Wet oxidation of wastewater containing hydrocarbons by novel supported Pd catalysts

Pd catalysts supported on TiO₂, ZrO₂, ZSM-5, MCM-41 and activated carbon were used in catalytic wet oxidation of hydrocarbons such as phenol, m-cresol and m-xylene. It was found that the Pd/TiO₂ catalyst was highly effective in the wet oxidation of hydrocarbon. The activities of catalysts with various hydrocarbon species, catalyst support, oxidation state of catalyst performed in a 3-phase slurry reactor show that reaction on Pd surface is more favorable than that in aqueous phase and that the active site is oxidized Pd in catalytic wet air oxidation of hydrocarbons. Based on the experimental results, a plausible reaction mechanism of wet oxidation of hydrocarbons catalyzed over Pd/TiO₂ catalyst was proposed. This catalyst is superior to other oxide catalysts because it suppressed the formation of hardly-degradable organic intermediates and polymer.     

Decane reforming reaction over Pt,Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite

Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on NaY- and HY-zeolite were examined as a catalyst for producing gasoline from n-decane via simultaneous reforming and cracking. The catalysts were prepared by calcining and reducing metal-ion-exchanged Y-zeolite with O₂ and H₂ at 300°C., respectively. Thus prepared catalysts were characterized by hydrogen chemisorption and temperature programmed desorption of ammonia. Pt-Ni/NaY and Pt-Ir/NaY bimetallic catalysts offered the improved activity maintenance compared to Pt/NaY monometallic catalyst. The catalysts supported on HY-zeolite showed higher selectivity toward C₅–C₇ and skeletal isomers of C₅–C₇- and C₈–C₁₀ than those of the catalysts supported on NaY-zeolite, which is a desired characteristic for increasing octane value of gasoline these days. However, deactivation with reaction time was much more pronounced on HY-zeolite-supported catalyst. When the catalyst was prcsulfided with H,S, the stability with time on stream was enhanced and the selectivity was quite different from that of the catalyst before presulfiding. The acidity of Y-zeolite and presulfiding of catalyst greatly influenced the activny, selectivity and stability of Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite in n-decane reforming reaction.     

Electrical properties of (Bi3.5La0.5)Ti3O12 thin-films prepared by liquid source misted chemical deposition

The ((Bi_3.5La_0.5)Ti₃O₁₂(BLT) thin-films used in this study were fabricated on a Pt(111)/SiO₂/Si(100) substrate by a Liquid Source Misted Chemical Deposition (LSMCD) technique. X-ray diffraction patterns showed that the BLT films were crystallized and no other phases were observed when annealed above 650 ‡C. Grain size and remnant polarizations increased with increase in the annealing temperature, while leakage current densities decreased. The remnant polarizations (Pr) increased from 2.0 to 4.8 and 19.0 μC/cm2 with increase in the annealing temperature from 650 to 700 and 750 ‡C, respectively. The BLT films annealed at 700 ‡C in O₂ showed a good fatigue resistance of reduced polarization by 10% after 10⁹ switching cycles when 9 V of bipolar voltage was applied at a frequency of 40 kHz.     

Enhanced hydrothermal stability of ZSM-5 formed from nanocrystalline seeds for naphtha catalytic cracking

We successfully synthesized hydrothermally stable ZSM-5 with crystalline nano seeds. We employed a template-free method using ZSM-5 crystalline nano seeds and sodium silicate as a silica source. The prepared ZSM-5 exhibited uniform crystal size and relative crystallinity greater than 100 %. The size of the crystalline nano seed in the scale of 100 nm was found to be the optimum size for obtaining uniform, highly crystalline ZSM-5 with structural stability. After P-modification, the synthesized ZSM-5 with the optimally sized seed showed high hydrothermal stability and improved catalytic naphtha cracking activity compared to a commercial ZSM-5 catalyst. In order to find the elements for the increased hydrothermal stability, the samples were evaluated by studying crystallinity, aluminum spectrum, and acidity using XRD, solid-state NMR, and NH₃-TPD, respectively after steaming at 800 °C for 24 h. It is speculated that the increased hydrothermal stability of the ZSM-5 resulted mainly from the increased aluminum structural stability.     

The catalytic activity and surface characterization of Ln2B2O7 (Ln=Sm, Eu, Gd and Tb; B=Ti or Zr) with pyrochlore structure as novel CH4 combustion catalyst

Ln₂B₂O₇ (Ln=Sm, Eu, Gd and Tb; B=Zr or Ti) with pyrochlore structure was prepared by sol–gel method for the high-temperature catalytic combustion. The crystal structure of Ln₂B₂O₇ was identified by XRD and their surface area was about 4 m²/g after calcinations at 1200 °C. Catalytic activity of methane combustion was observed for Ln₂Zr₂O₇ series and the best catalyst was Sm₂Zr₂O₇. Its relative reaction rate per unit surface area at 600 °C was 2 cm³/m² min, which was twice higher than that of Mn-substituted Sr hexaaluminate. From surface analysis by XPS, the low binding energy of each Ln element of Ln₂Zr₂O₇ compared to that of Ln₂Ti₂O₇, gave the catalytic activity of methane combustion.     

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.     

Anisotropic etching characteristics of platinum electrode forferroelectric capacitor

The effect of etch parameters of platinum etching using Cl₂ /CO plasma on the etching properties and the etch profiles was investigated. The etching characteristics with respect to substrate temperature are different in two temperature regions below and above 210°C and significantly depended on Cl₂ concentration in each temperature region. The etch rates of Pt were enhanced suddenly at the substrate temperature of around 210°C when Cl₂ concentration is 50-80%. The etch rates of Pt below 210°C did not change much with increasing temperature. The selectivity of Pt over SiO ₂ was governed by the etch rate of SiO₂ in the lower temperature region but determined by the etch rates of Pt in the higher temperature region. The anisotropy of etch profiles was high enough to achieve vertical pattern without etch residues in the lower temperature region for the application in fabricating 1-Gbit era. In the higher temperature region, however, the slopes of etch profiles due to the volatile products of Pt were found. XPS was used to analyze the surface atomic compositions after various etching treatments     

Preparation and characterization of vanado-, ferri-, and gallosilicate catalysts in the presence of fluoride ions

Vanado-, ferri-, and gallosilicate catalysts were prepared from the mixtures containing colloidal silica, corresponding metal source, tetrapropylammonium bromide, and NH₄F by hydrothermal crystallization at 175°C for 7 days. The pH value of the reaction mixture was low (pH<8) compared to the conventional methods. The metal compounds have higher solubilites in these conditions than conventional conditions (pH>10). The size distribution and the size of final products were found to be more homogeneous and larger than those of metallosilicates prepared in strong alkaline media. The characterization of metallosilicates with IF!, X-ray diffraction, SEM, EPR, and²⁹Si MAS NMR, indicated that corresponding metal atoms were successfully incorporated into the tetrahedral lattice sites of the ZSM-5 structure.     

Quaternary Pt-based electrocatalyst for methanol oxidation by combinatorial electrochemistry

The demonstration to apply the combinatorial method using a repeated cyclic voltammetry is reported to find the anodic material for DMFC that shows a higher electrocatalytic activity and that can replace a portion of precious metals with cheap ones. The activity of newly found electrocatalyst whose composition was determined through high-throughput screening was compared with that of commercially available Johnson–Matthey Pt(50)Ru(50). It was found Pt(77)Ru(17)Mo(4)W(2) was more active and stable than Pt(50)Ru(50) in methanol electro-oxidation. The repeated cyclic voltammetry makes the combinatorial method expand into a screening tool to find the electrocatalyst that not only showing an initial excellent performance but also being active in the long-run reaction.     

Novel Sn–Ce/Al2O3 Catalyst for the Selective Catalytic Reduction of NOx Under Lean Conditions

Effect of additives, Ce and Mn, on the catalytic performance of Sn/Al₂O₃ catalyst prepared by sol–gel method for the selective reduction of NO_x with propene under lean conditions was studied. Sn–Ce/Al₂O₃ catalysts exhibited higher activity than Sn/Al₂O₃ catalyst and the optimum Ce loading is 0.5–1%. The promoting effect of Ce is to enhance the oxidation of NO to NO₂ and facilitate the activation of propene, both of which are important steps for the NO_x reduction. The presence of oxygen contributes to the oxidation of NO and shows a promoting effect.