Effect of SiO2 nanoparticles on the phase transformation of TiO2 in micron-sized porous TiO2–SiO2 mixed particles

Spherical and nanoporous TiO₂ and TiO₂–SiO₂ mixed micro-particles with four different compositions (20/80, 50/50, 80/20, 90/10 in weight ratio of TiO₂/SiO₂) were prepared by spray drying method from colloidal mixtures of amorphous silica and anatase titania nanoparticles. The as-prepared particles were heat-treated at 900 °C for 0.5–5 h. The TiO₂ and TiO₂–SiO₂ particles were spherical in shape and the average particle diameter was about 1 μm. The anatase mass fraction and the specific surface area of TiO₂–SiO₂ (50 wt.% SiO₂) mixed particles were kept to 61.5% and 30.6%, respectively, of their initial values after 5 h heat-treatment whereas these values of TiO₂ particles were rapidly decreased to 13.0% and 1.2% of their initial values, respectively, within 30 min after heat-treatment. And the anatase mass fraction and specific surface area increased as SiO₂ content in the TiO₂–SiO₂ mixed particles increased.     

Synthesis of polyaniline-modified Fe3O4/SiO2/TiO2 composite microspheres and their photocatalytic application

Polyaniline-modified Fe₃O₄/SiO₂/TiO₂ composite microspheres have been successfully synthesized by sol–gel reactions on Fe₃O₄ microspheres followed by the chemical oxidative polymerization of aniline. The synthesized multilayer-structured composites were characterized by TEM, XRD, TGA, UV–vis diffuse reflectance spectra and magnetometer. The photocatalytic activity was evaluated by the photodegradation of methylene blue under visible light. The effect of polyaniline (PANI) amounts on the photocatalytic activity was investigated. The photocatalytic activity results show that the Fe₃O₄/SiO₂/TiO₂ composites with about 2.4 wt.%–4.1 wt.% PANI could show higher photocatalytic efficiency than that of Fe₃O₄/SiO₂/TiO₂. Furthermore, the PANI-Fe₃O₄/SiO₂/TiO₂ photocatalyst could be easily recovered using a magnet.     

Influence of TiO2 dimension and graphene oxide content on the self-cleaning activity of methylene blue-stained photocatalytic films

In the present study, TiO₂ and graphene oxide (GO)/TiO₂ composite films were simply fabricated by hot-plate spray coating technique. The influences of TiO₂ dimension and GO content on the self-cleaning activity of methylene blue (MB)-stained films were investigated. The matrix of anatase TiO₂ quasi-cubic and octahedral particles in diameter of 6–9 nm (ST film) degraded 80% stained dye, much higher than those either in bigger size (30–50 nm) or in flower morphology due to the nano effect. Moreover, the photocatalytic performance of such nanostructured film was strongly enhanced by the combination with GO sheets. Increasing GO content led to significant enhancement in film transmittance and MB adsorptivity. In the aspect of the self-cleaning activity for MB, the addition of GO up to 1 wt.% showed higher efficiency but excess content led to similar performance in comparison with pure TiO₂ film.     

Preparation and properties of sliver and nitrogen co-doped TiO2 photocatalyst

TiO₂ photocatalysts co-doped with different content of Ag and N were prepared by sol–gel method combined with microwave chemical method. The samples were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope (TEM), ultraviolet–visible diffuse reflectance spectrum (UV–vis) and photo-luminescence emission spectrum (PL). The photocatalytic activity was investigated by photocatalytic degradation of methylene blue (MB) under irradiation of fluorescent lamp. The results indicate that Ag and N co-doping can restrain the increase of grain size, broaden the absorption spectrum to visible light region, and inhibit the recombination of the photo-generated electron–hole pairs. Moreover, the photocatalytic activity of Ag–N–TiO₂ in MB degradation is remarkable improved. The degradation rate of the sample with Ag:TiO₂ = 0.05 at%, N:TiO₂ = 18.50 wt% in 5 h is 93.44%, which is much higher than that of Degussa P25 (39.40%).     

Preparation and properties of ce-doped TiO2 photocatalyst

TiO₂ nanoparticles doped with different content of Ce ion were prepared by sol–gel method. The samples were characterized by XRD, XPS, TEM, UV–Vis, and PL, the photocatalytic activity was evaluated by photocatalytic degradation of methylene blue (MB) under the irradiation of fluorescent lamp. The results indicate that Ce ion is incorporated into the lattice of TiO₂, which can restrain the increase of grain size, broaden the absorption region to visible light, and inhibit the recombination of the photo-generated electron and hole pairs. Moreover, the photocatalytic activity of Ce-TiO₂ in MB degradation is evidently enhanced. The MB degradation rate of the sample with Ce:Ti = 0.33% (molar ratio) in 8 h is 90.03%, which is much higher than that of P25 (68.19%).     

Formulation of mortars with nano-SiO2 and nano-TiO2 for degradation of pollutants in buildings

This paper reports on the design of cement mortars that use nano-SiO₂ (nS) and nano-TiO₂ (nT) particles, aiming to improve the durability of traditional building materials while giving new functionalities (aerial decontamination of pollutants). Samples with 0–2 wt.% nS, 0–20 wt.% nT, 0.45–7 wt.% superplasticizer (SP) and 0.45–0.58 water/binder weight ratio were prepared. The formulations of mortars were defined according to rheology and flow table measurements, then showing suitable workability. The temperature of hydration, compressive strength, water absorption, and photocatalytic degradation of pollutants (NO_x and Orange II dye) were also evaluated. In general, the rheological behavior and the temperature of hydration changed in distinct levels, depending on the dosage and type of nanoadditives, but nT influenced more significantly the results. However, such differences were not identified on the compressive strength and water absorption. In addition, NO_x photocatalytic degradation up to 1 h under solar light ranged from 65% to 80%, while Orange II degradation after 9 h under visible light changed from 18% to 50%.     

Photodegradation of bisphenol-A in a batch TiO2 suspension reactor

In this work, the photocatalytic behaviors of bisphenol-A (BPA), which has been listed as one of endocrine disrupting chemicals, were carried out in a batch TiO₂ suspension reactor. The photodegradation efficiency has been investigated under the controlled process parameters including initial BPA concentration (i.e., 1–50 mg L^?1), TiO₂ dosage (i.e., 5–600 mg/200 cm³), initial pH (i.e., 3–11), and temperature (i.e., 10–70 °C). It was found that the optimal conditions in the photoreaction process could be coped with at initial BPA concentration = 20 mg L^?1, TiO₂ dosage = 0.5 g L^?1 (100 mg/200 cm³), initial pH = 7.0, and temperature = 25 °C. According to the Langmuir–Hinshelwood model, the results showed that the photodegradation kinetics for the destruction of BPA in water also followed the first-order model well. The apparent first-order reaction constants (k_obs), thus obtained from the fittings of the model, were in line with the destruction-removal efficiencies of BPA in all the photocatalytic experiments. Based on the intermediate products identified in the study, the possible mechanisms for the photodegradation of BPA in water were also proposed in the present study.     

Synthesis and characterization of rice grains like Nitrogen-doped TiO2 nanostructures by electrospinning–photocatalysis

Rice grain-shaped Nitrogen-doped titanium dioxide (N–TiO₂) nano/mesostructures were fabricated through a combination of sol–gel and electrospinning methods. As-spun nanofibers were continuous and upon thermal treatment at 500° C for 1 h in air, the continuous fibers break into rice grain-shaped TiO₂ nanostructures of average diameter 50–80 nm. The nanostructures were characterized by spectroscopy, microscopy and powder X-ray diffraction. The rice grains consist of spherical particles of average diameter of ~ 18 nm and with N doping, their average diameters decrease from ~ 18 to ~ 12 nm. The presence of N in the TiO₂ lattice was confirmed by X-ray photoelectron spectroscopy (XPS). The band-gap of TiO₂ reduced from 3.19 eV to 2.83 eV upon increasing doping level of N from 0% to 5% (w/w), respectively. The N–TiO₂ rice grains showed an enhanced UV light-assisted photocatalysis compared to pure TiO₂ in the photodegradation of Alizarin Red S dye, an industrially important anthraquinone dye.     

Characterization and photocatalysis of Eu3+–TiO2 sol in the hydrosol reaction system

In this paper, 3.0 mol% lanthanide europium ion modified TiO₂ sol (Eu³⁺–TiO₂) was fabricated by chemical coprecipitation–peptization method with TiCl₄ as precursor. Eu³⁺–TiO₂ sol particles were characterized by X-ray diffraction (XRD), atomic force microscope (AFM), transmission electron microscope (TEM) and particle size distribution (PSD). Eu³⁺–TiO₂ sol particles prepared at low temperature (70 °C) had anatase semicrystalline structure. Eu³⁺–TiO₂ sol sample homogeneously dispersed in the aqueous medium and presented narrow distribution characterization with 7 nm in mean size. Interfacial adsorption experiment shows that small particle size and positive charge of sol particles contributed to the good adsorption of X-3B dye on the TiO₂ surface. The photoelectrochemical property was investigated about electrons transfer efficiency between dye molecule and TiO₂ particles. A novel hydrosol reaction system was designed to conduct X-3B photodegradation reaction. The excellent photocatalytic activity for X-3B degradation under visible light irradiation was ascribed to effective scavenging electrons by Eu³⁺ ion. Moreover, X-3B photocatalytic degradation mechanism under visible light excitation was proposed as photosensitization–photocatalysis.     

Three-dimensionally ordered macroporous Ti1−xTaxO2+x/2 (x = 0.025, 0.05, and 0.075) nanoparticles: Preparation and enhanced photocatalytic activity

Anatase phase, three-dimensionally ordered macroporous (3 DOM) Ti_1−xTa_xO_{2 + x / 2} (x = 0.025, 0.05, and 0.075) nanoparticles with macropore diameter 290 to 310 nm, wall thickness 50 to 80 nm, and particle size 10 to 12 nm were prepared by combination of the sol–gel chemistry and polystyrene (PS) templating procedure. The products exhibited relatively narrower band gaps and larger BET surface areas than those of the starting solitary 3 DOM metal oxides, and their photocatalytic activities for the degradation of an aqueous 4-nitrophenol remarkably enhanced compared with 3 DOM anatase TiO₂, Ta₂O₅, and Degussa P-25.     

Brazing of SiO2f/SiO2 composite modified with few-layer graphene and Invar using AgCuTi alloy

Due to the poor wettability of the AgCuTi alloy on the SiO_2f/SiO₂ composite, direct brazing of the composite with an Invar alloy could hardly achieve a reliable joint. To overcome that, the SiO_2f/SiO₂ composite was decorated with few-layer graphene (FLG) by a plasma enhanced chemical vapor deposition (PECVD) method. Sessile drop experiments indicate that the contact angle dropped from 123.8° to 50.7° after FLG was grown on the surface of the SiO_2f/SiO₂ composite. Afterwards, the effects of brazing temperature and Ti contents on the microstructure evolution and mechanical properties of joints (Invar/SiO_2f–SiO₂ modified with FLG) were investigated. The typical interface structure of the joint is SiO_2f–SiO₂/Ti₅Si₃ + TiO₂ + Cu_xTi_6 − xO(x = 2,3)/Ag(s,s) + Cu(s,s) + Cu–Ti blocks/wave-like Fe₂Ti + Ni₃Ti/Ag(s,s) + Cu(s,s) + Fe₂Ti + Ni₃Ti blocks/Invar. As the brazing temperature and Ti contents increase, the reaction layer on the SiO_2f/SiO₂ side becomes thicker and cracks gradually propagate. Meanwhile, a few dispersive Fe₂Ti + Ni₃Ti phases change into large-area wave-like compounds and more Cu–Ti compounds form with the increase of the Ti content. The microstructure evolution significantly affects the shear strength of the brazed joints. The highest shear strength is 26 MPa brazed at 860 °C for 10 min with 4.5 wt.% Ti content.     

Experimental investigation of the size effects of SiO2 nano-particles on the mechanical properties of binary blended concrete

In the current study, the size effects of SiO₂ nano-particles on compressive, flexural and tensile strength of binary blended concrete were investigated. SiO₂ nano-particles with two different sizes of 15 and 80 nm have been used as a partial cement replacement by 0.5, 1.0, 1.5 and 2.0 wt.%. It was concluded that concrete specimens containing SiO₂ particles with average diameter of 15 nm were harder than those containing 80 nm of SiO₂ particles at the initial days of curing. But this condition was altered at 90 days of curing. Also from the viewpoint of free energy, it can be concluded that the C–S–H gel formation around the particles with average diameter of 15 nm was more at the primary days of curing. This can be as a result of more nucleation sites that causes acceleration in early age strength. On the other hand, the growth probability of C–S–H gel around the 80 nm particles was more at 90 days of moist curing. This is due to the fact that the nucleus of strengthening gel could simply reach to the critical volume of nucleation that causes increase in the strength.     

A facile decoration of anatase Fe3O4/TiO2 nanocomposite with graphene quantum dots: Synthesis,characterization, and photocatalytic activity

A combination of electron-rich graphene quantum dots (GQDs) with Fe₃O₄/TiO₂ nanocomposites may develop an efficient electron transfer for enhanced photocatalytic activity. In this report, a facile decoration of GQDs with maltose precursor was synthesized and loaded onto magnetic anatase TiO₂ nanocomposites under hydrothermal methods. The as-synthetized magnetic TiO₂/GQDs nanocomposite resulted in a specific surface area of 38.00 m²/g and a total pore volume of 0.186 cm³/g. The HRTEM images showed a lattice plane distance of 0.350 nm related to the interplanar spacing of the anatase TiO₂ (1 0 1) plane and that of 0.299 nm observed for the in-plane lattice part of GQDs. The effects of magnetic loading ratio and GQDs loading onto TiO₂, pH, photocatalyst dosage, and methylene blue (MB) concentration were thoroughly evaluated to find the optimum conditions of mineralization MB for getting the highest photocatalytic efficiency. The removal efficiency of around 86.08 ± 3.62% was obtained at pH11, photocatalytic dose 400 mg/100 mL, and MB concentration 10 mg/L. Moreover, the photogenerated electron transfers and MB degradation mechanism by the resulting Fe₃O₄/TiO₂/GQD_S under irradiation of UVA light are proposed. The as-synthesized material improved meaningfully greater photocatalytic efficiency for degrading MB under UVA light irradiation than merely pure anatase TiO₂. Also, the predominant mechanism of MB degradation was direct oxidative decomposition through the photogenerated holes. The photocatalytic destruction of MB complied with the apparent first-order models under UVA light irradiation.     

Preparation,characterization and photocatalytic properties of terbium orthoferrite nanopowder

Perovskite-type terbium orthoferrite (TbFeO₃) nanopowder was synthesized through a polyacrylamide gel route. The as-synthesized particles were characterized by XRD, TEM, BET surface area, UV–visible absorption spectroscopy, and XPS. It is shown that the particles are uniformly and regularly shaped like spheres with an average size of ～50 nm, and have a BET specific surface area of 15.4 m² g^?1. The optical energy bandgap of the nanosized TbFeO₃ is obtained to be 1.98 eV. The photocatalytic activity of the TbFeO₃ particles was evaluated by the photodegradation of various organic dyes including methyl orange (MO), rhodamine B (RhB), methylene blue (MB), acid fuchsine (AF), and congo red (CR). It is demonstrated that the product exhibits a pronounced photocatalytic degradation of the dyes under visible-light irradiation. The photocatalytic efficiency is observed to depend on the dye type, and under the present experimental conditions it follows the sequence: CR > AF > MB > RhB > MO.     

Co-electrospinning fabrication and photocatalytic performance of TiO2/SiO2 core/sheath nanofibers with tunable sheath thickness

In this paper, core/sheath TiO₂/SiO₂ nanofibers with tunable sheath thickness were directly fabricated via a facile co-electrospinning technique with subsequent calcination at 500 °C. The morphologies and structures of core/sheath TiO₂/SiO₂ nanofibers were characterized by TGA, FESEM, TEM, FTIR, XPS and BET. It was found that the 1D core/sheath nanofibers are made up of anatase–rutile TiO₂ core and amorphous SiO₂ sheath. The influences of SiO₂ sheath and its thickness on the photoreactivity were evaluated by observing photo-degradation of methylene blue aqueous solution under the irradiation of UV light. Compared with pure TiO₂ nanofibers, the core/sheath TiO₂/SiO₂ nanofibers performed a better catalytic performance. That was attributed to not only efficient separation of hole–electron pairs resulting from the formation of heterojunction but also larger surface area and surface silanol group which will be useful to provide higher capacity for oxygen adsorption to generate more hydroxyl radicals. And the optimized core/sheath TiO₂/SiO₂ nanofibers with a sheath thickness of 37 nm exhibited the best photocatalytic performance.     

Growth of SiO2 hierarchical nanostructure on SiC nanowires using thermal decomposition of ethanol and titanium tetrachloride and its FTIR and PL property

Novel SiO₂ hierarchical nanostructure has been grown on SiC nanowires using thermal decomposition of a mixture of ethanol and titanium tetrachloride. Novel nanostructure was realized in one synthesis route. Based on SEM and TEM observations, the hierarchical nanostructure consists of core-shell SiC–SiO₂ main stem nanowire and a lot of SiO₂ nanorod branches grown on the main stem. A mean diameter of SiC central cores was about 40 nm and their lengths reach about 100 μm. The lengths and diameters of SiO₂ nanorod-like branches were ranged in 400–800 nm and 30–120 nm, respectively. The growth of core-shell SiC–SiO₂ nanowires obeyed vapor–liquid–solid mechanism and the SiO₂ nanorod-like branches grew via vapor–solid mechanism. The infrared absorption and photoluminescence properties of the grown nanostructure were investigated.     

Synthesis and Characterization of Urchin-like Mischcrystal TiO2 and Its Photocatalysis

The urchin-like mischcrystal TiO₂ using acid attapulgite as an introducer was synthesized after a subsequent low-temperature hydrolyzation and crystallization followed by removal of acid attapulgite. The samples were characterized by transmission electron microscope, X-ray diffraction, Fourier transform infrared spectra and X-ray photoelectron spectroscopy. Acid attapulgite plays a critical role in the morphology and crystal structure of TiO₂. The results suggest that the perfect urchin-like mischcrystal TiO₂ is fabricated when the mass ratio of TiO₂ and acid attapulgite is 0.7:1. The single urchin-like TiO₂ is comprised of a nanosphere and plentiful nanoneedles. The nanoneedles grow radially on the surface of the nanosphere. The urchin-like TiO₂ is around 100 nm, and the nanoneedles have a diameter ranging from 2 to 5 nm. It has been confirmed that the chemical groups of acid attapulgite have a significant influence on the growth of TiO₂. In addition, the urchin-like mischcrystal TiO₂ exhibits excellent activity to assist photodegradation of Rhodamine B aqueous solution under ultraviolet light, and the degradation rate is about 94.15% for 80 min. The photocatalytic kinetics can be well described by the pseudo-first rate equation.     

Adsorption and photocatalysis of nanocrystalline TiO2 particles prepared by sol–gel method for methylene blue degradation

Titanium dioxide (TiO₂) powders were synthesized by using TiO₂ colloidal sol prepared from titanium-tetraisopropoxide (TTIP) and used as a starting material by applying the sol–gel method. The effect of aging times and temperatures on physical and chemical properties of TiO₂ sol particles was systematically investigated. The results showed that the crystallinity and average particle size of TiO₂ can be successfully controlled by adjusting the aging time and temperature. The samples after calcination of TiO₂ powders were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and nitrogen adsorption measurements. In addition, the photocatalytic activity of synthesized TiO₂ powders was evaluated by studying the degradation of 10 ppm aqueous methylene blue dye under 32 W high pressure mercury vapor lamp with 100 mg of TiO₂ powders. The highest photocatalytic activity was observed in TiO₂ powder synthesized at 90 °C for 0 h attributed to the presence of anatase and rutile phases in an 80:20 ratio.     

High pressure behaviors of nanoporous anatase TiO2

High pressure behaviors of nanoporous anatase TiO₂ were studied using in situ Raman spectroscopy up to 37 GPa. The nanoporous anatase phase starts to transform into the baddeleyite phase with poor crystallinity at ～15.2 GPa, and the baddeleyite phase coexists with anatase phase up to 18.4 GPa. The baddeleyite form transforms into an amorphous phase above 20.5 GPa. Upon decompression, the amorphous phase recovers to the baddeleyite phase and then transforms to the α-PbO₂ phase. The phase transition from the baddeleyite phase to the amorphous form is reversible. The poor crystalline baddeleyite phase acts as an intermediate state in the amorphization process. The phase transitions of the nanoporous anatase TiO₂ are obviously different from the pressure-induced amorphization in the anatase TiO₂ nanoparticles. These results indicate that the porous microstructure plays important roles in the high pressure phase transitions of the nanoporous anatase TiO₂.     

Synthesis and photocatalytic activity of N-doped TiO2/ZrO2 visible-light photocatalysts

Visible-light responsive N-doped ZrO₂/TiO₂ photocatalysts were synthesized via a sol–gel process. To obtain the optimum nitrogen doping content and operational conditions for photodegradation of NO, several key factors (including nitrogen doping, initial NO concentration, light intensity, reactor temperature, etc.) were investigated under both UV and visible light irradiation. Physical characterization of the photocatalysts was performed using X-ray diffraction (XRD), UV–visible absorption spectroscopy, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR). The observed results suggest that nitrogen was doped in the lattice of TiO₂ and had an effect on the translation of phase, photodegradation activity, and visible-light response. Among synthesized photocatalysts, 0.1 M Zr and 0.15 M N supported on TiO₂ exhibited the best visible-light response and the highest NO photodegradation activity.