Superior Photostability and Photocatalytic Activity of ZnO Nanoparticles Coated with Ultrathin TiO2 Layers through Atomic‐Layer Deposition

Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO₂ layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO₂ layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO₂ nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO₂ coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO₂ coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO₂, and the photocatalytic activity to that of pure ZnO.     

Solvothermal synthesis of WO3/TiO2/carbon fiber composite photocatalysts for enhanced performance under sunlight illumination

Carbon fiber (CF)‐based WO₃/TiO₂ composite catalysts (WO₃/TiO₂/CF) were successfully synthesized by solvothermal method. The catalysts were characterized by XPS, SEM, BET, XRD, FTIR, Raman and UV–Vis. The analyses confirmed the WO₃/TiO₂ nanoparticles with high crystallinity deposited on the carbon structure. The photocatalytic degradation of Orange II azo dye under UV and sunlight illumination with the synthesized catalyst was explored. The composite catalyst displayed high performance (85%) for Orange II degradation while that of for WO₃/TiO₂ was found as 76%. The effects of CF amount, solution pH, initial dye concentration and catalyst dose on photocatalytic performance were studied. It was found that the degradation efficiency increased from 68% to 90% with the increasing CF amount from 3 wt% to 5 wt%, while the further increase in CF amount (7–10 wt%) decreased the photodegradation due to the blocking the active sites of WO₃/TiO₂. The enhanced photocatalytic efficiency was mainly attributed to the electrical properties of the CF and reduced bandgap.     

Quantitative evaluation of antibacterial activities of nanoparticles (ZnO,TiO2, ZnO/TiO2, SnO2, CuO,ZrO2, and AgNO3) incorporated into polyvinyl butyral nanofibers

Novel hybrid polyvinyl butyral nanofibers have been developed for antimicrobial applications. The nanofiber mats were obtained from a needleless rod electrospinning system. The novel inorganic antibacterial agents were incorporated into the nanofibers, and their antibacterial activity was compared. The obtained nanoparticle/nanofiber hybrid mats have a good surface morphology. The results indicated that the CuO, ZnO, ZnO/TiO₂, and AgNO₃ nanoparticle‐incorporated nanofiber layers have excellent antibacterial activity against to Escherichia coli compared with TiO₂, SnO₂, and ZrO₂ ones. Copyright © 2016 John Wiley & Sons, Ltd.     

The effects of solvent on photocatalytic properties of Bi2WO6/TiO2 heterojunction under visible light irradiation

Bi₂WO₆/TiO₂ heterojunction photocatalysts with two different microstructures were controllably fabricated via a facile two-step synthetic route. XRD, XPS, SEM, TEM, BET-surface, DRS, PL spectra, photoelectrochemical measurement (Mott-Schottky), and zeta-potential analyzer were employed to clarify structural and morphological characteristics of the obtained products. The results showed that Bi₂WO₆ nanoparticles/nanosheets grew on the primary TiO₂ nanorods. The TiO₂ nanorods used as a synthetic template inhibit the growth of Bi₂WO₆ crystals along the c-axis, resulting in Bi₂WO₆/TiO₂ heterostructure with one-dimensional (1D) morphology. The photocatalytic properties of Bi₂WO₆/TiO₂ heterojunction photocatalysts were strongly dependent on their shapes and structures. Compared with bare Bi₂WO₆ and TiO₂, Bi₂WO₆/TiO₂ composite have stronger adsorption ability and better visible light photocatalytic activities towards organic dyes. The Bi₂WO₆/TiO₂ composite prepared in EG solvent with optimal Bi:Ti ratio of 2:12 (S-TB2) showed the highest photocatalytic activity, which could totally decompose Rhodamine B within 10 min upon irradiation with visible light (λ > 422 nm), and retained the high photocatalytic performance after five recycles, confirming its stability and practical usability. The results of PL indicated that Bi₂WO₆ and TiO₂ could combine well to form a heterojunction structure which facilitated electron–hole separation, and lead to the increasing photocatalytic activity.     

Photocatalytic activity of TiO2-MO x composites in the reaction of hydrogen generation from aqueous isopropanol solution

The photocatalytic activity of the composites TiO₂-MO _x (M = Ni, Cu, Zn, Fe, Cr) was studied in the reaction of hydrogen generation from aqueous alcoholic suspensions under UV light. The samples modified by the oxides of the metals capable of being reduced from oxides under photocatalytic conditions showed a high catalytic activity. The studied modifiers were divided in three groups in terms of their effect of the photocatalytic activity of TiO₂: activating (NiO, CuO), inhibiting (Fe₂O₃), and indifferent (ZnO, Cr₂O₃).     

Investigations on the surface modification of ZnO nanoparticle photocatalyst by depositing Pd

In this paper, ZnO nanoparticle photocatalysts were modified by depositing Pd on their surfaces with a photoreduction method. We mainly investigated the modification mechanisms as well as the effects on the photocatalytic activity of ZnO nanoparticles of deposited Pd by means of XPS and SPS (Surface Photovoltage Spectroscopy), and the effects of Pd content on SPS responses were also discussed from the point of the electronic energy level. The results showed that the content of crystal lattice oxygen on the surface of ZnO nanoparticle decreased after an appropriate amount of Pd was deposited, while that of adsorbed oxygen increased, indicating that Pd was mainly deposited on the crystal lattice oxygen. At the same time, the intensity of SPS responses of ZnO nanoparticles remarkably decreased. In addition, the activity of ZnO nanoparticles could be greatly improved by depositing an appropriate amount of Pd in the gas phase photocatalytic oxidation of n-C₇H₁₆. Thus, it could be concluded that the increase in surface content of adsorbed oxygen could facilitate the photocatalytic reaction, and there were close relationships between the SPS response and photocatalytic activity, i.e. the weaker the SPS response, the higher the photocatalytic activity, of Pd-deposited ZnO nanoparticles.     

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.     

Flower-like Bi2WO6/ZnO composite with excellent photocatalytic capability under visible light irradiation

The photocatalytic ability of ZnO is improved through the addition of flower-like Bi₂WO₆ to prepare a Bi₂WO₆/ZnO composite with visible light activity. The composite is characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy with UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy and N₂ adsorption-desorption isotherms. After modification, the band gap energy of Bi₂WO₆/ZnO is reduced from 3.2 eV for ZnO to 2.6 eV. Under visible light irradiation, the Bi₂WO₆/ZnO composite shows an excellent photocatalytic activity for degrading methylene blue (MB) and tetracycline. The photo-degradation efficiencies of (0.3:1) Bi₂WO₆/ZnO for MB and tetracycline are approximately 246 and 4500 times higher than those of bare ZnO, respectively, and correspondingly, the photo-degradation rates for the two pollutants are approximately 120 and 200 times higher than those with bare ZnO, respectively. Moreover, the photocatalyst of (0.3:1) Bi₂WO₆/ZnO exhibits a higher transient photocurrent density of approximately 4.5 μA compared with those of bare Bi₂WO₆ and ZnO nanoparticles. The successful recombination of Bi₂WO₆ and ZnO enhances the photocatalytic activity and reduces the band gap energy of ZnO, which can be attributed to the effective separation of electron–hole pairs. Active species trapping experiments display that [O₂]^? is the major species involved during photocatalysis rather than ?OH and h⁺. This study provides insight into designing a meaningful visible-light-driven photocatalyst for environmental remediation.     

Selective photocatalytic oxidation of alcohols to aldehydes in water by TiO2 partially coated with WO3

Semiconductor TiO₂ particles loaded with WO₃ (WO₃/TiO₂), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO₃/TiO₂ catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO₂. In particular, a catalyst loading 7.6 wt % WO₃ led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO₂ surface of the catalyst, which is active for oxidation, is partially coated by the WO₃ layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO₂ surface. This suppresses subsequent decomposition of the aldehyde on the TiO₂ surface and results in high aldehyde selectivity. The WO₃/TiO₂ catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity.     

Visible light driven photocatalytic activity of ZnO/CuO nanocomposites coupled with rGO heterostructures synthesized by solid-state method for RhB dye degradation

Metal oxide frame works along with carbon materials have been attracting tremendous attention of researches as the potential materials for energy and environmental remediation. In the present work heterostructures of (ZnO/CuO)/rGO ternary nanocomposites were synthesized by solid-state method. The crystalline structure of the nanoparticles was obtained from the XRD analysis. Optical band gap of the ZnO nanoparticles (3.1 eV) is tuned to 2.8 eV in the synthesized (ZnO/CuO)/rGO ternary nanocomposites. Field emission scanning electron microscope images of the (ZnO/CuO)/rGO ternary nanocomposites revealed formation of well-developed flowers like morphology of (ZnO/CuO) nanoparticles on rGO sheets. Photoluminescence spectroscopy analysis of (ZnO/CuO)/rGO ternary nanocomposites show enhancement in the electron-hole pair separation and thereby diminishing electron-hole pairs recombination rates effectively. In the present work, the photocatalytic activity of the ZC₃G₁₅ ternary nanocomposites show 99% and 93% of degradation efficiency respectively against RhB dye and 4-chlorophenol for 20 min under visible light irradiation. Thus, the simple solid-state method provides the effective ternary nanocomposites heterostructures light harvesting material for energy and environmental remediation.     

TiO<Subscript>2</Subscript>/WO<Subscript>3</Subscript> photoanodes with enhanced photocatalytic activity for air treatment in a polymer electrolyte cell

The application of electrochemically enhanced photocatalysis in air treatment using a Nafion-based photoelectrochemical cell and TiO₂/WO₃ photoanodes for organic vapor photooxidation under both UV and visible light irradiation is briefly presented. In that direction, the obtained results regarding the preparation and characterization of the TiO₂/WO₃ photoanodes with enhanced photocatalytic activity are reviewed. Particular emphasis is given in the comparison of the photocatalytic behavior of bilayer TiO₂/WO₃ coatings, electrosynthesized on stainless steel mesh and powder C + mixed (WO₃ + TiO₂) photoanodes. The advantages of using a high surface area C + mixed (WO₃ + TiO₂) powder catalysts as photoanodes against their plain TiO₂ + C and WO₃ + C analogues are discussed.     

Photocatalytic decolourization of a new water-insoluble organic dye based on phenothiazine by ZnO and TiO2 nanoparticles

A new water-insoluble organic dye, namely, 2-((10-decyl-10H-phenothiazin-3-yl)methylene)malononitrile, was synthesized and fully characterized. It was envisioned that photocatalytic decolourization of a dye-containing long chain would pave the way for the photocatalytic remediation of wastewater containing toxic hydrophobic organic pollutants. Two commercially available nanoparticles, ZnO and TiO₂, were selected, and their photocatalytic decolourization of the dye from aqueous medium were compared. The black UV light irradiation of the colored samples in the presence of TiO₂ (P25) or ZnO resulted in their decolourization and the photocatalytic activity observed for TiO₂ (P25) was better than that of ZnO. The kinetic of decolourization indicated that the process was first-order from which the rate constant was calculated. Also, the effect of pHs on the kinetic of decolourization revealed a negligible effect, indicating that the pH, although it affects the catalysts but has no effect on the organic-based hydrophobic dye and thus no effect on the photocatalytic process.     

Bi2WO6/TiO2纳米管异质结构复合材料的多模式下的光催化活性比较

以TiO₂纳米管为模板,采用多组分自组装结合水热法制备Bi₂WO₆/TiO₂纳米管异质结构复合材料。通过多种技术如X射线衍射（XRD）,X射线光电子能谱（XPS）,N₂吸附-脱附,扫描电镜（SEM）,高分辨透射电镜（HRTEM）和紫外可见漫反射吸收光谱（UV-Vis DRS）考察所制备样品的组成、结构、形貌、光吸收和电子性质。Bi₂WO₆纳米片或纳米粒子分布在TiO₂纳米管上,形成异质结构。随后,通过在紫外、可见和微波辅助光催化模式下降解染料罗丹明B（RhB）来评价复合催化剂的光催化活性。与TiO₂纳米管和Bi₂WO₆相比,Bi₂WO₆/TiO₂-35纳米管在多模式下表现出更优异的光催化活性。与紫外和可见降解模式相比,Bi₂WO₆/TiO₂-35纳米管在微波辅助光催化模式下对RhB的降解效率最高。这种增强的光催化活性源于适量Bi₂WO₆的引入、纳米管独特的形貌特征和降解模式所引起的增强的量子效率。降解过程中的活性物种被证明是h⁺,·OH和·O₂^-自由基。而且,在微波辅助光催化模式下,可产生更多的·OH和·O₂^-自由基。     

The influence of nanostructured UV‐blockers on mechanical properties of carbon fiber epoxy composites during accelerated weathering condition

In a 3‐stage experimental approach, it was attempted to enhance the weathering performance of carbon fiber reinforced epoxy composites (CFRC). For this purpose, 2 types of UV‐blocking nanoparticles titanium dioxide (TiO₂) and zinc oxide (ZnO) were employed to separately be introduced into the composite matrix. In the first stage, the optimum content of nanoparticles was found to be 0.5 wt.% for both nanoparticles. The second stage of experiments revealed that addition of nanoparticles into CFRC could increase the strength of the composite around 6% to 12% depending on the nanoparticles used. In the third stage (weathering), it was demonstrated that nanoparticles significantly enhanced the weathering stability of CFRC. Finally, it was concluded that while TiO₂ could reinforce the composite more efficiently, ZnO nanoparticles provided a higher level of protection (62% improvement in weathering stability compared with neat composite). The higher protection efficiency of ZnO compared with TiO₂ was explained by its lower photocatalytic activity during weathering.     

Photocatalytic oxidation of organic dyes with visible-light-driven codoped TiO2 photocatalysts

A novel copper (II) and zinc (II) codoped TiO₂ photocatalyst was synthesized by a modified sol-gel method using titanium (IV) isopropoxide, Zn(NO₃)₂ · 6H₂O and copper(Il) nitrate as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and photo-luminescence spectra (PL). The XRD results showed undoped and Zn, Cu-codoped TiO₂ nanoparticles mainly including anatase phase and a tiny amount of Zn- and Cu-oxides exist in the mixed system, which is attributed to the decomposition of copper and zinc nitrates in the TiO₂ gel to form CuO and ZnO and randomly dispersed on the TiO₂ surface. On the basis of the optical characterization results, we found that the codoping of copper (II) and zinc (II) resulted a red shift of adsorption and lower recombination probability between electrons and holes, which were the reasons for high photocatalytic activity of Zn, Cu-codoped TiO₂ nanoparticles under visible light (λ > 400 nm). The photocatalytic activity of samples was tested for degradation of methyl orange (MO) in solutions. The results indicated that the visible-light driven capability of the codoped catalyst were much higher than that of the pure TiO₂ catalyst under visible irradiation. Because of the synergetic effect of copper (II) and zinc (II) element, the Zn, Cu-codoped TiO₂ catalyst will show higher quantum yield and enhance absorption of visible light. In the end, a key mechanism was proposed in order to account for the enhanced activity.     

One-pot synthesis of CuO/TiO2 nanocomposites for improved photocatalytic hydrogenation of 4-nitrophenol to 4-aminophenol under direct sunlight

The excellent photocatalytic hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with NaBH₄ in the aqueous medium is still a big challenge. Herein, we report a facile one-pot evaporation-induced self-assembly (EISA) method to synthesize a series of CuO/TiO₂ nanocomposites. The as-synthesized CuO/TiO₂ photocatalysts exhibit remarkable catalytic activity under direct sunlight in selective hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) due to the synergistic interaction of guest copper nanoparticles with host titanium dioxide (TiO₂) species. Especially, 5 wt% CuO/TiO₂ nanocomposite revealed superior reaction rate constant (k) value (0.306 min⁻¹) when compared to 3 wt% CuO/TiO₂ (0.192 min⁻¹) and 7 wt% CuO/TiO₂ (0.240 min⁻¹). Moreover, several characterization techniques (XRD, TEM, N₂ adsorption–desorption isotherm, DRS, and XPS) were executed to deeply investigate the effect of copper content on the bulk and interfacial properties of the catalysts. The characterization results proved that the superior photocatalytic hydrogenation over 5 wt% CuO/TiO₂ catalyst can be ascribed to moderate CuO loading as well as even dispersion of CuO species on the surface of active TiO₂ host, which can largely improve the light absorption ability within visible light region. Besides, the 5 wt% CuO/TiO₂ catalyst exhibits remarkable recyclability and durability, retaining its superior activity (above 95%) up to several repeating cycles, proving its practical applicability for hydrogenation reactions at domestic and industrial levels.     

Synthesis of Co3O4/WO3 Nanoheterojunction Photocatalyst for the Decomposition of Organic Pollutants Under Visible Light Irradiation

A highly efficient and visible light (λ ≥ 420 nm) responsive nanocomposite photocatalyst Co₃O₄/WO₃ was developed by dispersing p-type semiconductor Co₃O₄ on the surface of n-type semiconductor WO₃. The heterojunction Co₃O₄/WO₃ demonstrated higher photocatalytic activity than WO₃, Co₃O₄ and TiO₂ nanoparticles for the complete decomposition of 2-propanol in gas phase and phenol in aqueous phase and evolution of CO₂ under visible light irradiation. The highest photocatalytic efficiency of the composite Co₃O₄/WO₃ was observed when calcined at 300 °C for 2 h with 4.91 mol% Co₃O₄/WO₃. The enhanced photocatalytic efficiency of the heterojunction was discussed based on the unique relative energy band positions and profound absorption of visible light by the semiconductors.     

Selective aerobic photocatalytic oxidation of benzyl alcohol over spherical structured WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanocomposite under visible light irradiation

TiO₂/WO₃ nanocomposite with nanodisk morphology was prepared and successfully used as a photocatalyst. The nanocomposite was obtained via sonochemical and hydrothermal methods, using pomegranate juice as a capping agent. The products were characterized by FE-SEM imaging, BET, EDAX spectroscopy, X-ray diffraction, DRS, and FT-IR spectroscopy. TiO₂/WO₃ nanocomposite showed high sensitivity to absorb visible light in compared to TiO₂. In an optimized condition, the yield of the aerobic photocatalytic oxidation of benzyl alcohol derivatives reached to 65% for the TiO₂/WO₃ nanocomposite, while the conversion percent of the derivatives was less than 8% and 50% on the TiO₂ and WO₃ nanoparticles, respectively. Experimental results were supported by density functional theory (DFT) calculations. The DFT results in several solvents of different dielectric constants, confirmed the strong dependence of light absorption and photocatalytic activity to adsorption energy of the substrates on the surface of the nanoparticles (E_ad). In addition, the theoretical results showed an inverse correlation between the adsorption energy of benzyl alcohol and its conversion percent, accordance to the experimental trend.

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Mixed oxide/sulfide systems for photocatalysis

Mixed WO₃/WS₂ and ZnO/ZnS powders have been prepared by sulfidation of H₂WO₄ or ZnO. Photocatalytic degradation of phenol has been employed to test the photoactivity of the samples. The results indicated that the coupling of the two tungsten chalcogenides enhanced the rate of disappearance of the organic substrate. Unlikely, the ZnO/ZnS systems exhibited lower photocatalytic activitiy than pure ZnO. The different photocatalytic behaviour of the two mixed oxide/sulfide systems can be explained by a simultaneous displacement of electrons and holes between two different semiconductors.     

Titania supported copper catalysts for methanol synthesis from carbon dioxide

The effect of co-catalyst (ZnO or ZrO₂) has been tested for hydrogenation of CO₂ on CuO/TiO₂ and CuO/Al₂O₃. CuO−ZnO/TiO₂ catalyst showed the highest activity for methanol synthesis. Kinetic parameters were also determined.