Mesoporous TiO2–SiO2 aerogels with hierarchal pore structures

Freestanding blocks of binary oxides, TiO₂–SiO₂ aerogel containing highly ordered mesophase structures were successfully prepared by a new synthesis method involving partial solvent evaporation followed by supercritical extraction and drying. The new method allows the routine preparation of large, crack-free aerogels of high titanium content (i.e., Ti/Si ? 0.75 or up to 50 wt.% Ti), ordered mesopores (i.e., 2–20 nm), large surface area (i.e., 400–900 m² g^?1) and pore volume (i.e., 0.7–2.6 cm³ g^?1). Aerogels with well-ordered mesopores were obtained for Ti/Si atom ratios of 0.04–0.08. The size of ordered mesopore domains decreases with increasing titanium loading, and TS75 aerogels with Ti/Si = 0.75 display discontinuous microdomains of ordered mesoporosity within disordered phases interspersed with crystalline anatase TiO₂. The greater permeability of the TS75 pore network resulted in fifteen times better activity for photocatalytic oxidation of airborne trichloroethylene compared to commercial Degussa P25 TiO₂ and more than twice that TiO₂–SiO₂ aerogel (TS100) of similar titanium loading but with disordered and tortuous pore network.     

Comparison of microstructure,toughness, mechanical properties and work hardening of titanium/TiO2 and titanium/SiC composites manufactured by accumulative roll bonding (ARB) process

In this study, the effects of TiO₂ ceramic nanoparticles and SiC microparticles on the microstructure, mechanical properties and toughness of titanium/TiO₂ nanocomposite and titanium/SiC composite were investigated. To achieve this goal, TiO₂ and SiC ceramic particles were incorporated as the reinforcement in titanium through the ARB (accumulative roll bonding) process. By adding SiC ceramic particles, the mechanical properties of the composite and the nanocomposite were enhanced, while their toughness was decreased, as compared to TiO₂ nanoparticles. After applying 8 cycles of the ARB process, UTS in Ti/5 vol% SiC composite reached to about 1200 (MPa), as compared to that in Ti/0.5 wt% TiO₂ nanocomposite, which was about 1100 (MPa). Furthermore, toughness in the Ti/5 vol% SiC composite and the Ti/0.5 wt% TiO₂ nanocomposite was 60 and 29 J/m³, respectively. Finally, SEM and TEM images showed SiC microparticles clustering in Ti/SiC composite samples and a suitable distribution of TiO₂ nanoparticles in the Ti/TiO₂ nanocomposite. By adding TiO₂ nanoparticles, mechanical properties and work hardening coefficient were found to be increased, as compared to those of the monolithic samples. TiO₂ nanoparticles, after being distributed in the titanium matrix through the ARB process, caused pin dislocations. As clearly shown in TEM images, dislocation tangles around TiO₂ nanoparticles acted as the main mechanism improving the work hardening coefficient.     

Critical particle concentration in electrophoretic deposition

The role of particle concentration in electrophoretic deposition (EPD) was investigated with two different suspension systems. The first system consisted of positively charged TiO₂ nanoparticles dispersed in isopropanol with 1 vol% water. The second system consisted of negatively charged polystyrene (PS) microbeads dispersed in isopropanol. Constant voltage EPD was performed using suspensions with variable particle concentration (0.013–0.43 vol% TiO₂ and 0.06–11.4 vol% PS). Threshold concentration values were identified for both systems after EPD at 100 V (250 V cm^?1) for 1 min. Below these values the deposited mass deviated from the trend dictated by Hamaker's equation. Higher applied voltages and longer deposition times were tested and the results suggested that the threshold concentration did not depend on those parameters. A phenomenological model of particle deposition was proposed, which accounts for the local electrochemical conditions close to the substrate in relation to particle size.     

Recognition of dimethoate carried by bi-layer electrodeposition of silver nanoparticles and imprinted poly-o-phenylenediamine

Thin film of a molecular imprinted polymer based on electropolymerization method with sensitive and selective binding sites for dimethoate was developed. This film was cast on gold electrode by electrochemical polymerization in solution of o-phenylenediamine and template dimethoate via cyclic voltammetry scans and further deposition of Ag nanoparticles. The surface plasmon resonance and cyclic voltammetric signals were also recorded simultaneously during the electropolymerization, controlling the thickness of the polymer film to be 25 nm. The imprinted film showed high selectivity towards to dimethoate. The recognition between the imprinted sensor and target molecule was observed by measuring the variation amperometric response of the oxidation–reduction probe, K₃Fe(CN)₆, on electrode. Under the optimal experimental conditions, the peak currents were proportional to the concentrations of dimethoate in two ranges, from 1.0 to 1000 ng mL^?1 and from 1.0 to 50 μg mL^?1, with the detection limit of 0.5 ng mL^?1. Due to the high affinity, selectivity and stability the imprinted sensor provides a simple detection platform for organophosphate compounds.     

Electrochemical and peroxidase-catalyzed oxidation of epinephrine

Electrochemical and peroxidase-catalyzed oxidation of epinephrine (EPI) has been studied. In the electrochemical studies a single well-defined, 4e, 4H⁺, pH-dependent oxidation peak was observed in square wave and cyclic sweep voltammetry at edge plane pyrolytic graphite electrode. In the reverse sweep a redox couple was observed. The decay of the UV-absorbing intermediate generated and the first-order rate constants were calculated at different pH and were found to be ～6.3 × 10^?3 s^?1. The detection limit and sensitivity are found to be 17 × 10^?8 M and 2.325 μA μM^?1 respectively. At pH 7.2, the electro-oxidation product was characterized using NMR and DEPT studies as leucoadrenochrome. The peroxidase-catalyzed oxidation was carried out using horseradish peroxidase and initiated by adding H₂O₂. The identical spectral changes, rate constants and product formed during electrochemical and enzymatic oxidation suggest that the same intermediate species is generated during both the oxidations. A tentative pathway for the oxidation of EPI has been suggested. It is concluded that the electrochemical and peroxidase-catalyzed oxidation of EPI proceed by an identical pathway.     

Synthesis of TiO2(B)/SnO2 composite materials as an anode for lithium-ion batteries

A TiO₂(B) nanosheets/SnO₂ nanoparticles composite was prepared by the hydrothermal and chemical bath deposition (CBD) methods, and its electrochemical properties were investigated for use as the anode material of a lithium-ion battery. The as-prepared composites consisted of monoclinic-phase TiO₂(B) nanosheets and cassiterite structure SnO₂ nanoparticles, in which SnO₂ nanoparticles were uniformly decorated on the TiO₂(B) nanosheets. The TiO₂(B)/SnO₂ composites showed a higher reversible capacity and better durability than that of the pure TiO₂(B) for use as a battery anode. The composite electrodes exhibiting a high initial discharge capacity of 2239.1 mAh g⁻¹ and a discharge capacity of more than 868.7 mAh g⁻¹ could be maintained after 50 cycles at 0.1 C in a voltage range of 1.0–3.0 V at room temperature. The results suggest that TiO₂(B) nanosheets coated with SnO₂ could be suitable for use as a stable anode material for lithium-ion batteries. In addition, the coulombic efficiency of the nanosheets remains at an average of 93.1% for the 3rd–50th cycles.     

Electroanalysis of ascorbic acid (vitamin C) using nano-ZnO/poly(luminol) hybrid film modified electrode

Electrochemical analysis of ascorbic acid (AsA) in physiological condition using a new hybrid film modified electrode is described. Electrochemical polymerization of luminol in 0.1 M H₂SO₄ solution was carried out using ZnO nanoparticles (ZnO-NPs) coated glassy carbon electrode (GCE) as working electrode. This hybrid film coated electrode noted as poly(luminol)/ZnO-NPs hybrid film modified GCE (PLu/ZnO-NPs/GCE). The atomic force microscope (AFM) and scanning electron microscope (SEM) studies were demonstrated that PLu/ZnO-NPs hybrid film covered the electrode surface and the ZnO-NPs particle sizes were <100 nm. The visible blue colored organic–inorganic (PLu/ZnO-NPs) hybrid films were observed on the electrode surface. Electrochemical studies proved that PLu/ZnO-NPs hybrid film modified electrode is electroactive in the pH range from 1 to 11 and the poly(luminol) (PLu) redox peak was pH dependent with a slope of ?53 mV/pH. The PLu/ZnO-NPs modified electrodes electroactivity also investigated by catalyzing the oxidation of AsA, demonstrating its great potential applications in electroanalysis of AsA. The resulting, AsA electrochemical sensor exhibited a wide linear response range (from 1 × 10^?6 to 3.6 × 10^?4 M, r² = 0.9989), lower detection limit (1 × 10^?6 M) and fast response time (3 s) for AsA determination. Our results show that PLu/ZnO-NPs hybrid film provides a novel and efficient platform for the oxidation of AsA and realizing efficient electrocatalysis and that the materials have potential applications in the fabrication of electrochemical sensors. Analysis of commercial vitamin C samples using PLu/ZnO-NPs hybrid film modified electrode was demonstrated and the obtained results are good agreement with the labeled amount.     

Solvothermal fabrication of three-dimensionally sphere-stacking Sb–SnO2 electrode based on TiO2 nanotube arrays

TiO₂-NTs-based Sb–SnO₂ electrode with three-dimensionally sphere-stacking structure was successfully fabricated by the solvothermal method, followed by annealing at 500 °C for 1 h. The physico-chemical properties of electrodes were characterized through scanning electron spectroscopy (SEM), X-ray diffraction (XRD) and electrochemical measurements. SEM result showed that TiO₂-NTs/Sb–SnO₂ electrode has morphology of vertically sphere-stacking coralline. Compared with Ti/Sb–SnO₂, TiO₂-NTs/Sb–SnO₂ electrode has smaller grain size and greater specific surface area which can provide with more active sites. Compared with Ti/Sb–SnO₂ electrode, TiO₂-NTs/Sb–SnO₂ has a higher oxygen evolution potential and stronger phenol oxidation peak, indicating an improved catalytic activity for phenol degradation. The kinetic analysis of electrochemical phenol degradation showed that the first-order kinetics rate constant on TiO₂-NTs/Sb–SnO₂ electrode is 1.33 times as much as that on Ti/Sb–SnO₂, confirming that the sphere-stacking Sb–SnO₂ based on TiO₂ nanotube has a good electrocatalytic activity.     

Electrophotocatalytic decolorization of an azo dye on TiO2 self-organized nanotubes in a laboratory scale reactor

It was investigated the feasibility of decolorization of an azo dye (DG 26) using a large scale nanotubular TiO₂ structured electrode in a laboratory photoelectrochemical reactor (0.8 L). Catalyst was grown by anodic oxidation directly on Ti surface and its microstructure and crystalline structure were characterized with SEM and XRD. TiO₂/Ti photoactivity under different anodic polarization values was evaluated via photoelectrochemical tests. The nanostructured TiO₂ was used in a reactor as photo-anode under UV monochromatic irradiation (254 nm) and it was subjected to bias (+ 1.5 V vs. SCE). A comparison with photolysis and photocatalysis processes was carried out under the same operating conditions to evaluate the synergistic action of photocatalysis and TiO₂/Ti electrochemical polarization.Electrophotocatalysis was proven to be more effective than photocatalysis in DG 26 decolorization. Catalyst polarization resulted in synergistic effect on process yields. The complete decolorization of a 40 mg/L solution of DG 26 was achieved in 24 h, without adding chemical reagents, and catalyst durability was demonstrated over 360 h tests. Therefore, the work done is challenging to prove that the process (irradiation + catalyst + polarization) is feasible and effectively up-grading to pilot and demonstrative scale applications after a fluid dynamics optimization of the photoreactor.     

Novel one-step preparation of tungsten loaded TiO2 nanotube arrays with enhanced photoelectrocatalytic activity for pollutant degradation and hydrogen production

Highly ordered tungsten doped TiO₂ nanotube arrays (W-TiO₂NTs) were prepared in glycerol/fluoride electrolyte solution containing sodium tungstate via the electrochemical oxidation of a Ti substrate. The resulting arrays were characterized by XRD, SEM, and XPS. The 15 mM W-TiO₂NTs exhibited better photoelectrochemical activity than the TiO₂NTs and W-TiO₂NTs fabricated using other W concentrations under Xe illumination. The W ion was successfully introduced into the TiO₂ crystal lattice in the W^6 + form according to the XPS analysis, which enhanced the photoelectrocatalytic activity of the W-TiO₂NTs, as indicated by the efficient removal of Rhodamine B and the production of hydrogen.     

TiO2–SnO2 nanomaterials for gas sensing and photocatalysis

Nanopowders of TiO₂–SnO₂ over a full composition range extending from 100 mol% TiO₂ to 100 mol% SnO₂ are obtained by the sol–gel method from TTIP and SnCl₂·5H₂O precursors of Ti and Sn, respectively followed by calcination at 400 °C. The samples are characterized by means of BET, XRD and TEM. Optical properties of the prepared nanomaterials are studied as well. TEM images indicate that the nanoparticles are regular in shape. The specific surface area, SSA of TiO₂ is 95 m²/g while that of SnO₂ amounts to 129 m²/g. The highest SSA of 156 m²/g is achieved at 20 mol% of TiO₂. Occurrence of rutile, anatase and brookite polymorphic forms depends on the chemical composition of nanopowders. Formation of rutile-type solid solution of TiO₂–SnO₂ over the range of 0–80 mol% TiO₂ is confirmed by Vegard rule applied to lattice constants. Electronic band gap decreases with Ti content from 3.84 eV (100 mol% SnO₂) to 3.18 eV (100 mol% TiO₂).     

Novel spherical TiO2 supported PdNi alloy catalyst for methanol electroxidation

A novel PdNi/TiO₂ electrocatalyst for methanol oxidation is fabricated using spherical TiO₂ nanoparticles as support. The structural and electrochemical properties of the PdNi/TiO₂ catalyst are characterized by XRD, TEM and electrochemical analysis. The cyclic voltammograms of PdNi/TiO₂ catalyst show that there is a large methanol oxidation peak in about 0.882 V that is much bigger than that of the commercial PtRu/C catalyst in 0.7 V. The composite TiO₂ material has high catalytic activity without UV light illumination. The electrocatalytic activity and anti-poisoning capability of the PdNi/TiO₂ catalyst are promising, which may become a potential candidate for direct methanol fuel cell.     

Protective properties of Al2O3 + TiO2 coating produced by the electrostatic spray deposition method

Mechanical resistance of Al₂O₃ + TiO₂ nanocomposite ceramic coating deposited by electrostatic spray deposition method onto X10CrAlSi18 steel to thermal and slurry tests was investigated. The coating was produced from colloidal suspension of TiO₂ nanoparticles dispersed in 3 wt% solution of Al₂(NO₃)₃, as Al₂O₃ precursor, in ethanol. TiO₂ nanoparticles of two sizes, 15 nm and 32 nm, were used in the experiments. After deposition, coatings were annealed at various temperatures, 300, 1000 and 1200 °C, and next exposed to cyclic thermal and slurry tests. Regardless of annealing temperature and the size of TiO₂ nanoparticles, the outer layer of all coatings was porous. The first five thermal cycles caused a rapid increase of aluminum content of the surface layer to 30–37 wt%, but further increase in the number of thermal cycles did not affect the aluminum content. The oxidation rate of coating-substrate system was lower during the thermal tests than during annealing. The oxidation rate was also lower for smaller TiO₂ particles (15 nm) forming the coating than for the larger ones (32 nm). The protective properties of Al₂O₃ + TiO₂ coating against intense oxidation of substrate were lost at 1200 °C. Slurry tests showed that coatings annealed at 1000 °C had the best slurry resistance, but thermal tests had weakened this slurry resistance, mainly due to decreasing adhesion of the coating.     

Raman spectra and extended X-ray absorption fine structure characterization of La(2−x)/3NaxTiO3 and Nd(2−x)/3LixTiO3 microwave ceramics

A-site deficient perovskite compounds, La_(2?x)/3Na_xTiO₃ (0.02 ≤ x ≤ 0.5) and Nd_(2?x)/3Li_xTiO₃ (0.1 ≤ x ≤ 0.5) microwave ceramics, were investigated by Raman scattering. Nd_(2?x)/3Li_xTiO₃ (0.1 ≤ x ≤ 0.5) was also investigated by extended X-ray absorption fine structure (EXAFS) measurement. The Raman shifts of the E (239 cm^?1) and A₁ (322 cm^?1) modes of La_(2?x)/3Na_xTiO₃ were found to decrease with x. However, the E (254 cm^?1) and A₁ (338 cm^?1) of Nd_(2?x)/3Li_xTiO₃ were found to blueshift with x, which was caused by Li substitution. The redshift of the A₁ (471 cm^?1) phonon of Nd_(2?x)/3Li_xTiO₃ (0.1 ≤ x ≤ 0.3) indicates that O–Ti–O bonding forces lessen with Li concentration, which is consistent with the EXAFS result that Ti–O bond lengths increase for 0.1 ≤ x ≤ 0.3. For x > 0.3, the EXAFS result shows that Ti–O bond lengths decrease. Moreover, Ti–O bond lengths show strong correlation with the microwave dielectric constants of Nd_(2?x)/3Li_xTiO₃.     

Role of the effective electrical conductivity of nanosuspensions in the generation of TiO2 agglomerates with electrospray

Suspensions with varying volume fraction of TiO₂ nanoparticles and ionic strength were electrosprayed to obtain agglomerates of different characteristics, which were then deposited to produce films with tailored morphology, thickness, and porosity. The role of the nanoparticle volume fraction in both the effective electrical conductivity of TiO₂ nanosuspensions and the control of the size of agglomerates produced by electrospray was investigated. A simple modified equation for the effective electrical conductivity of TiO₂ nanoparticle suspensions was derived. The equation, which accounted for nanoparticles' diffuse ionic layer and their agglomeration in a liquid, showed that the effective electrical conductivity is not only a function of the liquid and particle conductivities, and the particle volume fraction but also a function of both the thickness of the adsorbed ionic layer on the particles and the particle size. Gradual increase of particle volume fraction resulted in an increase in the suspension's effective electrical conductivity, when the initial liquid conductivity was in the range of 10^?4–10^?3 S m^?1. When the liquid conductivity was in the range of 10^?3–10^?2 S m^?1; however, addition of particles did not have any significant effect on the effective electrical conductivity. Control over the size of the TiO₂ nanoparticle agglomerates was achieved by electrospraying suspensions with liquid electrical conductivity of the order of 10^?3 S m^?1 and by varying the particle volume fraction. Electrospray deposition of suspensions with TiO₂ volume fraction=0.04% resulted in a more compact film with lower porosity and showed better water-splitting performance.     

One-pot electrochemical synthesis of graphene by the exfoliation of graphite powder in sodium dodecyl sulfate and its decoration with platinum nanoparticles for methanol oxidation

We demonstrate a method which directly grows large areas of graphene on carbon paper and glassy carbon (GC) substrates from graphite powder and anionic surfactant, sodium dodecyl sulfate, assisted electrochemical exfoliation. The electrochemically reduced graphene has been carefully characterized by scanning electron microscopy (SEM) and electrochemical techniques. Particularly, SEM images show enhanced growth of graphene structures formed of ‘urchin’ objects. The CV spectra illustrate that a variety of the oxygen-containing functional groups has been thoroughly removed from the graphite plane via electrochemical reduction. Potential peak (Ep) of graphene electrode in [Fe(CN)₆]^3−/4− solution is as small as 212 mV which is 168 mV smaller than that of graphite electrode. This could be attributed to the high quality graphene accelerating the electron transfer rate in [Fe(CN)₆]^3−/4− electrochemistry. Finally, platinum was electro reduced onto the GC and graphene modified GC based electrodes for use in methanol oxidation. The catalytic activities of graphene-supported Pt nanoparticles and Pt-GC electrocatalysts for methanol oxidation were 1900 and 915.5 A g⁻¹ Pt, which can reveal the particular properties of the exfoliated graphene supports.     

Synthesis of a graphene–carbon nanotube composite and its electrochemical sensing of hydrogen peroxide

Graphene, whose structure consists of a single layer of sp²-hybridized carbon atoms, provides an excellent platform for designing composite nanomaterials. In this study, we have demonstrated a facile process to synthesize graphene–multiwalled carbon nanotube (MWCNT) composite. The graphene–MWCNT composite material is endowed with a large electrochemical surface area and fast electron transfer properties in Fe(CN)₆^3?/4? redox species. A graphene–MWCNT composite modified electrode exhibits good performance in terms of the electrocatalytic reduction of H₂O₂; a sensor constructed from such an electrode shows a good linear dependence on H₂O₂ concentration in the range of 2 × 10^?5 to 2.1 × 10^?3 mol L^?1. The detection limit is estimated to be 9.4 × 10^?6 mol L^?1. This study provides a new kind of composite modified electrode for electrochemical sensors.     

Hollow Fe2O3 polyhedrons: One-pot synthesis and their use as electrochemical material for nitrite sensing

In this paper, hollow hematite nano-polyhedrons (Fe-HNPs) were synthesized via a facile solution route. The abundance of high indexed facets was demonstrated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. A new electrochemical biosensor for nitrite determination was then proposed by using the hematite hollow nanopolyhedron as the sensing layer. Electrochemical tests showed that the Fe-HNPs could act as efficient enzyme-like electron mediators for nitrite oxidation. As a result, the Fe₂O₃ modified biosensor exhibited excellent performance for the determination of nitrite with a response time of <10 s, linear range between 0.009 and 3 mM, and sensitivity as 19.83 μA mM^?1. A high selectivity and long-term stability toward nitrite oxidation in the presence of glucose and l-ascorbic (AA) was also observed at their maximum physiological concentrations, which made this novel Fe₂O₃ nanomaterial bounded with high indexed facets promising for sensing applications in medicine, biotechnology and environmental chemistry.     

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.     

Synthesis,characterization and electrochemical performance of Sn3F3PO4 anode material for lithium-ion batteries

Tin fluorophosphate (Sn₃F₃PO₄) powder was synthesized via a microemulsion route. Physical properties of the synthesized material were investigated by means of X-ray powder diffractometry (XRD) and field emission scanning electron microscopy (FE-SEM). The investigation showed that the synthesized powder was crystalline Sn₃F₃PO₄ with needle-like morphology with a thickness of 300–500 nm and length of 5–10 μm. The electrochemical performance of the synthesized powder as a negative electrode for Li-ion batteries was studied. The results showed that the synthesized Sm₃F₃PO₄ possessed an initial discharge capacity of 1370 mAh g^?1 and charge capacity of 968 mAh g^?1 in a potential range of 0.005–3 V. In addition, the material showed capacity retention of 70.8% after 30 cycles at a constant current density of 100 mA g^?1.