Antimicrobial Properties of TiO2 Microparticles Coated with Ca- and Cu-Based Composite Layers

The ability of TiO₂ to generate reactive oxygen species under UV radiation makes it an efficient candidate in antimicrobial studies. In this context, the preparation of TiO₂ microparticles coated with Ca- and Cu-based composite layers over which Cu(II), Cu(I), and Cu(0) species were identified is presented here. The obtained materials were characterized by a wide range of analytical methods, such as X-ray diffraction, electron microscopy (TEM, SEM), X-ray photoelectron (XPS), and UV-VIS spectroscopy. The antimicrobial efficiency was evaluated using qualitative and quantitative standard methods and standard clinical microbial strains. A significant aspect of this composite is that the antimicrobial properties were evidenced both in the presence and absence of the light, as result of competition between photo and electrical effects. However, the antibacterial effect was similar in darkness and light for all samples. Because no photocatalytic properties were found in the absence of copper, the results sustain the antibacterial effect of the electric field (generated by the electrostatic potential of the composite layer) both under the dark and in light conditions. In this way, the composite layers supported on the TiO₂ microparticles’ surface can offer continuous antibacterial protection and do not require the presence of a permanent light source for activation. However, the antimicrobial effect in the dark is more significant and is considered to be the result of the electric field effect generated on the composite layer.     

A calorimetric analysis of a polymer electrolyte fuel cell and the production of H2O2 at the cathode

A calorimeter has been constructed and used to measure the total heat production of a single polymer electrolyte fuel cell that is operated on hydrogen and oxygen at 50 °C and 1 bar. The cell had a SolviCore Catalyst Coated Backing and Nafion membranes 112, 115 and 117. We report that the total heat production plus the power production corresponds to the enthalpy of formation of water for cell potentials above 0.55 V. For cell potentials less than 0.55 V, we measured a linear decrease in the reaction enthalpy with decreasing cell potential. This effect was obtained independently of membrane thickness and current density. We propose therefore that the main power loss at low cell potentials and the inflection point in the polarisation curve is due to hydrogen peroxide formation at the cathode. The total heat production was decomposed into reversible and irreversible effects (non-ohmic and ohmic). The non-ohmic part was evaluated using Tafel plots. We show that it is possible to determine the overpotential of an electrode also from its thermal signature.     

Significant enhancement of the oxidation of CO by H2 and/or H2O on a FeO x /Pt/TiO2 catalyst

Oxidation of CO on the FeO _x /Pt/TiO₂ catalyst is markedly enhanced by H₂ and/or H₂O at 60 °C, but no such enhancement is observed on the Pt/TiO₂ catalyst, but shift reaction (CO + H₂O → H₂ + CO₂) does not occur on the FeO _x /Pt/TiO₂ catalyst at 60 °C. DRIFT-IR spectroscopy reveals that the fraction of bridge bonded CO increases while that of linearly bonded CO decreases on the FeO _x loaded Pt/TiO₂ catalyst. The in-situ DRIFT IR spectra proved that the bridged CO is more reactive than the linearly bonded CO with respect to O₂, and the reaction of the bridge-bonded CO with O₂ as well as of the linearly bonded CO is markedly enhanced by adding H₂ to a flow of CO + O₂. From these results, we deduced that the promoting effect of H₂ and/or H₂O is responsible for the preferential oxidation (PROX) reaction of CO on the FeO _x /Pt/TiO₂ catalyst, and a following new mechanism via the hydroxyl carbonyl or bicarbonate intermediate is proposed for the oxidation of CO in the presence of H₂O.      

Influence of the V2O5 Loading on the Structure and Activity of V2O5/TiO2 SCR Catalysts for Vehicle Application

In this paper the effect of the vanadium oxide loading on the surface vanadia structure and the activity as well as selectivity in the catalytic reduction of NO with NH₃ was studied for a V₂O₅/TiO₂ model system. A series of TiO₂ (WO _x stabilized anatase) supported vanadia catalysts with varying loadings were characterized by laser Raman spectroscopy, ⁵¹V MAS-NMR, V K XANES. To determine the acidic properties, DRIFTS measurements were done with pyridine adsorbed on the samples. The measurements indicate that with increasing active phase loading square pyramidal coordinated surface vanadia species are replaced by an amorphous highly dispersed vanadium oxide phase with a coordination like V₂O₅. In addition, the ratio of Brønsted to Lewis acid sites is shifted from a comparatively low to an equal level at high loadings. This structural change is accompanied by a clearly improved catalytic activity and selectivity.     

Nd2O3掺杂对MnCoNi系NTC热敏电阻电性能的影响

采用传统固相法制备了Co_0.7-xMn_2.1Ni_0.2Nd_xO₄(X=0,0.04,0.06,0.08)样品。利用X射线衍射、SEM、阻值测量等手段,研究了微量Nd₂O₃掺杂对MnCoNi系NTC热敏电阻材料的影响。研究结果表明：在0≤X≤0.08掺杂范围内,随着Nd₂O₃掺杂量的增加,MnCoNi系NTC热敏电阻的晶相结构和阻温特性并没有改变,晶粒变小,电阻率和B值分别由202.8Ω.cm、3432K,上升到2944.7Ω.cm、4152K;老化特性得到显著提高,△R₂₅/ R₂₅和△B_25/50/ B_25/50变化率分别由1.15%,0.75%降至0.31%,0.22%。     

The Effect of Chelating Agent on the Catalytic and Structural Properties of Sm2Zr2O7 as a Methane Combustion Catalyst

The Sm₂Zr₂O₇ of pyrochlore structure was studied as a catalyst for high temperature combustion. It was prepared by the sol-gel method with and without acetylacetone as a chelating agent. The order of crystallinity and the surface area were improved when acetylacetone was used. The catalytic activity of CH₄ combustion was also enhanced and superior to that of Mn-substituted hexaaluminate above 550 °C.     

Comparison of Two Preparation Methods in the Redox Properties of Pd/CeO<Subscript>2</Subscript>/Ta/Si Model Catalysts: Spin Coating Versus Sputter Deposition

Pd/CeO₂/Ta/Si model catalysts were prepared by spin coating and sputter deposition method, and characterized by means of AFM, SEM and in situ XPS, especially focusing on the redox properties of Ce and Pd elements. Compared with thin CeO₂ films (about 2.2nm), the thicker ones (about 22nm) maintained Ce⁴⁺ oxidation state even after treatment with H₂ up to 500°C while the presence of Pd facilitated the reduction of ceria. The reduction of ceria brought about following that of PdO, which was explained by the spillover of hydride in Pd to CeO₂ originating from hydrogen adsorption on the Pd surface. Compared with the sputter deposition method, spin coating produced the smaller size of Pd particles, thus leading to formation of the stable PdO species against hydrogen. Based on these results, a schematic model of Pd/CeO₂/Ta/Si was suggested and it might be assumed that spin coating method provided with an environment similar to the conventional impregnation.     

Effect of SiO2 nanoparticle addition on the characteristics of a new organic-inorganic hybrid membrane

Poly(vinylidene fluoride) composite membranes filled with different weight fractions of SiO₂ nanoparticles have been prepared by a blending method. Cation-exchange groups were introduced by the copolymerization of glycidyl methacrylate with divinylbenzene and subsequent sulfonation. These hybrid membranes have been characterized by Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and water uptake and ion-exchange capacity measurements. Membrane potential and membrane conductivity measurements have been carried out with different counter ions to investigate the relationship between ionic migration and the SiO₂ nanoparticle content. The counter-ion transport number and permselectivity of these membranes are found to be highly dependent on the SiO₂ content in the membrane phase and the nature of the counter ion. Membrane conductance was analyzed in terms of phenomenological coefficients using non-equilibrium thermodynamic principles. It can be concluded that these hybrid membranes exhibit high thermal stability, improved selectivity, and moderate membrane conductivity, and may be suitable for use in the electro-driven separation processes.     

Modeling of the photocatalytic decomposition of gaseous benzene in a TiO2 coated optical fiber photoreactor

Photocatalytic decomposition of benzene in an air stream in a continuous TiO₂-coated optical fiber photoreactor (OFP) was demonstrated to be effective at relatively short retention times. An increase in TiO₂ coating thickness, fiber length and retention time improved the decomposition of benzene; however, excessive TiO₂ coating thickness and optical fiber length may hamper the reaction. The UV light intensity distribution on and within the optical fiber was modeled using Snell’s law and UV light energy balance. The modeled profile indicated that the UV light intensity decreased rapidly along the axial and radial directions of the optical fiber. A mathematical model combining the continuity equations and Langmuir–Hinshelwood surface kinetics was established to adequately describe the reaction behavior of benzene decomposition in the OFP with only single TiO₂-coated fiber.     

Development of a Pt/TiO2 catalyst on an anodic alumite film for catalytic decomposition of formaldehyde at room temperature

A Pt/TiO₂ catalyst was prepared on an anodic alumite film and employed in the catalytic decomposition of formaldehyde at room temperature. The results show that the catalyst exhibits good activity toward the decomposition of formaldehyde at room temperature when the anodic alumite film is treated in hot water. Moreover, in accordance with the process requirements, the developed catalyst can be formed into various shapes such as a mesh, plate, fin, serrate etc., because aluminum can be formed into any shapes.     

The effect of argon shielding gas at plasma spray process on the structure and properties of MoSi2 coating

In this work, MoSi₂ powder was agglomerated for using it in atmospheric plasma spray (APS) process. MoSi₂ coatings were manufactured by APS and argon-shrouded plasma spray (ASPS) processes. Phase composition and structural properties of coatings were analyzed using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Also, the mechanical properties of coatings (such as microhardness and adhesion strength) were evaluated. Using the ASPS method, the coatings were found to have a low porosity and highly homogeneous structure. In addition, the argon protection gas was used to prevent the oxidation of the powder. Finally, the ASPS method revealed better microhardness and bending strength results for the corresponding tests.     

Insights on the SO2 poisoning of Pt3Co/VC and Pt/VC fuel cell catalysts

SO₂ poisoning of carbon-supported Pt₃Co (Pt₃Co/VC) catalyst is performed at the cathode of proton exchange membrane fuel cells (PEMFCs) in order to link previously reported results at the electrode/solution interface to the FC environment.First, the surface area of Pt₃Co/VC catalyst is rigorously characterized by hydrogen adsorption, CO stripping voltammetry and underpotential deposition (upd) of copper adatoms. Then the performance of PEMFC cathodes employing 30 wt.% Pt₃Co/VC and 50 wt.% Pt/VC catalysts is compared after exposure to 1 ppm SO₂ in air for 3 h at constant cell voltage of 0.6 V. In agreement with results reported for the electrode/solution interface, the Pt₃Co/VC is more susceptive to SO₂ poisoning than Pt/VC at a given platinum loading.Both catalysts can be recovered from adsorbed sulfur species by running successive polarization curves in air or cyclic voltammetry (CV) in inert atmosphere. However, the activity of Pt₃Co/VC having ∼3 times higher sulfur coverage is recovered more easily than Pt/VC. To understand the difference between the two catalysts in terms of activity recovery, platinum-sulfur interaction is probed by thermal programmed desorption at the catalyst/inert gas interface and CV at the electrode/solution interface and in the FC environment.     

Development of New Cu0–ZnII/Al2O3 Catalyst Supported on Copper Metallic Foam for the Production of Hydrogen by Methanol Steam Reforming

Copper metallic foam with thermal conductive properties, manufactured by S.C.P.S., has been investigated as a support for catalysts to improve thermal exchange inside the reactor for the endothermic steam reforming of methanol. Thus, we have developed a procedure for the in situ preparation of a Cu⁰–Zn^II/Al₂O₃ catalyst onto the copper metallic foam. The foam-based Cu⁰–Zn^II/Al₂O₃ catalyst shows an activity three times as high as commercial catalysts for a conversion of 74% of methanol into hydrogen.     

Effect of the preparation method on the surface coverage of Mo/Al2O3 catalysts

Two series of Mo/Al₂O₃ catalysts were prepared by equilibrium adsorption and incipient wetness impregnation methods. The effect of preparation method on the surface coverages of the calcined catalysts was investigated by the combined use of CO₂ chemisorption, low temperature CO adsorption and ion scattering spectroscopy (ISS). For a given Mo loading, the CO₂ and CO adsorption results showed little difference between the two preparation methods. As previously noted, the CO₂ chemisorption method overestimated the Mo surface coverage. In contrast to the adsorption methods, the ISS technique gave different Mo surface coverage values for a given Mo content of the two series of catalysts. This apparent discrepancy was attributed to different repartition of the Mo phase between the internal and external surfaces which can only be detected by ISS. This interpretation is supported by the observed agreement between the coverage values measured from ISS and low temperature CO adsorption for presumably uniform catalysts obtained by the equilibrium adsorption method.     

Role of the nature of the acid sites in the oxydehydrogenation of propane on a VPO/TiO2 catalyst. An in situ FT-IR spectroscopy investigation

Catalytic activity and surface acidity during the oxydehydrogenation of propane over a VPO/TiO₂ catalyst were determined by a dynamic in situ FT-IR spectroscopy technique at 350°C. Pyridine was used as a probe molecule for the acidity measurements. The obtained results show that propene formation is linked to Brønsted acid sites and that water increases the number of these sites which, in turn, increases propene selectivity.     

Electrochemical characterization of adsorbed bilirubin oxidase on Vulcan XC 72R for the biocathode preparation in a glucose/O2 biofuel cell

A new biocathode was built and tested. It consisted of bilirubin oxidase adsorbed on Vulcan XC 72 R and immobilized into a Nafion^® matrix. The possibility of direct electron transfer between bilirubin oxidase and Vulcan XC 72 R was also demonstrated. The kinetics on biocathode were enhanced by including 2,2′-azinobis-3-ethylbenzothiazoline-5-sulfonic acid in the catalytic film. A first order reaction rate was observed for oxygen concentrations lower than 22%. A complete kinetic investigation of the system was shown. A biofuel cell test performed with this biocathode and Au₇₀Pt₃₀ nanoparticles as anode catalyst permitted to reach a power density of 170 μW cm⁻² at a cell voltage of 0.6 V, which is superior to what can be obtained with the concentric design.     

Role of surface state on the electron flow in modified TiO2 film incorporating carbon powder for a dye-sensitized solar cell

An investigation of surface-related traps in nanostructured TiO₂ films modified by the incorporation of carbon powder was conducted by the potential-step chronoamperometric method. For the modification of the morphology and surface state of the nanoporous TiO₂ electrode, the incorporation of carbon into the white TiO₂ powder was accomplished. In the chronoamperometric data, all of the transients showed an initial fast phase (<1 s) followed by a slower phase which is related to the trap filling process. The trap-filling period of the carbon incorporated TiO₂ film becomes longer, as the applied negative potential increases, due to the widely distributed traps induced by the increased surface area. Furthermore, the film capacitance was derived as a function of the applied bias by integrating the current to time curves of the chronoamperometric data. The accumulated charge of the carbon incorporated TiO₂ film increases prominently in two regions. The dominant increase shown in the positive region (−0.7 to −0.9 V vs. Ag/AgCl at pH 13) of the flat band potential implies that the electron occupancy in the surface-related traps is increased. At a more negative potential (below −1.2 V vs. Ag/AgCl), electrons from the conduction band of the TiO₂ film substantially influence the total current, thereby inducing an exponential increase in the current. Therefore, it is found that most of the traps are located in the positive region of the flat band potential, since the Fermi level of the nanostructured TiO₂ film is positioned at −1.14 V vs. Ag/AgCl at pH 13. The trap sites in the sub-bandgap region of the TiO₂ film are important in the electron transport of photoinjected electrons from dye molecules and partially charge recombination with redox electrolyte in operating dye-sensitized solar cell. The influence of charge trap formed by increased surface states on the electron transport and electron transfer was investigated by photovoltage and photocurrent transient measurements.