Molybdenum nitride for the direct decomposition of NO

The physico-chemical properties of passivated -Mo₂N have been investigated. The material showed high activities for NO direct decomposition: nearly 100% NO conversion and 95% N₂ selectivity were achieved at 450C. The amount of O₂ taken up by -Mo₂N increased with temperature rise and reached 3133.9 molg^–1 at 450C; we conclude that there formation of Mo₂O_xN_y occurred. This oxygen-saturated -Mo₂N material was catalytically active: NO conversion and N₂ selectivity were 89 and 92% at 450C. We found that by means of H₂ reduction at 450C, Mo₂O_xN_y could be reduced back to -Mo₂N and the oxidation/reduction cycle is repeatable; such a behaviour and the high oxygen capacity (3133.9 molg^–1) of -Mo₂N suggest that -Mo₂N is a promising catalytic material for automobile exhaust purification.     

A study of the acidic and catalytic properties of pure and sulfated zirconia–titania and zirconia–silica mixed oxides

Protonated pyridine (PyH⁺) was not found on ZrO₂ (Z) or ZrO₂–TiO₂ (ZT), but was detected on sulfated oxides (ZS, ZTS) by IR spectroscopy. In contrast, ZrO₂–SiO₂ samples containing about 30–80 mol% ZrO₂ showed Brønsted acidity both in nonsulfated (ZS) and sulfated (ZSS) forms. The total acidity was determined by NH₃TPD. Introduction of sulfate ions increased the sitespecific catalytic activity (TOF) in the conversion of cyclopropane or nhexane. The effect of sulfate ions was more significant on samples rich in zirconia. Results suggest that Zr is homogeneously distributed in ZS samples rich in silica. Zirconiabound dimeric sulfate, generating strong acidity, could not be formed in these preparations due to the absence of fairly large ZrO₂ domains.     

Synthesis, Characterization and Optimum Reaction Conditions of Oligo-N, N′-bis (2-hydroxy-1-naphthalidene) Thiosemicarbazone

The oxidative polycondenzation reaction conditions of N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone (HNTSC) using air oxygen, H₂O₂ and NaOCl were studied in an aqueous alkaline medium between 50–90°C. Oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone was characterized by ¹H-NMR, FT-IR, UV-Vis, size exclusion chromatography (SEC) and elemental analysis techniques. Solubility testing of oligomer was investigated using organic solvents such as DMF, THF, DMSO, methanol, ethanol, CHCl₃, CCl₄, toluene acetonitrile, ethyl acetate, concentrated H₂SO₄ and an aqueous alkaline solution. Using NaOCl, H₂O₂ and air O₂ oxidants, conversion to oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone (OHNTSC) of N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone was found to be 85, 80 and 76%, respectively, in an aqueous alkaline medium. According to the SEC analyses, the number-average molecular weight, weight-average molecular weight and polydispersity index values of OHNTSC synthesized were found to be 1050 gmol^–1 1715 gmol^–1 and 1.63, using NaOCl, and 2137, 2957 gmol^–1 and 1.38, using air O₂ and 2155 gmol^–1 4164 gmol^–1 and 1.93, using air H₂O₂, respectively. Also, TG analysis was shown to be unstable of oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone against thermo-oxidative decomposition. The weight loss of OHNTSC was found to be 97.29% at 900°C.     

Synthesis of HFC-134a over CrF3/AlF3 catalysts

The effect of the structure of AlF₃ supports in CrF₃/AlF₃ catalysts and their activity were studied, and a selection of suitable reaction conditions for fluorination of trichloroethylene and HCFC-133a was made. We found that neither AlF₃ (- and -modifications) nor CrF₃/-AlF₃ exhibits significant activity for the reaction of HF with CCl₂=CHC1 or CF₃CH₂Cl. However, CrF₃/-AlF₃ exhibits high activity, which increases with increasing surface area and decreasing crystallite size of the -AlF₃ support, and that dramatically affects the fiuorination of CF₃CH₂Cl. Investigation of a series of CrF₃/-AlF₃ catalysts shows that the turnover rates per unit of the total surface area and of the free CrF₃ surface area significantly increase with increasing content of Cr³⁺ loading. Optimum temperature for the reaction of HF with CCl₂=CHCl is 260°C, while with CF₃CH₂Cl it is 350°C, with flow ratios HFTCE = 61 andHFHCFC-133a = 101.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Study of the Supported K2MoO4 Catalyst for Methanethiol Synthesis by One Step from High H2S-Containing Syngas

ESR and XPS are used to study the Mo-based catalysts MoO₃/K₂CO₃/SiO₂ and K₂MoO₄/SiO₂ prepared with two kinds of precursors, (NH₄)₆Mo₇O₂₄4H₂O and K₂MoO₄. The catalytic properties of the catalysts for methanethiol synthesis from high H₂S-containing syngas are explored. The activity assay shows that the two catalysts have much the same activity for the reaction. By the ESR characterization of both functioning catalysts, the resonant signals of oxo-Mo(V) (g=1.93), thio-Mo(V) (g=1.98) and S (g=2.01 or 2.04) can be detected. In the catalyst MoO₃/SiO₂ modified with K₂CO₃, as increasing amounts of K₂CO₃ are added, the content of oxo-Mo(V) increases, but thio-Mo(V) decreases. The XPS characterization indicates that Mo has mixed valence states of Mo⁴⁺, Mo⁵⁺ and Mo⁶⁺, and that S includes three kinds of species: S^2– (161.5 eV), [S–S]^2– (162.5 eV) and S⁶⁺ (168.5 eV). Adding K₂CO₃ promoter to the catalysts, the Mo species of high valence state is easily sulphided and reduced to Mo₂S and oxo-M(V), and the derivation of [S–S]^2– and S^2– species from S is promoted simultaneously. The methanethiol synthesis is favored if the mole ratio of (Mo⁶⁺ + Mo⁵⁺)/Mo⁴⁺ 0.8 and S^2–/[S–S]^2– is kept at a value of about 1.     

Active-oxygen species on non-reducible rare-earth-oxide-based catalysts in oxidative coupling of methane

From supplementary in situ Raman spectroscopic studies of active-oxygen species on non-reducible rare-earth-oxide-based catalysts in the oxidative coupling of methane (OCM) and structural adaptability considerations, further support has been obtained for our proposal that there may be an active and elusive precursor (of O₂ ^– and O₂ ^2– adspecies), most probably O₃ ^2– formed from reversible redox coupling of an O₂ adspecies at an anionic vacancy with a neighboring O^2– in the surface lattice. This active precursor may initiate H abstraction from CH₄ and be itself converted to OH^–+O₂ ^–, or it may abstract an electron from the oxide lattice and be converted to O₂ ^2–+O^–. The prospect of developing this type of OCM catalysts is discussed.     

Acid‐catalyzed isobutane–isobutylene alkylation in liquid carbon dioxide solution

Liquid carbon dioxide was studied as a solvent for the isobutane–isobutylene alkylation. The acid catalysts in the reaction were anhydrous HF (AHF), pyridinium–poly(hydrogen fluoride) complex (PPHF), concentrated sulfuric acid and trifluoromethanesulfonic acid (TFSA). The effect of the acid–hydrocarbon volume ratio, temperature and residence time on the alkylate quality were studied over the temperature range of 50 T 0 °C. Carbon dioxide as a competing weak base decreases the acidity of the system which parallels the alkylate quality. In the case of HF and TFSA catalysts, solvent CO₂ increased the octane number of the alkylate product (RON 95.6 for HF and 88.0 for TFSAcatalyzed alkylation with CO₂ solvent).     

Properties ofSrMO 3-δ(M=Fe,Co) as oxygen electrodes in alkaline solution

Strontium ferrates and cobaltates with compositions SrFeO_3- (0.060.40) and SrCoO_3- (0.040.30) were synthesized. The dependence of the oxygen electrode properties on the value was examined in 1 mol dm^–3 KOH solution. In the SrFeO_3- series, the samples with 0.24<<0.29, showed the highest activity in both oxygen evolution and reduction reactions. In contrast, no strong dependence on the value was observed in SrCoO_3-, which also showed a high catalytic activity for oxygen evolution.     

FTIR spectroscopic investigation of the active sites on different types of silica catalysts for methane partial oxidation to formaldehyde

Several commercial silica samples showing different catalytic activities in the partial oxidation of methane (MPO) to formaldehyde have been investigated using FTIR technique. Two IR absorption bands at 893 and 909 cm^–1, observed upon dehydroxylation of the silica catalysts and assigned to reactive siloxane sites on the surface (strained siloxane bridges), were found to disappear upon heating in methane at high temperature. The catalytic activity increases together with the intensity of the bands due to such strained sites in the different SiO₂ samples.     

A chemically regenerative redox fuel cell

A novel chemically regenerative redox fuel cell is described. The electrode reactions are based on the following redox reactions: cathodic reaction: anodic reaction: VO ₂ ⁺ +2H⁺+e VO²⁺+H₂O (E ₀ +1V), SiW₁₂O ₄₀ ^5– SiW₁₂O ₄₀ ^4– +e (E ₀ 0V). Regeneration of the oxidant by direct oxidation with O₂ was achieved by using the soluble heteropoly acid catalysts, H₃PMo₁₂O₄₀ or H₅PMo₁₀V₂O₄₀, whereas regeneration of the tungstosilicic acid, H₃SiW₁₂O₄₀, was accomplished by direct reduction with H₂ utilizing small amounts of Pt, Pd, Rh, Ru or the soluble Pd-4, 4, 4, 4'-tetrasulphophthalocyanine complex as catalysts. Some aspects of the regeneration kinetics and their influence on the overall performance of the redox fuel cell are discussed.     

Catalytic behaviour and characterisation of CuO1−z(La2O3)z/2 based catalysts deposited on γ-Al2O3 and prepared in situ with 0.0 ⩽z⩽1.00, without and with addition of Pd

(CuO)_1–z(La₂O₃)_z/2 based catalysts with 0.0z1.0 supported on -Al₂O₃ have been prepared in situ and the phases formed have been identified by XRD, SEM and TEM/EDS studies. The catalyst with z=0.5 exhibited the best catalytic activity for oxidation of CO (T ₅₀=295 and 390C with degrees of conversions of 93 and 92% at 450C under rich and lean conditions, respectively) and C₃H₆ (291 and 414C; 93 and 83%) and reduction of NO (405C; 60 and 0%). This catalyst contained appreciable amounts of the perovskite phase LaAl_1–xCu_xO₃ and the enhanced catalytic properties are ascribed to the presence of this phase. Addition of Pd to this catalyst implied that the degree of conversion of NO increased and that the light-off temperatures for all involved gas species decreased. Ageing experiments revealed that LaAl_1–xCu_xO₃ decomposed and that Cu containing Pd particles were formed during this procedure which in turn deteriorated the catalytic properties of the catalyst.     

Nucleation and growth kinetics of Ag7NO11 on a platinum single crystal electrode

The process of electrochemical deposition of Ag₇NO₁₁ on a platinum single crystal anode from 5M AgNO₃ is investigated. The nucleation and growth rates are measured at different constant overpotentials. The orientation of the Ag₇NO₁₁ crystals with respect to the substrate surface is determined in the case of deposition on glassy carbon and on the 100, 111 and 110 faces of a platinum single crystal.     

New polyisobutylene based model ionomers

Three-arm star polyisobutylene ionomers (¯M_n=8800) with terminal SO₃ M (M=K or Ca²) groups were synthesized and their mechanical properties investigated. Compression molded films displayed high elongations, i.e., -1000% for Ca² ionomers with lower values for the K counterions. Strain induced crystallinity was observed at higher elongations. Mechanical properties in general compared favorably with conventional covalently linked rubbery networks and were comparable and in some cases superior to EPDM-based ionomers carrying randomly distributed SO₃ M groups.For the first two parts see Proceedings, 28th IUPAC Macromolecular Symposium, Amherst, MA, July 11–16, 1982, p. 905 and 906     

On the NiMoO4 oxidative dehydrogenation of propane to propene: some physical correlations with the catalytic activity

The - and -phases of NiMoO₄ have been investigated with different techniques (X-ray diffraction, electrical conductivity, IR spectroscopy) in order to tentatively rationalise the different catalytic activities observed in the oxidative dehydrogenation of propane to propene. XRD analyses have shown that at 595 ° C, the -phase is already present but a temperature of 700 ° C is required to obtain a full conversion into a pure -phase. Electrical conductivity showed the presence of anionic vacancies. It is proposed that propene is formed by the reaction of propane with surface O^2- anions. The -phase is almost twice more selective in propene formation than the -phase for comparable conversion at identical temperatures. This could derive from different oxygen environments on the active catalytic site.     

Critical solution point and chain dimension of branched-polystyrene solutions

Summary Critical solution point and chain dimension were measured for branched polystyrene(BPS) in solution as a function of molecular weight(M) and compared with those for linear polystyrene(LPS). The critical concentration _c of BPS was quite different from that of LPS at a fixed M, but the same at a fixed overlap-concentration ^*, i.e., plots of _c vs. ^* fall on a single straight line for both BPS and LPS (gf_c ^*). Reduced critical temperature _c defined by gt_c=(–T_c)/ [T_c: critical temperature, : the -temperature] was related to _c as _{c c} ² for BPS, whereas _{c c} for LPS.     

The role of Ni2+ diffusion on the reducibility of NiO/MgO system: A combined TRP-XPS study

The progressive dissolution of nickel ions in the lattice of MgO matrix, promoted by the calcination temperature, has been monitored using XPS. The reducibility of Ni/MgO catalysts is affected by the modification of the surface chemical composition. TPR peaks have been correlated with several NiO forms. Both XPS and TPR results indicate a different behaviour pattern for the supported and physically mixed NiO/MgO systems, and this has been attributed to the different available contact area between NiO and MgO. The formation of both NiO rich and MgO rich NiO-MgO solid solutions, with the tendency to evolve towards the bulk solid solution, has been invoked to explain the substantial changes in the TPR pattern of the different air calcined systems.     

Lean NOx catalysis over alumina‐supported catalysts

aluminasupported catalysts show promise as lean NO_x catalysts. The role of alumina in influencing the structural and chemical properties of the active phase supported on it is discussed using some effective aluminabased lean NO_x catalysts. These include Ag/Al₂O₃, CoO_x/Al₂O₃ and SnO₂/Al₂O₃. Alumina plays an important role in stabilizing Ag in the oxidic phase and cobalt in the 2+ oxidation state. For SnO₂/Al₂O₃, alumina increases the SnO₂ surface area. On both Ag/Al₂O₃ and SnO₂/Al₂O₃, alumina also participates actively in the NO_x reduction reaction. An active organic intermediate is formed on Ag or Sn oxide which reacts with NO_x subsequently on alumina to form N₂.     

Formation and reactions of isocyanic acid during the catalytic reduction of nitrogen oxides

Reactions which can produce and consume isocyanic acid (HNCO) over two types of catalysts active for the reduction of nitrogen oxides have been investigated. More than 1000 ppm HNCO can be produced by the reduction of 3000 ppm NO with H₂/CO mixtures over a Pt/SiO₂ catalyst. Complete hydrolysis of HNCO to ammonia and carbon dioxide occurs if even weakly catalytic materials, such as CeO₂/SiO₂ and BaO/SiO₂, are placed downstream. Isocyanic acid is also involved as an intermediate in the reaction of nitromethane over CoZSM5 and CuZSM5 under the conditions of hydrocarbon SCR. In the initial stages of reaction there is complete conversion through to N₂ with CuZSM5 but the process stops at ammonia with CoZSM5 at temperatures below 350°C. In both cases, but especially with CoZSM5, isocyanic acid becomes observable as the catalyst deactivates during continuous exposure at temperatures below about 290°C. In situ FTIR measurements indicate that deactivation is due to a reaction between isocyanic acid and ammonia which generates cyclic striazine compounds.     

Composition dependence of the oxygen-evolution reaction rate on Ir x Ti1−x O2 mixed-oxide electrodes

Mudcrack-free oxide films of Ir _x Ti_1–x O₂ (0 < x 1) on titanium substrates were obtained, and the effects of the oxide composition on the rate of oxygen-evolution reaction were investigated. At x 0.6, Ir-rich grains appear on the mudcrack-free surface. In the purely single-phase region (0 < x 0.5), the pseudo-capacitive charge is proportional to the surface composition, x _s, and the exchange-current density for the oxygen-evolution reaction increases linearly with x _s at 0.2 x _s 0.5, with an extrapolated intercept at x _s 0.15, below which the oxides are inactive.