Shielded Sliding Discharge-Assisted Hydrocarbon Selective Catalytic Reduction of NOx over Ag/Al2O3 Catalysts Using Diesel as a Reductant

The nonthermal plasma generated in a shielded sliding discharge reactor was used to reform diesel for the hydrocarbon-selective catalytic reduction (HC-SCR) of NO_x on Ag/Al₂O₃ catalysts. Compared with raw diesel, the reformed diesel enhanced the NO_x reduction efficiency, mitigated hydrocarbon poisoning of the catalyst and reduced the fuel penalty for the HC-SCR reaction. The NO_x conversion values obtained with a commercial Ag/Al₂O₃ catalyst exceeded that of a 2.0 wt% Ag/Al₂O₃ catalyst prepared by wet impregnation. A significant amount of NH₃ was produced as a by-product during the HC-SCR reaction, which suggests that further NO_x conversion enhancement can be achieved by placing a second NH₃-SCR catalyst in series with the Ag/Al₂O₃ catalyst.     

Laser assisted selective chemical metalization of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films

Thick aluminum oxide films are prepared on Al plates by anodizing. On the ceramic surface thus obtained a very thin Ag film is deposited via vacuum thermal evaporation. The Ag/Al₂O₃/Al samples prepared are irradiated by Nd:YAG laser through a suitable metal mask in order to remove the top metal film in the exposed areas. Thus, a negative silver image of the copied mask is obtained. Further, the samples are processed in Ni electroless chemical bath activated by the rest of silver. All processing steps are studied by scanning electron microscopy (SEM). EDS X-ray mapping is applied to study the final distribution of Al and Ni in the processed areas. In addition, the DC conductivity of the fabricated Ni wires obtained is measured. The proposed new method for selective chemical deposition of electroconductive Ni onto laser microstructured Ag/Al₂O₃/Al samples is simple, versatile and not restricted to the metal/ceramic system studied as well as to the electroless deposited metal.     

Formation of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> bilayer using atomic layer deposition and its application to dynamic random access memory

To enhance film conformality together with electrical property suitable for dynamic random access memory (DRAM) capacitor dielectric, the effects of oxidant and post heat treatment were investigated on aluminum and titanium oxide (Al₂O₃–TiO₂) bilayer (ATO) thin film formed by atomic layer deposition method. For the conformal deposition of Al₂O₃ thin film, the O₃ oxidant required a higher deposition temperature, more than 450 °C, while H₂O or combined oxygen sources (H₂O+O₃) needed a wide range of deposition temperatures ranging from 250 to 450 °C. Conformal deposition of the TiO₂ thin film was achieved at around 325 °C regardless of the oxidants. The charge storage capacitance, measured from the ATO bilayer (4 nm Al₂O₃ and 2 nm TiO₂) deposited at 450 °C for Al₂O₃ and 325 °C for TiO₂ with O₃ oxidant on the phosphine-doped poly silicon trench, showed about 15% higher value than that of 5 nm Al₂O₃ single layer thin film without any increase of leakage current. To maintain the improved electrical property of the ATO bilayer for DRAM application, such as enhanced charge capacitance without increase of leakage current, upper electrode materials and post heat treatments after electrode formation must be selected carefully. Dedicated to Professor Su-Il Pyun on the occasion of his 65th birthday.     

Formation and properties of the Fe<Subscript>8</Subscript>V<Subscript>10</Subscript>W<Subscript>16–x</Subscript>Mo<Subscript>x</Subscript>O<Subscript>85</Subscript> type solid solution

Solid solution phases of a formula Fe₈V₁₀W_16–xMo_xO₈₅ where 0≤x≤4, have been obtained, possessing a structure of the compound Fe₈V₁₀W₁₆O₈₅. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe₂WO₆ and WO₃. The increase of the Mo⁶⁺ ions content in the crystal lattice of Fe₈V₁₀W₁₆O₈₅ causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe₈V₁₀W_16–xMo_xO₈₅ solid solution phases have been recorded.     

Two color up-conversion emissions of Er<Superscript>3+</Superscript>-doped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanopowders prepared by non-aqueous sol-gel method

Er³⁺-doped Al₂O₃ nanopowders have been prepared by the non-aqueous sol-gel method using the aluminum isopropoxide as precursor, acetylacetone as a chelating agent, nitric acid as a catalyzer, and hydrated erbium nitrate as a dopant under isopropanol environment. The different phase structure, including three crystalline types of (Al, Er)₂O₃ phases, α, γ, θ, and an Er–Al–O stoichiometric compound phase, Al₁₀Er₆O₂₄, was observed for the 0.01–0.5 mol% Er³⁺-doped Al₂O₃ nanopowders at the sintering temperature of 1,000 °C. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the ²H_11/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, were detected by a 978 nm semiconductor laser diodes excitation. With increasing Er³⁺ doping concentration from 0.01 to 0.1 mol%, the intensity of the green and red emissions increased with a decrease of the intensity ratio of the green to red emission. When the Er³⁺ doping concentration rose to 5 mol%, the intensity of the green and red emissions decreased with an increase of their intensity ratio. The maximum intensity of both the green and red emissions with the minimum of intensity ratio was obtained, respectively, for the 0.1 mol% Er³⁺-doped Al₂O₃ nanopowders composed of a single α-(Al,Er)₂O₃ phase. The intensity ratio of the green emission at 523 and 545 nm increased monotonously for all Er³⁺ doping concentrations. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er³⁺-doped Al₂O₃ nanopowders.     

<Emphasis Type="Italic">In situ</Emphasis> XPS study of the size effect in the interaction of NO with the surface of the model Ag/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/FeCrAl catalysts

The interaction of NO with the surface of model Ag/Al₂O₃/FeCrAl catalysts containing Ag nanoparticles of different size (1 and 3 nm) was studied. The use of the Auger parameter α_Ag (E _b(Ag3d_5/2) + E _kin(Ag MVV)) made it possible to reliably identify the change in the chemical state of silver cluster upon their interaction with О₂ and NO. The oxygen treatment leads to the oxidation of small Ag nanoparticles (1 nm) and formation of AgO _x clusters resulted in the intensive formation of nitrite—nitrate structures on the step of the interaction with NO. These structures are localized on both the silver clusters and Al₂O₃ surface. An increase in the size of Ag⁰ nanoparticles to 3 nm results in an increase in the stability of these structures and impedes the Ag⁰ → AgO _x transition, due to which the formation of surface groups NO₂ ^–/NO₃ ^– is suppressed. The data obtained make it possible to explain the dependence of the activity of the Ag/Al₂O₃ catalysts in the selective reduction of NO on the Ag nanoparticle size.     

Specific heat on Sr<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> and Sr<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>7</Subscript>

Summary Specific heats on the single crystals of Sr₂Nb₂O₇, Sr₂Ta₂O₇ and (Sr_1-xBa_x)₂Nb₂O₇ were measured in a wide temperature range of 2-600 K. Heat anomalies of a λ-type were observed at the incommensurate phase transition of T_INC (=495 K) on Sr₂Nb₂O₇ and at the super-lattice phase transition of T_SL (=443 K) on Sr₂Ta₂O₇; the transition enthalpies and the transition entropies were estimated. Furthermore, a small heat anomaly was observed at the low temperature ferroelectric phase transition of T_LOW (=95 K) on Sr₂Nb₂O₇. The transition temperature T_LOW decreases with increasing Ba content x and it vanishes for samples of x>2%.     

X-ray photoelectron spectroscopic study of the interaction of supported metal catalysts with NO<Subscript>x</Subscript>

The reactions of the platinum and rhodium model catalysts applied to aluminum oxide with NO_x (10 Torr NO + 10 Torr O₂) were studied by X-ray photoelectron spectroscopy. The reaction conducted at room temperature formed on the surface of the oxide support the NO _3,s ^? nitrate ions characterized by the N1s line at 407.4 eV and O1s line at 533.1 eV and the NO _2,s ^? nitrite ions characterized by the N1s line with a binding energy of 404.7 eV. At the same time, the Pt4f and Rh3d lines of the supported platinum particles are shifted toward higher binding energies by 0.5–1.0 eV and 0.7–1.2 eV, respectively. It is assumed that the binding energies increase due to changes in the chemical state of the platinum metal in which oxygen is dissolved. The reaction of NO_x with Pt/Al₂O₃ at 200°C forms platinum oxide defined by the Pt4f _7/2 line with a binding energy of 72.3 eV.     

FTIR-ATR <Emphasis Type="Italic">in situ</Emphasis> observation on the efflorescence and deliquescence processes of Mg(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> aerosols

The efflorescence and deliquescence processes of Mg(NO₃)₂ aerosol particles deposited on ZnSe substrate have been investigated through in situ Fourier transform infrared-attenuated total reflection (FTIR-ATR) technique at the molecular level. At relative humidity (RH) of ∼3%, Mg(NO₃)₂ particles existed as amorphous states. The amorphous Mg(NO₃)₂ particles were transformed into crystalline Mg(NO₃)₂ · nH₂O (n ≤ 5) with slight increasing of RH. Thermodynamically stable Mg(NO₃)₂·6H₂O crystals were gradually formed on the particle surface and started to be dissolved at the saturation point (∼53% RH). At the same time, a continuous phase transition from Mg(NO₃)₂ · nH₂O (n≤5) to Mg(NO₃)₂·6H₂O occurred on the particle surface. This led the solid particles to completely deliquesce at 76% RH, which was much higher than the saturation point of 53% RH. In the efflorescence process, Mg(NO₃)₂ droplets entered into the supersaturated region due to the gradual evaporation of water. Finally, amorphous particles were formed when RH decreased below 5%. In the FTIR-ATR spectra of the supersaturated Mg(NO₃)₂ droplets, the absorbance of the symmetric stretching vibration of NO ₃ ⁻ (v ₁- NO ₃ ⁻ ) clearly became stronger. It resulted from the continuous formation of solvent share ion pairs (SIPs), and even the contact ion pairs (CIPs) between Mg²⁺ and NO ₃ ⁻ . Supported by the Trans-Century Program Foundation for the Talents by the Ministry of Education of China, the National Natural Science Foundation of China (Grant Nos. 20073004, 20473012, and 20673010), the 111 Project (B07012), and the State Key Laboratory of Physical Chemistry for Solid Surface of Xiamen University     

Facile preparation and electrochemical properties of large-scale Li<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript>3</Subscript>O<Subscript>8</Subscript> nanobelts

Large-scale Li_1+x V₃O₈ nanobelts were successfully fabricated using filter paper as deposition substrate through a simple surface sol–gel method. The nanobelts were as long as tens of micrometers with widths of 0.4–1.0 μm and thickness of 50–100 nm. The nanobelts were characterized by X-ray diffration (XRD), Fourier infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The formation mechanism of the nanobelts was investigated, showing that the morphology of the nanobelts is mainly determined by the calcination temperature. Electrochemical properties of the Li_1+x V₃O₈ nanobelts were characterized by charge–discharge experiments, and the results demonstrate that the Li_1+x V₃O₈ nanobelts exhibit a high discharge capacity (278 mAh g⁻¹) and excellent cycling stability.     

Nox reduction with CO over supported Pd catalysts under simulated post Euro-IV diesel exhaust conditions

The catalytic reduction of NO_x with CO over Pd/Al₂O₃ and Pd/TiO₂/Al₂O₃ under simulated post Euro-IV diesel exhaust conditions was studied. The catalytic activities obtained by using various Pd and TiO₂ loadings and total amounts of reductant and the influence of H₂ and H₂O was investigated.     

Ni基催化剂催化燃油重整耦合选择性催化还原NOx反应

分别以La₂O₂CO₃, CeO₂, ZrO₂和Al₂O₃为载体, 采用浸渍法制备了Ni基重整催化剂, 并以正十二烷模拟车载燃油进行催化重整反应以同时制备小分子碳氢化合物(HCs)和H₂, 考察了其在4wt%Ag/Al₂O₃上选择性催化还原(HC-SCR)氮氧化物(NO_x)的性能. 采用N₂吸附-脱附、X射线粉末衍射、H₂程序升温还原和热重等手段对Ni基催化剂进行了表征. 结果表明, 随着重整催化剂氧化还原性能增强, 产物中H₂浓度增加, 可参与SCR反应的HCs含量减少, 从而导致重整-SCR耦合体系上NO_x净化活性温度窗口向低温移动, NO_x最高转化率降低. Ni/ZrO₂+Ag/Al₂O₃耦合体系中H₂/HCs符合SCR反应所需的最优比例, 在柴油车典型排气温度范围内表现出良好的NO_x净化能力. 同时, 在Ni/ZrO₂+Ag/Al₂O₃耦合体系上考察了其燃油重整-SCR的活性稳定性. 结果显示, 重整催化剂的耐久性有待进一步提高.     

LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> and LiCoO<Subscript>2</Subscript> composite cathode materials obtained by mechanical activation

New composite cathode materials xLiMn₂O₄/(1 ? x) LiCoO₂(x = 0.7, 0.6, 0.5 и 0.4) were obtained by mechanical activation. According to scanning electron microscopy data, the process was accompanied by pronounced dispersion and fine mixing of the initial components. In the course of the preparation and electrochemical cycling of the composites, LiMn₂O₄ and LiCoO₂ partially reacted, leading to the replacement of manganese with cobalt in the structure of spinel, which was detected by powder X-ray diffraction (XRD), IR and X-ray photoelectron spectroscopy (XPS), and cyclic chronopotentiometry. The specific discharge capacity of composites was ～100 mAh/g.     

Spectrokinetic study of the mechanism of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction with propylene over ZrO<Subscript>2</Subscript> in excess oxygen

It has been demonstrated by quantitative spectrokinetic measurements that, on the surface of zirconia stabilized as a tetragonal phase, the rate-limiting step of the selective catalytic reduction of nitrogen oxides (SCR of NO _x ) with propylene is the interaction of surface nitrates with C₃H₆ yielding organic nitro compounds. It is hypothesized that propylene reacts not with the nitrates themselves but with the activated complex NO₂ ^ads whose structure is intermediate between the structures of the monodentate NO₃ ^? and NO₂ species. Deep C₃H₆ oxidation exerts an adverse effect on the rate of the SCR of NO _x with propylene, and the interaction between O₂ and NO, which yields NO₂ and NO₃ ^? stimulates further nitrogen reduction to N₂. The effect of the reaction between oxygen and O₂N?C _n H _m on the NO _x reduction rate is variable and is determined by the C₃H₆/NO _x ratio. A generalized scheme of the SCR of NO _x with propylene on the surface of ZrO₂ partially stabilized as a tetragonal phase has been developed by comparing experimental data of this study and data available from the literature.     

Chemical solution processing and characterization of Ba(Zr,Ti)O<Subscript>3</Subscript>/LaNiO<Subscript>3</Subscript> layered thin films

Ba(Zr,Ti)O₃/LaNiO₃ layered thin films have been synthesized by chemical solution deposition (CSD) using metal-organic precursor solutions. Ba(Zr,Ti)O₃ thin films with smooth surface morphology and excellent dielectric properties were prepared on Pt/TiO _x /SiO₂/Si substrates by controlling the Zr/Ti ratios in Ba(Zr,Ti)O₃. Chemically derived LaNiO₃ thin films crystallized into the perovskite single phase and their conductivity was sufficiently high as a thin-film electrode. Ba(Zr,Ti)O₃/LaNiO₃ layered thin films of single phase perovskite were fabricated on SiO₂/Si and fused silica substrates. The dielectric constant of a Ba(Zr_0.2Ti_0.8)O₃ thin film prepared at 700°C on a LaNiO₃/fused silica substrate was found to be approximately 830 with a dielectric loss of 5% at 1 kHz and room temperature. Although the Ba(Zr_0.2Ti_0.8)O₃ thin film on the LaNiO₃/fused silica substrate showed a smaller dielectric constant than the Ba(Zr_0.2Ti_0.8)O₃ thin film on Pt/TiO _x /SiO₂/Si, small temperature dependence of dielectric constant was achieved over a wide temperature range. Furthermore, the fabrication of the Ba(Zr,Ti)O₃/LaNiO₃ films in alternate thin layers similar to a multilayer capacitor structure was performed by the same solution deposition process.     

Properties of the surface layer and catalytic activity of Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> with Pt or Pd additives in the oxidation of hydrogen

The catalytic activity in the oxidation of hydrogen (in the gaseous state in the presence of excess oxygen) has been studied for samples of Pt(Pd)/Ta₂O_5−x, formed by reduction with hydrogen. The samples obtained had greater activity than the traditional catalysts Pt(Pd)/Al₂O₃. According to X-ray diffraction analysis and electron microscopic studies, Ta₂O_5−x becomes amorphous with the formation of more reduced non-stoichiometric oxygen-deficient tantalum oxides with a surface layer of catalyst. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 180–185, May–June, 2008.     

Low Temperature Plasma Assisted Catalytic Reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in Simulated Marine Diesel Exhaust

Plasma Assisted Catalytic Reduction (PACR) of NO _x has been investigated at laboratory scale for gas stream compositions representative of marine diesel exhausts. PACR NO _x reduction in excess of 90% was measured at 350°C, a plasma specific energy of 60 J/l and two NO _x concentrations (1,200 and 1,800 ppm). PACR NO _x reduction of over 50% was measured for simulated marine engine conditions at 250°C, 60 J/l and 1,200 ppm NO _x . The performance under these conditions could be increased, achieving a peak of ∼74% NO _x reduction, although at a relatively high plasma power. Water, present in diesel exhaust, was shown to inhibit the poisoning effects of fuel sulphur using SO₂ as a representative exhaust component. The PACR system performance demonstrated tolerance to simulated fuel sulphur levels of up to 1% for the duration of the tests. PACR performance was also shown to be sensitive to the amount of hydrocarbon reductant used.     

Effect of metal substitution for cobalt on the oxygen adsorption properties of YBaCo<Subscript>4</Subscript>O<Subscript>7</Subscript>

YBaCo₄O₇ compound is capable to intake and release a large amount of oxygen in the temperature range of 200–400°C. In the present study, the effect of Zn, Ga and Fe substitution for Co on the oxygen adsorption/desorption properties of YBaCo₄O₇ were investigated by thermogravimetry (TG) method. Due to fixed oxidation state of Zn2+ ions, the substitution of Zn²⁺ for Co²⁺ suppresses the oxygen adsorption of YBaCo_4−xZn_xO₇. The substitution of Ga³⁺ for Co³⁺ also decreases the oxygen absorption capacity of YBaCo_4−xGa_xO₇. This can be explained by the strong affinity of Ga³⁺ ions towards the GaO₄ tetrahedron. Compared with Zn- and Ga-substituted samples, the drop of oxygen adsorption capacity is smallest for Fe-substituted samples because of the similar changeability of oxidation states of Co and Fe ions.     

Effects of Ni-ion doping on electrochemical characteristics of spinel LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> powders prepared by a spray-drying method

Spinel LiMn_2−x Ni _x O₄ compounds doped with a range of Ni (x=0–0.06) were synthesized by a spray-drying method. The structure and morphology characteristics of the powders were studied in detail by means of X-ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy. The XRD data reveal that all the samples have well-defined spinel structure, but, with the increase in Ni content, the doped lithium manganese spinels have smaller lattice constant. The undoped and doped spinel LiMn₂O₄ particles are fine, narrowly distributed, and well crystallized. The electrochemical characteristics of the samples are measured in the coin-type cells in a potential range of 3.2–4.35 V vs Li/Li⁺. All cyclic voltammogram curves exhibit two pairs of redox reaction peaks, but, among them, there are some differences about the peak split. With the increase in the Ni content, the specific capacities of the samples decrease slightly, but their cyclic ability increases.