Extension of the single-event microkinetic model to alkyl substituted monoaromatics hydrogenation on a Pt catalyst

The Single-Event Micro Kinetic (SEMK) methodology, which had been successfully applied to benzene hydrogenation on a Pt catalyst, has now been extended toward substituted monoaromatics, that is, toluene and o-xylene. The single event concept Combined with thermodynamic constraints. allowed to significantly reduce the number of adjustable parameters. In addition to the number of unsaturated nearest neighbor carbon atoms, H-atom addition rate and equilibrium coefficients were assumed to depend on the carbon atom type, that is, secondary or tertiary. This leads to three additional :reaction families compared to benzene hydrogenation: Gas. phase toluene and o-xylene hydrogenation experiments were performed on 0.5 wt % Pt/ZSM-22 in a temperature range from 423 to 498 K, a total pressure range from 1 to 3 MPa, H-2 inlet partial pressures between 100 and 600 kPa and aromatic inlet partial pressures between 10 and 60 kPa. A simultaneous regression of the :SEMK,Model to an experimental data set consisting of 39 toluene and 37 o-xylene hydrogenation experiments resulted in activation energies of H additions to tertiary:carbon:atoms:that are 10.5 kJ mol(-1) higher than to secondary carbon atoms. This can be related to the steric hindrance experienced during H addition to a carbon atom bearing a substituent. The presence of a substituent on the aromatic king was found not to affect the Chemisorption enthalpies. The reaction path analysis has been carried out via differential contribution analysis and identified that the hydrogenation first, occurs at secondary carbon atoms, prior to the hydrogenation of the tertiary carbon atoms in the hydrogenation Sequence. This is in line with the distribution of hydrocarbon species on the catalyst surfac

Liquid-phase hydrogenation of bio-refined succinic acid to 1,4-butanediol using bimetallic catalysts

open access articleDevelopment of a Crotalaria juncea based biorefinery produce large quantity of waste glycerol after trans-esterification of the juncea seeds. This glycerol, after purification, is used as a substrate for producing succinic acid on a microbial route. Hydrogenation of this bio-refined succinic acid is carried out under high pressure in order to produce 1,4- butanediol (BDO) using a batch slurry reactor with cobalt supported ruthenium bimetallic catalysts, synthesized inhouse. It is demonstrated that, using small amounts of ruthenium to cobalt increases the overall hydrogenation activity for the production of 1,4-butanediol. Hydrogenation reactions are carried out at various operating temperatures and pressures along with changes in the mixing ratios of ruthenium chloride and cobalt chloride hexahydrate, which are used to synthesize the catalyst. The Ru-Co bimetallic catalysts are characterized by XRD, FE-SEM and TGA. Concentrations of the hydrogenation product are analyzed using Gas chromatography-Mass spectrometry (GC-MS). Statistical analysis of the overall hydrogenation process is performed using a Box-Behnken Design (BBD)

Factors affecting the extent of branching in fischertropsch synthesis products with iron-based catalysts

Branched products are mainly formed during secondary isomerization reactions, and not in the main synthesis reaction itself. The extent of branching is a function of the catalyst formulation. High acidity and a low hydrogenation strength of the catalyst (normally found in catalysts with a high basicity) favour branching. The latter can be explained by the fact that the rate of skeletal isomerization of alkenes is much higher than the rate of hydrogenation. If the former rate is higher than the latter, hydrogenation will take place rapidly before any isomerization can occur. Little variation with time on stream is observed in the extent of branching with non-acidic catalysts. Acidic catalysts yield initially a much more branched product, the extent of which decreases with time on stream, to eventually reach levels only marginally higher than those observed with non-acidic catalysts. The extent of branching is different for products with different carbon numbers. It does not follow a random probability pattern, as results from a hydrocarbon synthesis in which single carbon units are linked to the growing chains at random places, but rather a pattern which depends on the hydrogenation strength of the catalyst used. With low hydrogenation strength catalysts, branching occurs preferentially in the lighter products. Branching is favoured in the heavier products when higher hydrogenation strength catalysts are used. This is explained in terms of the higher surface mobility of lighter products

"Narrow" Graphene Nanoribbons Made Easier by Partial Hydrogenation

It is a challenge to synthesize graphene nanoribbons (GNRs) with narrow widths and smooth edges in large scale. Our first principles study on the hydrogenation of GNRs shows that the hydrogenation starts from the edges of GNRs and proceeds gradually toward the middle of the GNRs so as to maximize the number of carbon-carbon $\pi$-$\pi$ bonds. Furthermore, the partially hydrogenated wide GNRs have similar electronic and magnetic properties as those of narrow GNRs. Therefore, it is not necessary to directly produce narrow GNRs for realistic applications because partial hydrogenation could make wide GNRs "narrower"

Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions

The selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO₂, ZnO, γ-Al2O₃, CeO₂ is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 °C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO₂ and γ-Al₂O₃. In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature

Highly active iridium(I) complexes for the selective hydrogenation of carbon-carbon multiple bonds

New iridium(I) complexes, bearing a bulky NHC/phosphine ligand combination, have been established as extremely efficient hydrogenation catalysts that can be used at low catalyst loadings, and are compatible with functional groups which are often sensitive to more routinely employed hydrogenation methods

Zipping and unzipping of nanoscale carbon structures

We demonstrate theoretically that hydrogenation and annealing applied to nanoscale carbon structures play a crucial role in determining the final shape of the system. In particular, graphene flakes characterized by the linear and non-hydrogenated zigzag or armchair edges have high propensity to merge into a bigger flake or a nanotube (the formation of a single carbon-carbon bond lowers the total energy of the system by up to 6.22 eV). Conversely, the line of the $sp^2$ carbon bonds (common for pure carbon structures such as graphene or a carbon nanotube) converted into the $sp^3$ type by hydrogenation shows an ability to disassemble the original structure by cutting it along the line of the modified bonds. These structural transformations provide us with an understanding of the behavior of mobile carbon structures in solution and a distinct scenario of how to preserve the original structure which would be a crucial issue for their application in carbon-based electronics.Comment: 7 pages, 6 figure

Development of covalent triazine frameworks as heterogeneous catalytic supports

Covalent triazine frameworks (CTFs) are established as an emerging class of porous organic polymers with remarkable features such as large surface area and permanent porosity, high thermal and chemical stability, and convenient functionalization that promotes great potential in heterogeneous catalysis. In this article, we systematically present the structural design of CTFs as a versatile scaffold to develop heterogeneous catalysts for a variety of chemical reactions. We mainly focus on the functionalization of CTFs, including their use for incorporating and stabilization of nanoparticles and immobilization of molecular complexes onto the frameworks

Evolution of PAHs in photodissociation regions: Hydrogenation and charge states

Various studies have emphasized variations of the charge state and composition of the interstellar polycyclic aromatic hydrocarbon (PAH) population in photodissociation regions (PDRs). We aim to model the spatial evolution of the charge and hydrogenation states of PAHs in PDRs. We focus on the specific case of the north-west (NW) PDR of NGC 7023 and also discuss the case of the diffuse interstellar medium (ISM). The physical conditions in NGC 7023 NW are modelled using a state-of-the-art PDR code. We then use a new PAH chemical evolution model that includes recent experimental data on PAHs and describes multiphoton events. We consider a family of compact PAHs bearing up to 96 carbon atoms. The calculated ionization ratio is in good agreement with observations in NGC 7023 NW. Within the PDR, PAHs evolve into three major populations: medium-sized PAHs (50<Nc<90) are normally hydrogenated, larger PAHs (Nc>90) can be superhydrogenated, and smaller species (Nc<50) are fully dehydrogenated. In the cavity, where the fullerene C60 was recently detected, all the studied PAHs are found to be quickly fully dehydrogenated. PAH chemical evolution exhibits a complex non-linear behaviour as a function of the UV radiation field because of multiphoton events. Steady state for hydrogenation is reached on timescales ranging from less than a year for small PAHs, up to 10000 years for large PAHs at Av=1. We identified critical reactions that need more studies. Our new model allows us to rationalize the observational constraints without any fitting parameter. PAHs smaller than 50 carbon atoms are not expected to survive in the NGC 7023 NW PDR. A similar conclusion is obtained for the diffuse ISM. Carbon clusters turn out to be end products of PAH photodissociation, and the evolution of these clusters needs to be investigated further to evaluate their impact on the chemical and physical evolution of PDRs.Comment: 16 pages, 10 figures; Accepted for publication in A&