Photocatalytic hydrogen production by Au–MxOy (MAg,Cu, Ni) catalysts supported on TiO2

Au–M_xO_y (MAg, Cu, Ni) nanoparticles supported on TiO₂–P25 were prepared by the deposition–precipitation method and were evaluated for the photocatalytic water splitting reaction for hydrogen production, using a mixture of water–methanol (1:1). The combinations of Au–Cu₂O/TiO₂ and Au–NiO/TiO₂ effectively increased the hydrogen production (2064 and 1636 μmol·h^− 1·g^− 1) obtained by Au/TiO₂ (1204 μmol·h^− 1·g^− 1). The higher photoactivities achieved by Au–Cu₂O and Au–NiO nanoparticles deposited on TiO₂ were attributed to an enhancement of the electron charge transfer from TiO₂ to the Au–M_xO_y systems and the effect of surface plasmon resonance of gold nanoparticles.     

The effect of TiO2 particle size on the characteristics of Au–Pd/TiO2 catalysts

The nanocrystalline TiO₂ materials with average crystallite sizes of 9 and 15 nm were synthesized by the solvothermal method and employed as the supports for preparation of bimetallic Au/Pd/TiO₂ catalysts. The average size of Au–Pd alloy particles increased slightly from sub-nano (< 1 nm) to 2–3 nm with increasing TiO₂ crystallite size from 9 to 15 nm. The catalyst performances were evaluated in the liquid-phase selective hydrogenation of 1-heptyne under mild reaction conditions (H₂ 1 bar, 30 °C). The exertion of electronic modification of Pd by Au–Pd alloy formation depended on the TiO₂ crystallite size in which it was more pronounced for Au/Pd on the larger TiO₂ (15 nm) than on the smaller one (9 nm), resulting in higher hydrogenation activity and lower selectivity to 1-heptene on the former catalyst.     

Enhanced production of benzyl alcohol in the gas phase continuous hydrogenation of benzaldehyde over Au/Al2O3

Exclusive hydrogenation of benzaldehyde to benzyl alcohol in gas phase continuous operation (393–413 K, 1 atm) was achieved over Au/Al₂O₃, Au/TiO₂ and Au/ZrO₂. Synthesis of Au/Al₂O₃ by deposition–precipitation generated a narrower distribution (2–8 nm) of smaller (mean = 4.3 nm) Au particles relative to impregnation (1–21 nm, mean = 7.9 nm) with increased H₂ uptake under reaction conditions and higher benzaldehyde turnover. Switching reactant carrier from ethanol to water resulted in a significant enhancement of selective hydrogenation rate over Au/Al₂O₃ with 100% benzyl alcohol yield, attributed to increased available reactive hydrogen. This response extends to reaction over Au/TiO₂ and Au/ZrO₂.     

Visible light-driven mesoporous Au–TiO2/SiO2 photocatalysts for advanced oxidation process

Au–TiO₂/SiO₂ heterogeneous catalysts with different Au contents were successfully synthesized by a facile hydrothermal process and their photocatalytic activity towards reduction of Rose Bengal (RB), Methyl Blue (MB), Rhodamine B (RhB) and Congo Red (CR) was investigated in the presence of sodium borohydride (NaBH₄) for advanced oxidation process (AOP). The results reveal that 3 wt% Au loaded in TiO₂/SiO₂ can significantly degrade high RB concentration dye (>95%, 0.3 g/L, 12 pH) within 20 min of irradiation time. All catalysis reaction followed the pseudo-first order rate reaction with high correlation coefficient. The effect of loading of Au nanoparticles (1–5 wt%) along with variation in dye concentration (100–500 ppm), pH of solution (2–12), catalysts dosage (0.1–0.5 g/L), and reaction temperature (30–80 °C) were also studied. The present works shows the superior performance of Au–TiO₂/SiO₂ heterogeneous catalysts to be related to the high dispersion of Au nanoparticles in the TiO₂/SiO₂ and to the catalytic effect between gold and TiO₂.     

Characterization of charging effect of citrate-capped Au nanoparticle pentacene device

Capacitance–voltage hysteresis for a non-volatile memory was realized in a metal–pentacene–insulator–silicon (MPIS) device using gold (Au) nanoparticles (NPs) intervened between pentacene and SiO₂ insulator. A memory window higher than 2.0 V was obtained under (±) 5 V programming sweeping range. The SiO₂ as thick as 30 nm was adopted as the dielectric layer, and 3-aminopropyl-triethoxysilane (APTES) was used for self-assembling of Au NPs monolayer. In addition, citrate-functionalized Au NPs was dip-coated and used as charge storage elements. Formation of a monolayer of the Au NPs was confirmed by HR-SEM and AFM. Capacitance–voltage hysteresis in this study was resulted from the charge storage in the layer of Au NPs.     

Liquid phase selective hydrogenation of phthalic anhydride to phthalide over titania supported gold catalysts

Au/TiO₂ catalysts with different gold loadings were prepared by deposition–precipitation method and used for the liquid phase hydrogenation of phthalic anhydride. All the studied Au/TiO₂ catalysts exhibited excellent activity with high selectivity (>92%) to phthalide under mild reaction conditions (180 °C and 3.0 MPa H₂). Specially, catalysts with 2–3 wt.% gold loading were highly active and selective for the formation of phthalide. When reused, the catalyst showed a certain deactivation, but still was highly selective to phthalide. The deactivation was attributed to the leaching of gold, collapse of the pore structure and accumulation of organic species on the surface.     

Photocrosslinkable acid urethane dimethacrylates from renewable natural oil and their use in the design of silver/gold polymeric nanocomposites

Castor oil-based acid urethane macromers were prepared and employed for obtaining Ag/Au/polymer nanocomposites. Structure and UV induced photopolymerization of the macromers were investigated by spectral methods. The polymerization rate and the degree of conversion decreased with about 10% in the presence of 2.5 wt.% silver nanoparticles (Ag NPs). For the diacid macromer, the surface plasmon intensity increased with irradiation time (the optical density of the absorption maximum (430 nm) attained 2.3 after 600 s), whereas a diminished efficiency was found for Ag NPs in situ generated. Transmission electron microscopy and X-ray photoelectron spectroscopy confirmed uniform distribution of the spherical nanoparticles (0.6 nm (Ag NPs); 5 nm (Au NPs)) and the appearance of Ag 3d_3/2, Ag 3d_5/2, Au 4f_7/2 and Au 4f_5/2 peaks corresponding to Ag (0) or Au (0). Environmental scanning electron microscope with energy-dispersive X-ray detector, contact angle and mechanical parameters measurements complemented the above observations.     

Ambient temperature CO oxidation over gold nanoparticles (14 nm) supported on Mg(OH)2 nanosheets

Au/Mg(OH)₂ catalysts with two different sizes (4 and 14 nm) of Au nanoparticles (NPs) have been prepared by depositing pre-fabricated Au NPs onto Mg(OH)₂ nanosheets (NSs). It was found that 14 nm Au NPs supported on Mg(OH)₂ exhibited unexpected activity for CO oxidation at ambient temperature that could be comparable with those of Au NPs of 4 nm. The Mg(OH)₂ support was suggested to be responsible for the observed catalytic activity of larger gold supported catalysts.     

Synthesis,characterization, and photocatalytic properties of ZnO nano-flower containing TiO2 NPs

In this study, TiO₂-impregnated ZnO nano-flowers were synthesized by one-pot hydrothermal process. Aqueous suspension containing ZnO precursor and commercial TiO₂ NPs (P25) is heated at 140 °C for 2 h. The morphology and structure of as-synthesized particles were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD), which revealed that TiO₂ NPs were attached on the surface of ZnO flower. It was observed that the presence of TiO₂ NPs in the hydrothermal solution could sufficiently decrease the size of ZnO flower. The hybrid nanostructure, with unique morphology, obtained from this convenient method (low temperature, less time, and less number of reagents) was found to be effective photocatalyst under UV-irradiation.     

Photocatalytic degradation of dairy effluent using AgTiO2 nanostructures/polyurethane nanofiber membrane

Dairy effluent (DE) is environmentally toxic and needs special attention. Photocatalytic degradation of DE was studied using novel polyurethane (PU)-based membranes. Typically, silver–titanium dioxide nanofibers (AgTiO₂ NFs) and silver–titanium dioxide nanoparticles (AgTiO₂ NPs) were individually incorporated in PU electrospun nanofibers to overcome the mandatory sophisticated separation of the nanocatalysts, which can create a secondary pollution, after the treatment process. These nanomembranes were characterized in SEM, TEM, XRD and UV studies. The polymeric electrospun nanofibers were smooth and continuous, with an average diameter of about 550 nm, and held their nanofibrous morphology even after more than 2 h of photocatalytic degradation of DE, due to the good stability of PU in the aqueous solutions, which indicates good imprisoning of the functional photocatalysts. The PU–AgTiO₂ NPs and PU–AgTiO₂ NFs were effective materials for degradation of DE, even after two successive cycles. PU–AgTiO₂ NPs and PU–AgTiO₂ NFs showed a maximum degradation of 75% and 95%, respectively after 2 h. The significant enhancement of degradation in the PU–Ag–TiO₂ NPs and PU–Ag–TiO₂ NFs is attributed to the photoactivity of Ag–TiO₂ material under visible light irradiation.     

Preparation and photocatalytic activity of silver and TiO2 nanoparticles/montmorillonite composites

Ag–TiO₂/montmorillonite (Ag–TiO₂/MMT) was synthesized as photocatalyst using TiCl₄ hydrolysis to introduce nanosized TiO₂ into the interlayer space of the montmorillonite (MMT). Stable pillared TiO₂/MMT was obtained by calcination at 500 °C, then silver was loaded by reduction of silver nitrate. The physico–chemical properties of the photocatalyst were determined by X-ray diffraction (XRD), infrared spectroscopy (IR), atomic absorption spectrophotometer (AAS), nitrogen gas adsorption (BET method) and UV–Visible spectra. The photooxidation activity for methylene blue (M.B.) degradation was as follows: Ag–TiO₂/MMT > TiO₂/MMT > TiO₂(P25). Among them Ag–TiO₂/MMT had the highest photooxidation activity because of its larger specific surface caused by pillaring and loading of silver for improving its light absorption.     

Transparent and flexible films of new segmented polyurethane nanocomposites incorporated by NH2-functionalized TiO2 nanoparticles

In this work, TiO₂ nanoparticles are surface modified by NH₂-terminated organic moieties arised from 4,4′-methylene diphenyl diisocyanate (MDI). These nanoparticles are incorporated into ether-based segmented polyurethane (SPU) matrix. MDI is utilized as monomer together with poly(tetramethylene oxide) (PTMO) comonomer for preparing the final polymer as well. The NH₂-functionalized TiO₂ nanoparticles are covalently linked to the NCO terminals of the resulting SPU macromolecules during film preparation stage. Therefore, in addition to butylene glycol, these surface modified nanoparticles with enhanced organophilicity could play the role of the second chain extender of NCO-capped SPU macromolecules through formation of urea linkages. Optical and thermal behaviors of the transparent and flexible film (SPU/TiO₂–MDI) is compared with those of unmodified TiO₂ (SPU/TiO₂) and TiO₂-unloaded SPU films. Though the particle loading is only 5 wt.%, incorporation of TiO₂ and TiO₂–MDI nanoparticles into the SPU polymer enhances significantly the light absorption in UV region at 300–400 nm. SEM images of the prepared films clearly show a considerable decrease in particle aggregation for TiO₂–MDI into SPU matrix compared to that of unmodified TiO₂. TG analyses indicate a one-step decomposition pattern with onset temperatures of about 360 and 380 °C for neat SPU and SPU/TiO₂–MDI, respectively. Moreover, DTA thermograms of both nanocomposites show obviously two exothermic phase transitions in the thermal range of 330–440 °C.     

Au/MnO2–TiO2 catalyst for preferential oxidation of carbon monoxide in hydrogen stream

The catalytic activity of nanosize gold catalysts supported on MnO₂–TiO₂ and prepared by deposition–precipitation method has been investigated for preferential oxidation of carbon monoxide in H₂ stream. The catalysts were characterized by inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, nitrogen sorption, transmission electron microscopy, and X-ray photoelectron spectroscopy. The influence of pH in the preparation process and the amount of MnO₂ loading on the catalytic properties of the Au/MnO₂–TiO₂ catalysts were also studied. Fine dispersion of gold nanoparticles on all the supports was obtained. Especially, Au/MnO₂–TiO₂ with MnO₂/TiO₂ mol ratio of 2:98, showed a mean Au particle size of 2.37 nm. The nanosized support constrained the size of gold. The addition of MnO₂ on Au/TiO₂ catalyst improved the selectivity of CO oxidation without sacrificing CO conversion in hydrogen stream between 50 and 100 °C. This could be attributed to the interactions of gold metal with MnO₂–TiO₂ support and the optimum combination of metallic and electron-deficient gold on the catalyst surface.     

Low temperature sintering and microwave dielectric properties of TiO2 ceramics

The TiO₂ ceramics were prepared by a solid-state reaction in the temperature range of 920–1100 °C for 2 h and 5 h using TiO₂ nano-particles (Degussa-P25 TiO₂) as the starting materials. The sinterability and microwave properties of the TiO₂ ceramics as a function of the sintering temperature were studied. It was demonstrated that the rutile phase TiO₂ ceramics with good compactness could be readily synthesized from the Degussa-P25 TiO₂ powder in the temperature range of 920–1100 °C without the addition of any glasses. Moreover, the TiO₂ ceramics sintered at 1100 °C/2 h and 920 °C/5 h demonstrated excellent microwave dielectric properties, such as permittivity (Ɛ_r) value >100, Q × f  > 23,000 GHz and τ_f ≅ 200 ppm/°C.     

Effect of microstructural evolution on wettability and tribological behavior of TiO2 nanotubular arrays coated on Ti–6Al–4V

Self-organized TiO₂ nanotubular arrays were fabricated by electrochemical anodization of Ti–6Al–4V plates in an NH₄F/H₃PO₄ electrolyte. The effect of microstructural evolutions on the wettability and tribological behavior of the TiO₂ nanotubes was investigated. Based on the XRD profiles of the fabricated material, the characteristic TiO₂ peaks were not recognized after anodization; however, highly crystalline TiO₂ (anatase and rutile) was formed due to crystallization during annealing at 500 °C for 1.5 h. The nanotube arrays were converted entirely to rutile at 700 °C. From a microstructure point of view, a highly ordered nanotube structure was achieved when the specimen was annealed at 500 °C, with a length of 0.72 μm and a pore diameter of 72 nm. Further increasing the annealing temperature to 700 °C resulted in the complete collapse of the tubular structure. The results indicate that the improved wettability of the anodized specimens was due to the combination of the effects of both the surface oxide layer and the increased surface roughness achieved after anodization. Moreover, the wear resistance and wettability of the sample annealed 500 °C were improved due to the high hardness (435 HV) and low coefficient of friction (0.133–168) of the highly crystalline structure of the TiO₂ nanotubes.     

Effect of Pt or Pd doping on stability of TiO2 nanoparticle suspension in water

Stability of suspensions of TiO₂ nanoparticles synthesized by the flame aerosol reactor (FLAR) could be altered by doping TiO₂ nanoparticles with Pt, Pd, or Pt–Pd dopants. It was found that doping of TiO₂ with Pd or Pt could contribute to the control of the agglomeration of TiO₂ suspended in water. With the change of doping content, the isoelectric point (IEP) of stable TiO₂ suspension decreased gradually from 5 to 3.6 while the specific surface area was increased from 43.27 to 60.84 m²/g. With pH > 6.0, 2 wt% Pt–Pd/TiO₂ suspension exhibited the lowest agglomeration behavior. The plausible intrinsic structures of Pt, Pd, and Pt–Pd doped TiO₂ nanoparticles were proposed and discussed with respect to their IEP based on the DLVO theory.     

Preparation of dye sensitized solar cell by using supercritical carbon dioxide drying

Dye-sensitized solar cells (DSSC) derived from TiO₂ aerogel film electrodes were fabricated. TiO₂ aerogels were obtained by using sol–gel method and supercritical carbon dioxide (sc-CO₂) drying. First, TiO₂ wet gels were obtained by sol-gel method. Then, the solvents in the TiO₂ wet gels were replaced by acetone. The TiO₂ aerogels were obtained by using sc-CO₂ drying from the TiO₂ wet gels. The conditions of sc-CO₂ drying were at 313, 323 K and 7.8–15.5 MPa. The electrodes with TiO₂ aerogel films were obtained by deposition of the aerogels on glass substrates. The electrodes with TiO₂ aerogel films and a commercial particle film of various thickness were obtained by repetitive coatings and calcinations. The amount of dye adsorbed on the TiO₂ films with sc-CO₂ drying was higher than that of commercial particle film. The amount of dye adsorbed on the TiO₂ films increased with increasing surface area of the TiO₂ film. DSSCs were assembled by using the TiO₂ aerogel film electrodes and their current–voltage performance was measured. The power performance of DSSC made by supercritical drying was higher than that of commercial particles. The DSSC with the film electrode made at 313 K and 15.5 MPa showed the best power performance (J_sc = 7.30 mA/cm², V_oc = 772 mV, η = 3.28%).     

Colossal permittivity in (In1/2Nb1/2)xTi1−xO2 ceramics prepared by a glycine nitrate process

(In + Nb) co-doped TiO₂ nanoparticles with very low dopant concentrations were prepared using a glycine nitrate process. A pure rutile—TiO₂ phase with a dense microstructure and homogeneous dispersion of dopants was achieved. By doping TiO₂ with 1.5% (In + Nb) ions, a very high dielectric permittivity of ε′ = 42,376 and low loss tangents of tanδ = 0.06 (at room temperature) were achieved. The large conduction activation energy at the grain boundary decreased with decreasing dopant concentration. The colossal permittivity was primarily attributed to the internal barrier layer capacitor (IBLC) effect. The dominant effect of interfacial polarization at the non–Ohmic sample–electrode contact was observed when the dopant concentration was ≤1.0 mol%. Interestingly, the sample–electrode contact and resistive–outer surface layer effects, i.e., surface barrier layer capacitor (SBLC) effect, has also an effect on the colossal dielectric response in (In + Nb) co-doped TiO₂ ceramics.     

The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.     

Synthesis and characterization of NH4PO3 based composite with superior proton conductivity for intermediate temperature fuel cells

In this work, we prepared NH₄PO₃/MO₂ (MSi, Ti) composite materials with various amounts of TiO₂ using a sol–gel method, which are potential for application as electrolytes for intermediate temperature fuel cells (150–250 °C). The effect of the amount of TiO₂ on the conductivities of the composite was investigated systematically by an impedance spectroscopy within the temperature range of 50–275 °C under different atmospheres. The composite SiTiO10APP (10 mol% TiO₂) showed high proton conductivity, 0.001–0.043 S cm^?1 at 150–250 °C. The maximum conductivities are 0.043 S cm^?1 at 225 °C under humid H₂ and 0.0085 S cm^?1 at 175 °C under humid air, respectively. A thermogravimetric analysis showed the composite had high thermal stability below 300 °C. Moreover, it was found that the microstructure has significant effect on the conductivity of the composites at higher temperature.