Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2

Strong metal-support interaction in nickel/niobium pentoxide and nickel/titania catalysts

EXAFS studies of Ni/Nb20, and Ni/Ti02 catalysts reduced at 773 K show evidence for the presence of a short Ni-Nb (Ti) and a long Ni-Nb (Ti) bond. The results provide evidence for considerable structural reorganization of the support in the vicinity of the Ni particles.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2.

Anatase-rutile transformation in Fe/TiO2, Th/TiO2 and Cu/TiO2 catalysts and its possible role in metal-support interaction

Based on in-situ Mossbauer and X-ray diffraction studies, it is shown that in the Fe/TiO2 catalyst, the anatase-rutile transformation of the TiO2 support is facilitated by the Fe2+ ions formed during the reduction. The transformation occurs at lower temperatures in Th/TiO2 and Cu/TiO2 compared to pure TiO2. In general, the transformation of anatase to rutile seems to occur at or below the temperature (approximately 770 K) at which strong-metal-support-interaction manifests itself.

An in situ EXAFS investigation of bimetallic Cu---Ni/γ-Al2O3 catalysts

In situ EXAFS investigations have been carried out on Ni/γ-Al2O3 and Cu---Ni/γ-Al2O3 catalysts with different metal loadings, and prepared by different procedures. As-prepared Ni/γ-Al2O3 on calcination gives NiO and NiAl2O4-like phases on the surface, the proportion of the latter increasing with the increase in calcination temperature; the proportion of the NiO-like phase, on the other hand, increases with the metal loading. The reducibility of Ni/γ-Al2O3 to give metallic Ni on the surface directly depends on the proportion of the NiO-like phase present before reduction. Co-impregnating with Cu suppresses the formation of the surface aluminate and thereby favours the reduction to metallic Ni. This conclusion is clearly substantiated by our studies of bimetallic catalysts containing varying Cu/Ni ratios and also those prepared by the two-stage impregnation procedure.

Four decades of research in solid state chemistry

Solid state chemistry was in its infancy when the author got interested in the subject. In this article, the author outlines the manner in which the subject has grown over the last four decades, citing representative examples from his own contributions to the different facets of the subject. The various aspects covered include synthesis, structure, defects, phase transitions, transition metal oxides, catalysts, superconductors, metal clusters and fullerenes. In an effort to demonstrate the breadth and vitality of the subject, the author shares his own experiences and aspirations and gives expression to the agony and ecstacy in carrying out experimental research in such a frontier area in India.

Strong metal-support interaction in Ni/TiO2 catalysts: in situ EXAFS and related studies

In situ EXAFS and X-ray diffraction investigations of Ni/TiO2 catalysts show that NiTiO3 is formed as an intermediate during calcination of catalyst precursors prepared by the wet-impregnation method; the intermediate is not formed when ion-exchange method is used for the preparation. On hydrogen reduction, NiTiO3 gives rise to Ni particles dispersed in the TiO2(rutile) matrix. The occurrence of the anatase-rutile transformation of the TiO2 support, the formation and subsequent decomposition/reduction of NiTiO3 as well as the unique interface properties of the Ni particles are all factors of importance in giving rise to metal-support interaction. Active TiO2(anatase) prepared from gel route gives an additional species involving Ni3+.

Synergitic Promotion of Electrooxidation of Methanol of Carbon-Supported PT-SN Catalysts

Electrooxidation of methanol in sulphuric acid on carbon-supported electrodes containing Pt-Sn bimetal catalysts prepared by an in-situ route is reported, The catalysts have been characterized employing chemical analyses, XRD, and XANES data in conjunction with electrochemistry. This study suggests that the Sn content in Pt-Sn bimetals produces: (i) a charge transfer from Sn to Pt and (ii) an increase in the coverage of adsorbed methanolic residues with the Sn content. From the electrode-kinetics data, it is inferred that while the electrodes of (3:3) Pt-Sn/C catalyst involve a 2-electron rate-limiting step akin to Pt/C electrodes, it is shifted to only 1-electron on (3:2) Pt-Sn/C, (3:3) Pt-Sn/C, and (3:4) Pt-Sn/C electrodes.

EXAFS investigations of Ni/gamma-Al2O3 and Ni/AlPO4 catalysts and their precursors

In-situ EXAFS investigations have been carried out on Ni/gamma-Al2O3 catalysts with different metal loadings and prepared from different precursors. When the calcined precursors are reduced in hydrogen, the proportion of nickel metal formed varies with the nature of the precursor employed; NiAl2O4 is the unreduced product. The metal loading does not have any significant effect on the proportion of metal formed except in the case of the catalyst prepared by wet-impregnation, where appreciable metal is obtained only when the loading is greater than 10wt%. Ni/AlPO4 catalysts do not show the formation of NiAl2O4 and reduction to metal is complate, unlike with the Ni/gamma-Al2O3 catalysts which show only partial reduction to metal.

Oxidation of methanol on the surfaces of model Cu/ZnO catalysts containing Cu1+ and Cu-0 species

Interaction of CH3OH with Cu clusters deposited on ZnO films grown on a Zn foil as well as on a ZnO(0001)Zn crystal, has been examined by X-ray photoelectron spectroscopy. On clean Cu clusters, reversible molecular adsorption or formation of CH3O is observed. However if the Cu clusters are pretreated with oxygen, both CH3O and HCOO- species are produced. Model Cu/ZnO catalyst surfaces, containing both Cu1+ and Cu-0 species, show interesting oxidation properties. On a Cu-0-rich catalyst surface, only CH3O species is formed on interaction with CH3OH. On a Cu1+-rich surface, however, HCOO- ion is the predominant species.

Universal behaviour in erosive burning of solid propellants

This paper considers the extensive data and correlations on the erosive burning of solid propellants. A relatively simple nondimensional relationship between the ratio of the actual to nonerosive burn rate (eta) and a quantity g, which is the product of g(0)-the ratio of free stream mass flux to the mass flux from the surface for nonerosive condition-and Re-0(m), where Re-0 is the Reynolds number based on the nonerosive mass flux of the propellant and port diameter, is shown to correlate most data within the accuracies of the experiments with m = -0.125. This shows the above relationship to account for the effects of pressure, aluminum, even up to a proportion of 17%, burn rate catalysts, and motor size. It is concluded that the suggested correlation between eta and g may be adopted universally for most practical propellants. (C) 1997 by The Combustion Institute.

Oxidation and decomposition of NH3 over combustion synthesized Al2O3 and CeO2 supported Pt, Pd and Ag catalysts

The catalytic oxidation and decomposition of NH3 have been carried out over combustion synthesized Al2O3 and CeO2 supported Pt, Pd and Ag catalysts using temperature programmed reaction (TPR) technique in a packed bed tubular reactor. Metals are ionically dispersed over CeO2 and fine metal particles are found on Al2O3. NH3 oxidation occurs over 1% Pt/Al2O3, 1% Pd/Al2O3 and 1% Ag/Al2O3 at 175, 270 and 350 C respectively producing N-2, NO, N2O and H2O, whereas 1% Pt/CeO2, 1% Pd/CeO2 and 1% Ag/CeO2 give N-2 along with NO, N2O and H2O at 200, 225 and 250degreesC respectively. N-2 predominates over other nitrogen-containing products during the reaction on all catalysts. At less O-2 concentration, N-2 and H2O are the only products obtained during NH3 Oxidation. NH3 decomposition over all the catalysts occurs above 450degreesC.

A comparative study of Pt/CeO2 catalysts for catalytic partial oxidation of methane to syngas for application in fuel cell electric vehicles

In the framework of a project aimed at developing a reliable hydrogen generator for mobile polymer electrolyte fuel cells (PEFCs), particular emphasis has been addressed to the analysis of catalysts able to assure high activity and stability in transient operations (frequent start-up and shut-down cycles). In this paper, the catalytic performance of 1 at.% Pt/ceria samples prepared by coprecipitation, impregnation and combustion, has been evaluated in the partial oxidation of methane. Methane conversion and hydrogen selectivity of 96 and 99%, respectively, associated with high stability during 100h of reaction under operative conditions (start-up and shut-down cycles), have been obtained. (C) 2002 Elsevier Science B.V. All rights reserved.

NO Reduction Over Noble Metal Ionic Catalysts

In last 40 years, catalysis for NO (x) removal from exhaust gas has received much attention to achieve pollution free environment. CeO(2) has been found to play a major role in the area of exhaust catalysis due to its unique redox properties. In last several years, we have been exploring an entirely new approach of dispersing noble metal ions in CeO(2) and TiO(2) for redox catalysis. We have extensively studied Ce(1-x) M (x) O(2-delta) (M = Pd, Pt, Rh), Ce(1-x-y) A (x) M (y) O(2-delta) (A = Ti, Zr, Sn, Fe; M = Pd, Pt) and Ti(1-x) M (x) O(2-delta) (M = Pd, Pt, Rh, Ru) catalysts for exhaust catalysis especially NO reduction and CO oxidation, structure-property relation and mechanism of catalytic reactions. In these catalysts, lower valent noble metal ion substitution in CeO(2) and TiO(2) creates noble metal ionic sites and oxide ion vacancy. NO gets molecularly adsorbed on noble metal ion site and dissociatively adsorbed on oxide ion vacancy site. Dissociative chemisorption of NO on oxide ion vacancy leads to preferential conversion of NO to N(2) instead of N(2)O over these catalysts. It has been demonstrated that these new generation noble metal ionic catalysts (NMIC) are much more catalytically active than conventional nano crystalline noble metal catalysts especially for NO reduction.

Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta): New water gas shift (WGS) catalysts

Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) and Ce(0.67)Fe(0.33)O(2-delta) have been synthesized by a new low temperature sonochemical method using diethylenetriamine as a complexing agent. Due to the substitution of Fe and Pt ions in CeO(2), lattice oxygen is activated in Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). Hydrogen uptake studies show strong reduction peaks at 125 C in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) against a hydrogen uptake peak at 420 degrees C in Ce(0.67)Fe(0.33)O(2-delta). Fe substituted ceria, Ce(0.67)Fe(0.33)O(2-delta) itself acts as a catalyst for CO oxidation and water gas shift (WGS) reactions at moderate temperatures. The rate of CO conversion in WGS with Pt free Ce(0.65)Fe(0.33)O(2-delta) is 2.8 mu mol g(-1) s(-1) at 450 C and with Pt substituted Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) is 4.05 mu mol g(-1) s(-1) at 275 degrees C. Due to the synergistic interaction of the Pt ion with Ce and Fe ions in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta), the catalyst showed much higher activity for CO oxidation and WGS reactions compared to Ce(0.67)Fe(0.33)O(2-delta). A reverse WGS reaction does not occur over Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). The catalyst also does not deactivate even when operated for a long time. Nearly 100% conversion of CO to CO(2) with 100% H(2) selectivity is observed in WGS reactions even up to 550 degrees C. (C) 2011 Elsevier B.V. All rights reserved.