased at higher loading amount. This behavior, not observed in TiO₂ films modified with Ag micro-grid, can be attributed to the relationship between the energetic positions and the metal clusters size.     

Preparation of photo-catalytic copolymer grafted asymmetric membranes (N-TiO<Subscript>2</Subscript>-PMAA-g-PVDF/PAN) and their application on the degradation of bentazon in water

Nitrogen-doped titanium dioxide (N–TiO₂) was prepared and supported on a novel copolymer grafted membrane matrix to avoid the problems associated with the removal of spent photocatalyst from treated water. Membranes of poly (methacrylic acid) grafted onto poly (vinylidene difluoride) and blended with poly (acrylonitrile) (PMAA-g-PVDF/PAN) were prepared through a dry–wet phase inversion technique. Methacrylic acid side chains were grafted onto an activated PVDF backbone by the method of reversible addition fragmentation chain transfer polymerization and then the novel photocatalytic asymmetric membranes of N–TiO₂–PMAA-g-PVDF/PAN were prepared. The casting solutions were blended with 1–5 % N–TiO₂ before immersion into the coagulation bath. PVDF and PAN offer several advantages which include: mechanical strength and toughness, chemical resistance, unaffected by long-term exposure to UV radiation, low weight, and thermal stability. N–TiO₂ was prepared through sol-gel synthesis. The photocatalytic membranes were evaluated by degradation process of herbicide bentazon in water. Photodegradation studies revealed that the optimum photocatalyst loading was 3 % N–TiO₂ and the optimum pH was 7 for the degradation of bentazon in water. UV–Vis, TOC and LC–MS analyses confirmed the successful photodegradation of bentazon. A bentazon removal efficiency of 90.1 % was achieved at pH 7. N–TiO₂–PMAA-g-PVDF/PAN membranes were successfully prepared and characterized. These photocatalytic membranes showed great potential as a technology for the effective removal of pesticides from water. According to literature, N–TiO₂–PMAA-g-PVDF/PAN asymmetric photocatalytic membranes have not been prepared before for the purpose of treating agricultural wastewater.     

Coupling copper and hydrogenated TiO2 to bare TiO2 structures for improved photocatalytic performance

Coupling of metals and hydrogenated TiO₂ (HT) to bare TiO₂ may improve synergistically the photocatalytic activity of TiO₂ for pollutant decomposition. Herein, we address this issue by investigating the photocatalytic performances of Cu‐loaded HT (CuHT)/bare TiO₂ (CuHTT) heterojunction nanocomposites for the degradation of harmful n‐butanol under simulated solar light illumination. CuHTT with a CuHT‐to‐TiO₂ composition ratio of 0.1 showed a photocatalytic efficiency exceeding those of four reference photocatalysts, exhibiting the advantages of improved visible light absorption efficiency, charge carrier separation, and adsorption capacity. Increasing the CuHT‐to‐TiO₂ ratio from 0.01 to 0.1 improved the photocatalytic efficiency of CuHTT, whereas a further increase to 0.9 resulted in a decreased photocatalytic efficiency. Moreover, the photocatalytic efficiency improved as relative humidity increased from 20% to 70%, decreasing upon its further increase to 95%. The efficiencies of n‐butanol to CO₂ conversion over CuHTT were lower than the corresponding decomposition efficiencies. Incompletely oxidized CO and three organic vapors (butanal, propanal, and 1‐propanol) were determined as major intermediates. A possible mechanism for CuHTT‐catalyzed photodegradation under simulated solar illumination was proposed.     

Au Nanoparticles as Interfacial Layer for CdS Quantum Dot-sensitized Solar Cells

Quantum dot-sensitized solar cells based on fluorine-doped tin oxide (FTO)/Au/TiO₂/CdS photoanode and polysulfide electrolyte are fabricated. Au nanoparticles (NPs) as interfacial layer between FTO and TiO₂ layer are dip-coated on FTO surface. The structure, morphology and impedance of the photoanodes and the photovoltaic performance of the cells are investigated. A power conversion efficiency of 1.62% has been obtained for FTO/Au/TiO₂/CdS cell, which is about 88% higher than that for FTO/TiO₂/CdS cell (0.86%). The easier transport of excited electron and the suppression of charge recombination in the photoanode due to the introduction of Au NP layer should be responsible for the performance enhancement of the cell.