Potassium-doped Ni-MgO-ZrO catalysts for dry reforming of methane to synthesis gas

Ni/K-MgO-ZrO catalysts for dry reforming of methane, with a range of Mg/Zr ratios and each containing about 10 wt% Ni, were prepared via Ni nitrate impregnation on MgO-ZrO supports synthesized by co-precipitation using KCO. It was found that a proportion of the potassium of the precipitant remained in the samples and improved the stability of the catalysts in the reaction. It was also shown that reduction of the catalysts at 1,023 K without calcination in air is necessary for stable and high activity; calcination in air at 1,073 K gives a deterioration of the catalytic properties, leading to rapid deactivation during the reaction. The order of the CH conversions of the reduced catalysts after 14 h on stream was as follows: Ni/K-MgZr ~ Ni/K-Mg ≥ Ni/K-MgZr Ni/K-Zr. A catalyst with 0.95 wt% K on MgO-ZrO with a Mg:Zr mole ratio of 5:2 showed the best resistance to deactivation. Experiments in a microbalance system showed that there was only negligible coke deposition on the surface of this sample. This behaviour was attributed to the presence of Ni nanoparticles with a diameter of less than 10 nm located on a MgO/NiO solid solution shell doped by K ions; this in turn covers a core of tetragonal ZrO and/or a MgO/ZrO solid solution. This conclusion was supported by EDS/TEM, XPS, XRD and H chemisorption measurements. © 2013 Springer Science+Business Media New York.

Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

Application of heterogeneous catalysts prepared by mechanochemical synthesis

Mechanochemical synthesis has the potential to provide more sustainable preparative routes to catalysts than the current multistep solvent-based routes. In this review, the mechanochemical synthesis of catalysts is discussed, with emphasis placed on catalysts for environmental, energy and chemical synthesis applications. This includes the formation of mixed-metal oxides as well as the process of dispersing metals onto solid supports. In most cases the process involves no solvent. Encouragingly, there are several examples where the process is advantageous compared with the more normal solvent-based methods. This can be because of process cost or simplicity, or, notably, where it provides more active/selective catalysts than those made by conventional wet chemical methods. The need for greater, and more systematic, exploration of this currently unconventional approach to catalyst synthesis is highlighted.

Effect of methanol concentration on oxygen reduction reaction activity of Pt/C catalysts

The oxygen reduction reaction (ORR) activity of Pt/C catalysts was investigated in electrolytes of 0.5 mol/L H2SO4 containing varying concentrations of methanol in a half-cell. It was found that the ORR activity was improved notably in an electrolyte of 0.5 mol/L H2SO4 containing 0.1 mol/L CH3OH as compared with that in 0.5 mol/L H2SO4, 0.5 mol/L H2SO4 containing 0.5 mol/L CH3OH, or 0.5 mol/L H2SO4 containing 1.0 mol/L CH3OH electrolytes. The same tendency for improved ORR activity was also apparent after commercial Nafion (R) NRE-212 membrane was hot-pressed onto the catalyst layers. The linear sweep voltammetry results indicate that the ORR activities of the Pt/C catalyst were almost identical in the 0.5 mol/L H2SO4 + 0.1 mol/L CH3OH solution before and after coated with the Nafion (R) membrane. Electrochemical impedance spectroscopy results demonstrated that the resistance of the Nafion (R) membrane is smaller in the electrolyte of 0.5 mol/L H2SO4 + 0.1 mol/L CH3OH than in other electrolytes with oxygen gas feed. This exceptional property of the Nafion (R) membrane is worth investigating and can be applied in fuel cell stacks to improve the system performance. (c) 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Selective Hydrogenation of Acetylene over Pd-Boron Catalysts: A Density Functional Theory Study

Boron-modified Pd catalysts have shown excellent performance for the selective hydrogenation of alkynes experimentally. In the current work, we investigated the hydrogenation of acetylene on boron-modified Pd(111) and Pd(211) surfaces, utilizing density functional theory calculations. The activity of acetylene hydrogenation has been studied by estimating the effective barrier of the whole process. The selectivity of ethylene formation is investigated from a comparison between the desorption and the hydrogenation of ethylene as well as comparison between the ethylene and the 1,3-butadiene formation. Formation of subsurface carbon and hydrogen on both boron-modified Pd(111) and Pd(211) surfaces has also been evaluated, since these have been reported to affect both the activity and the selectivity of acetylene hydrogenation to produce ethylene on Pd surfaces. Our results provide some important insights into the Pd B catalysts for selective hydrogenation of acetylene and also for more complex hydrogenation systems, such as stereoselective hydrogenation of longer chain alkynes and selective hydrogenation of vegetable oil.

Tailoring ionic liquid catalysts: structure, acidity and catalytic activity of protonic ionic liquids based on anionic clusters, [(HSO4)(H2SO4)x]− (x = 0, 1, or 2)

Aiming at inexpensive Brønsted-acidic ionic liquids, suitable for industrial-scale catalysis, a family of protonic ionic liquids based on nitrogen bases and sulfuric acid has been developed. Variation of the molar ratio of sulfuric acid, χH2SO4, was used to tune acidity. The liquid structure was studied using 1H NMR and IR spectroscopies, revealing the existence of hydrogen-bonded clusters, [(HSO4)(H2SO4)]−, for χH2SO4 > 0.50. Acidity, quantified by Gutmann Acceptor Number (AN), was found to be closely related to the liquid structure. The ionic liquids were employed as acid catalysts in a model reaction; Fischer esterification of acetic acid with 1-butanol. The reaction rate depended on two factors; for χH2SO4 > 0.50, the key parameter was acidity (expressed as AN value), while for χH2SO4 > 0.50 it was the mass transport (solubility of starting materials in the ionic liquid phase). Building on this insight, the ionic liquid catalyst and reaction conditions have been chosen. Conversion values of over 95% were achieved under exceptionally mild conditions, and using an inexpensive ionic liquid, which could be recycled up to eight times without diminution in conversion or selectivity. It has been demonstrated how structural studies can underpin rational design and development of an ionic liquid catalyst, and in turn lead to a both greener and economically viable process.

Origin of double dinitrogen release feature during fast switching between lean and rich cycles for NOx storage reduction catalysts

The performance of NOx storage and reduction over 1.5 wt% Pt/20 wt% KNO3/K2Ti8O17 and 1.5 wt% Pt/K2Ti8O17 catalysts has been investigated using combined fast transient kinetic switching and isotopically labelled (NO)-N-15 at 350 degrees C. The evolution of product N-2 has revealed two significant peaks during 60 s lean/1.3 s rich switches. It also found that the presence of CO2 in the feed affects the release of N-2 in the second peak. Regardless of the presence/absence of water in the feed, only one peak of N-2 was observed in the absence of CO2. Gas-phase NH3 was not observed in any of the experiments. However, in the presence of CO2 the results obtained from in situ DRIFTS-MS analysis showed that isocyanate species are formed and stored during the rich cycles, probably from the reaction between NOx and CO, in which CO was formed via the reverse water-gas shift reaction. 

Self-cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Correlation of Static Ageing Effects on Automotive Catalysts

This study identifies and analyzes the effect that aging time and temperature have on the CO light-off activity of three-way catalyst samples, aged in a static air (oxidizing) atmosphere. The bench aging time (BAT) equation proposed by the Environmental Protection Agency (EPA), which describes aging as dependent upon time at temperature, was used to calculate a range of oven aging times and temperatures based on a RAT-A engine bench aging cycle.

CO light-off tests carried out on cores aged between 800 and 900 °C have shown that it is the aging temperature that has the greatest effect on catalyst deterioration for static aging testing, with aging time having little effect. These results were in contradiction to the BAT equation, an industry norm for the aging of catalysts. This demonstrates that static aging, whilst showing how temperature affects aging, gives little or no time effects. The results have shown that static aging is not representative of actual aging on a vehicle.

Progressive aging conducted at a temperature of 1000 °C was shown to cause a decrease in catalyst activity as the aging time increased. However, even in these extreme conditions, static aging gave a slower rate of aging with time when compared to engine aging as defined by the BAT equation. Overall, static aging in air has been shown to produce a greater increase in aging due to temperature than predicted by the BAT equation, but less aging due to aging time.

Advanced Ceramic Substrate with Ordered and Designed Micro-Structure for Applications in Automotive Catalysts

This study describes an innovative monolith structure designed for applications in automotive catalysis using an advanced manufacturing approach developed at Imperial College London. The production process combines extrusion with phase inversion of a ceramic-polymer-solvent mixture in order to design highly ordered substrate micro-structures that offer improvements in performance, including reduced PGM loading, reduced catalyst ageing and reduced backpressure.

This study compares the performance of the novel substrate for CO oxidation against commercially available 400 cpsi and 900 cpsi catalysts using gas concentrations and a flow rate equivalent to those experienced by a full catalyst brick when attached to a vehicle. Due to the novel micro-structure, no washcoat was required for the initial testing and 13 g/ft3 of Pd was deposited directly throughout the substrate structure in the absence of a washcoat.

Initial results for CO oxidation indicate that the advanced micro-structure leads to enhanced conversion efficiency. Despite an 79% reduction in metal loading and the absence of a washcoat, the novel substrate sample performs well, with a light-off temperature (LOT) only 15 °C higher than the commercial 400 cpsi sample.

To test the effects of catalyst ageing on light-off temperature, each sample was aged statically at a temperature of 1000 °C, based on the Bench Ageing Time (BAT) equation. The novel substrate performed impressively when compared to the commercial samples, with a variation in light-off temperature of only 3% after 80 equivalent hours of ageing, compared to 12% and 25% for the 400 cpsi and 900 cpsi monoliths, respectively.

Synthesis of , of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs’ catalysts

A series of alpha,beta-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (>= 90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids.