DRIFTS/MS/Isotopic Labeling Study on the NO-Moderated Decomposition of a Silica-Supported Nickel Nitrate Catalyst Precursor

In the preparation of silica-supported nickel oxide from nickel nitrate impregnation and drying, the replacement of the traditional air calcination step by a thermal treatment in 1% NO/Ar prevents agglomeration, resulting in highly dispersed NiO. The mechanism by which NO prevents agglomeration was investigated by using combined in situ diffuse reflectance infrared fourier transform (DRIFT) spectroscopy and mass spectrometry (MS). After impregnation and drying, a supported nickel hydroxynitrate phase with composition Ni(3)(NO(3))(2)(OH)(4) had been formed. Comparison of the evolution of the decomposition gases during the thermal decomposition of Ni(3)(NO(3))(2)(OH)(4) in labeled and unlabeled NO and O(2) revealed that NO scavenges oxygen radicals, forming NO(2). The DRIFT spectra revealed that the surface speciation evolved differently in the presence of NO as compared with in O(2) or Ar. It is proposed that oxygen scavenging by NO depletes the Ni(3)(NO(3))(2)(OH)(4) phase of nitrate groups, creating nucleation sites for the formation of NiO, which leads to very small (similar to 4 nm) NiO particles and prevents agglomeration.

Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction

On-stream deactivation during a water gas shift (WGS) reaction over gold supported on a ceria-zirconia catalyst was examined. Although the fresh catalyst has very high low temperature (<200 degrees C) for WGS activity, a significant loss of CO conversion is found under steady-state operations over hours. This has been shown to be directly related to the concentration of water in the gas phase. The same catalyst also undergoes thermal deactivation above 250 degrees C, and using a combined experimental and theoretical approach, a common deactivation mechanism is proposed. In both cases, the gold nanoparticles, which are found under reaction conditions, are thought to detach from the oxide support either through hydrolysis, <200 degrees C, or thermally, > 200 degrees C. This process reduces the metal-support interaction, which is considered to be critical in determining the high activity of the catalyst.

Pulse-response TAP studies of the reverse water-gas shift reaction over a Pt/CeO2 catalyst

The temporal analysis of products (TAP) technique was successfully applied for the first time to investigate the reverse water-gas shift (RWGS) reaction over a 2% Pt/CeO2 catalyst. The adsorption/desorption rate constants for CO2 and H-2 were determined in separate TAP pulse-response experiments, and the number of H-containing exchangeable species was determined using D-2 multipulse TAP experiments. This number is similar to the amount of active sites observed in previous SSITKA experiments. The CO production in the RWGS reaction was studied in a TAP experiment using separate (sequential) and simultaneous pulsing Of CO2 and H-2. A small yield of CO was observed when CO2 was pulsed alone over the reduced catalyst, whereas a much higher CO yield was observed when CO2 and H-2 were pulsed consecutively. The maximum CO yield was observed when the CO2 pulse was followed by a H-2 pulse with only a short (1 s) delay. Based on these findings, we conclude that an associative reaction mechanism dominates the RWGS reaction under these experimental conditions. The rate constants for several elementary steps can be determined from the TAP data. In addition, using a difference in the time scale of the separate reaction steps identified in the TAP experiments, it is possible to distinguish a number of possible reaction pathways. (c) 2005 Elsevier Inc. All rights reserved.

Low-temperature oxidation reactions of ethane over a Pt/Al2O3 catalyst

Oxidative dehydrogenation of ethane was performed under conventional microreactor and TAP reactor conditions over a Pt/Al2O3 catalyst between 100 and 600 degreesC. During TAP studies, no ethene was produced whereas under flow conditions small but significant ethene formation was observed. This is consistent with a mechanism involving the gas-phase production of ethene rather than via a surface reaction. In comparison, both hydrogen and methane formation were found under TAP conditions and the trends with temperature and surface oxide composition are interpreted in terms of successive dehydrogenation steps on the catalyst surface. It is further observed that periodic introduction of the reactants can minimize deactivation processes. (C) 2003 Elsevier Inc. All rights reserved.

Ethylene oxidation over platinum: In situ electrochemically controlled promotion using Na-beta'' alumina and studies with a Pt(111)/Na model catalyst

Electrochemically modified ethylene oxidation over a PI film supported on the Na+ ion conductor beta '' alumina has been studied over a range of conditions encompassing both promotion and poisoning, The system exhibits reversible behavior, and the data are interpreted in terms of (i) Na-enhanced oxygen chemisorption and (ii) poisoning of the surface by accumulation of Na compounds. At low Na coverages the first effect results in increased competitive adsorption of oxygen at the expense of ethylene, resulting in an increased rate, At very negative catalyst potentials (high Na coverage) both effects operate to poison the system: the increased strength of the Pt-O bond and coverage of the catalytic surface by compounds of Na strongly suppress the rate, Kinetic and spectroscopic results for ethylene oxidation over a Pt(111)-Na model catalyst shed light on important aspects of the electrochemically controlled system, Low levels of Na promote the reaction and high levels poison it, mirroring the behavior observed under electrochemical control and strongly suggesting that sodium pumped from the solid electrolyte is the key species, XP and Auger spectra show that under reaction conditions, the sodium exists as a surface carbonate. Post-reaction TPD spectra and the use of (CO)-C-13 demonstrate that CO is formed as a stable reaction intermediate, The observed activation energy (56 +/- 3 kJ/mol) is similar to that measured for CO oxidation under comparable conditions, suggesting that the rate limiting step is CO oxidation. (C) 1996 Academic Press, Inc.

Catalyst distribution and carbon nanotube morphology in multilayer forests by mixed CVD processes

Carbon nanotubes can be grown as forests of aligned fibers on a substrate with a catalyst coated prior to or added during synthesis. A major process interruption can initiate the growth of second and successive layers of forest on top or at the base of the existing layers which are thereby lifted up. We report on the generation of multilayer CNT forests where the first forest is generated either by catalyst coinjection (CCI) of ferrocene with hydrocarbon (xylene) or by catalyst predeposition (CPD) of iron followed with hydrocarbon (acetylene). Subsequent layers are then produced by CCI alone to give uniform (all CCI) or mixed (CPD and CCI) structures to study the distribution of the iron catalyst and CNT morphology and to determine whether the CPD forest templates or otherwise influences the growth of subsequent CCI forests. The bottom-up base growth of second and subsequent CCI forests is reaction rate controlled. CCI multilayer forests accumulate catalyst (iron) in a variety of distinct locations. A pre-existing CPD forest modifies subsequent CCI forest initiation, morphology, and catalyst distribution but does not itself accumulate catalyst or change appearance. © 2009 American Chemical Society.

Development of a heterogeneous catalyst for lignocellulosic biomass conversion:Glucose dehydration by metal chlorides in a silica-supported ionic liquid layer

An attempt is made to immobilize the homogeneous metal chloride/EMIMCl catalyst for glucose dehydration to 5-hydroxymethylfurfural. To this end, ionic liquid fragments were grafted to the surface of SBA-15 to generate a heterogenized mimick of the homogeneous reaction medium. Despite a decrease in the surface area, the ordered mesoporous structure of SBA-15 was largely retained. Metal chlorides dispersed in such ionic liquid film are able to convert glucose to HMF with much higher yields as is possible in the aqueous phase. The reactivity order CrCl > AlCl > CuCl > FeCl is similar to the order in the ionic liquid solvent, yet the selectivity are lower. The HMF yield of the most promising CrCl-Im-SBA-15 can be improved by using a HO:DMSO mixture as the reaction medium and a 2-butanol/MIBK extraction layer. Different attempts to decrease metal chloride leaching by using different solvents are described. © 2013 American Institute of Chemical Engineers Environ Prog.

An efficient Cu(II)-bis(oxazoline)-based polymer immobilised ionic liquid phase catalyst for asymmetric carbon–carbon bond formation

The asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene and the Mukaiyama-aldol reaction between methylpyruvate and 1-phenyl-1-trimethylsilyloxyethene have been catalysed by heterogeneous copper(II)-bis(oxazoline)-based polymer immobilised ionic liquid phase (PIILP) systems generated from a range of linear and cross linked ionic polymers. In both reactions selectivity and ee were strongly influenced by the choice of polymer. A comparison of the performance of a range of Cu(II)-bis(oxazoline)-PIILP catalyst systems against analogous supported ionic liquid phase (SILP) heterogeneous catalysts as well as their homogeneous counterparts has been undertaken and their relative merits evaluated.

Regeneration mechanism of a Lean NOx Trap (LNT) catalyst in the presence of NO investigated using isotope labelling techniques

The presence of NO during the regeneration period of a Pt-Ba/Al O Lean NO Trap (LNT) catalyst modifies significantly the evolution of products formed from the reduction of stored nitrates, particularly nitrogen and ammonia. The use of isotope labelling techniques, feeding NO during the storage period and NO during regeneration allows us to propose three different routes for nitrogen formation based on the different masses detected during regeneration, i.e. N (m/e = 28), N N (m/e = 29) and N (m/e = 30). It is proposed that the formation of nitrogen via Route 1 involves the reaction between hydrogen and NO released from the storage component to form NH mainly. Then, ammonia further reacts with NO located downstream to form N . In Route 2, it is postulated that the incoming NO reacts with hydrogen to form NH in the reactor zone where the trap has been already regenerated. This isotopically labelled ammonia travels through the catalyst bed until it reaches the regeneration front where it participates in the reduction of stored nitrates ( NO ) to form N N. The formation of N via Route 3 is believed to occur by the reaction between incoming NO and H . The modification of the hydrogen concentration fed during regeneration affects the relative importance of H or NH as reductants and thus the production of N via Route 1 and N N via Route 2.

An investigation of the role of surface nitrate species in the oxidation of propene on a Pt-based diesel oxidation catalyst

Enhancing the low temperature activity of diesel oxidation catalysts is important for cold-start conditions and the possible importance of nitrate species in oxidation reactions has been proposed although definitive evidence has not been reported. To investigate the possible role of surface nitrates, their adsorption and reactivity on a Pt-based diesel oxidation catalyst have been investigated using the Short Time on Stream (STOS) transient kinetic technique. The results provide for the first time definitive evidence for the oxidation of propene by some of these nitrate-type species. © The Royal Society of Chemistry 2013.

Understanding the Optimal Adsorption Energies for Catalyst Screening in Heterogeneous Catalysis

The fundamental understanding of the activity in heterogeneous catalysis has long been the major subject in chemistry. This paper shows the development of a two-step model to understand this activity. Using the theory of chemical potential kinetics with Bronsted-Evans-Polanyi relations, the general adsorption energy window is determined from volcano curves, using which the best catalysts can be searched. Significant insights into the reasons for catalytic activity are obtained.

Ambient Temperature Hydrocarbon Selective Catalytic Reduction of NOx Using Atmospheric Pressure Nonthermal Plasma Activation of a Ag/Al2O3 Catalyst

Atmospheric pressure nonthermal-plasma-activated catalysis for the removal of NOx using hydrocarbon selective catalytic reduction has been studied utilizing toluene and n-octane as the hydrocarbon reductant. When the plasma was combined with a Ag/Al2O3 catalyst, a strong enhancement in activity was observed when compared with conventional thermal activation with high conversions of both. NOx and hydrocarbons obtained at temperature at temperature ≤250 °C, where the silver catalyst is normally inactive. Importantly, even in the absence of an external heat source, significant activity was obtained. This low temperature activity provides the basis for applying nonthermal plasmas to activate emission control catalysts during cold start conditions, which remains an important issue for mobile and stationary applications.

Aqueous phase reforming of xylitol over Pt-Re bimetallic catalyst: Effect of the Re addition

The aqueous phase reforming (APR) of xylitol was studied in a continuous fixed bed reactor over three catalysts: Pt/Al2O3, Pt/TiO2 and Pt-Re/TiO2. The data obtained in the case of the monometallic Pt catalysts was compared to the bimetallic Pt-Re sample. The effect of Re addition on the catalyst stability, activity, product formation and selectivity toward hydrogen and alkanes was studied. The bimetallic catalyst demonstrated a higher selectivity to alkanes compared to the monometallic samples. The monometallic catalyst was more selective toward hydrogen formation. A plausible reaction scheme explaining differences in selectivity toward hydrogen and alkanes was proposed and discussed.

Assessing the surface modifications following the mechanochemical preparation of a Ag/Al2O3 selective catalytic reduction catalyst

The surface modification of a mechanochemically prepared Ag/Al O catalyst compared with catalysts prepared by standard wet impregnated methods has been probed using two-dimensional T -T NMR correlations, HO temperature programmed desorption (TPD) and DRIFTS. The catalysts were examined for the selective catalytic reduction of NO using n-octane in the presence and absence of H. Higher activities were observed for the ball milled catalysts irrespective of whether H was added. This higher activity is thought to be related to the increased affinity of the catalyst surface towards the hydrocarbon relative to water, following mechanochemical preparation, resulting in higher concentrations of the hydrocarbon and lower concentrations of water at the surface. DRIFTS experiments demonstrated that surface isocyanate was formed significantly quicker and had a higher surface concentration in the case of the ball milled catalyst which has been correlated with the stronger interaction of the n-octane with the surface. This increased interaction may also be the cause of the reduced activation barrier measured for this catalyst compared with the wet impregnated system. The decreased interaction of water with the surface on ball milling is thought to reduce the effect of site blocking whilst still providing a sufficiently high surface concentration of water to enable effective hydrolysis of the isocyanate to form ammonia and, thereafter, N. This journal is © The Royal Society of Chemistry.