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.

Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow

Platinum is one of the most widely used hydrogenation catalysts. Here we describe the translation of batch reactions to continuous flow, affording tunable C=O versus C=C hydrogenation over a Pt/SiO2 catalyst, resulting in high steady state activity and single-pass yields in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol under mild conditions. Negligible catalyst deactivation occurs under extended flow operation due to removal of reactively-formed poisons from the reaction zone. Process intensification imparts a four-fold enhancement in cinnamyl alcohol productivity.

Nanoengineering heterogeneous catalysts for the selective hydrogenation of key agrochemical derivatives

Rapidly rising world populations have sparked growing concerns over global food production to meet this increasing demand. Figures released by The World Bank suggest that a 50 % increase in worldwide cereal production is required by 2030. Primary amines are important intermediates in the synthesis of a wide variety of fine chemicals utilised within the agrochemical industry, and hence new 'greener' routes to their low cost manufacture from sustainable resources would permit significantly enhanced crop yields. Early synthetic pathways to primary amines employed stoichiometric (and often toxic) reagents via multi-step protocols, resulting in a large number of by-products and correspondingly high Environmental factors of 50-100 (compared with 1-5 for typical bulk chemicals syntheses). Alternative catalytic routes to primary amines have proven fruitful, however new issues relating to selectivity and deactivation have slowed commercialisation. The potential of heterogeneous catalysts for nitrile hydrogenation to amines has been demonstrated in a simplified reaction framework under benign conditions, but further work is required to improve the atom economy and energy efficiency through developing fundamental insight into nature of the active species and origin of on-stream deactivation. Supported palladium nanoparticles have been investigated for the hydrogenation of crotononitrile to butylamine (Figure 1) under favourable conditions, and the impact of reaction temperature, hydrogen pressure, support and loading upon activity and selectivity to C=C versus CºN activation assessed.

Acetylene hydrogenation over structured Au-Pd catalysts

Acknowledgements We thank the University of Aberdeen for financial support and Dr K. McManus (University of Aberdeen) for performing preliminary experiments with these samples. Electron microscopy and EDS were performed by RTB at the Electron Microscopy Facility, University of St Andrews.

Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

We acknowledge the contribution of Dr. N. Perret to this work. EPSRC support for free access to the TEM/SEM facility at the University of St. Andrews and financial support to Dr. X. Wang and Y. Hao through the Overseas Research Students Award Scheme (ORSAS) are also acknowledged.

Palladium Sulfide – A Highly Selective Catalyst for the Gas Phase Hydrogenation of Alkynes to Alkenes

Acknowledgements The support of the Spanish Government (projects CTQ2014-52956-C3-2-R and CTQ2014-52956-C3-3-R) is recognized.

Selective gas phase hydrogenation of nitroarenes over Mo2C supported Au-Pd

Peer reviewed

Determination of toluene hydrogenation kinetics with neutron diffraction

Total neutron scattering has been used to follow the hydrogenation of toluene-d₈ to methylcyclohexane-d₁₄ over 3 wt% platinum supported on highly ordered mesoporous silica (MCM-41) at 298 K and under 150 mbar D₂ pressure. The detailed kinetic information so revealed indicates that liquid reorganisation inside pores is the slowest step of the whole process. Additionally, the results were compared with the reaction performed under 250 mbar D₂ pressure as well as with toluene-h₈ hydrogenation using D₂ at 150 mbar.

Catalytic reactions with palladium supported on mesocellular foam : Applications in hydrogenation, isomerization, and C-C bond forming reactions

The major part of this thesis concerns the development of catalytic methodologies based on palladium nanoparticles immobilized on aminopropyl-functionalized siliceous mesocellular foam (Pd0-AmP-MCF). The catalytic activity of the precursor to the nanocatalyst, PdII-AmP-MCF is also covered by this work. In the first part the application of Pd0-AmP-MCF in Suzuki-Miyaura cross-coupling reactions and transfer hydrogenation of alkenes under microwave irradiation is described. Excellent reactivity was observed and a broad range of substrates were tolerated for both transformations. The Pd0-AmP-MCF exhibited high recyclability as well as low metal leaching in both cases. The aim of the second part was to evaluate the catalytic efficiency of the closely related PdII-AmP-MCF for cycloisomerization of various acetylenic acids. The catalyst was able to promote formation of lactones under mild conditions using catalyst loadings of 0.3 - 0.5 mol% at temperatures of up to 50 oC in the presence of Et3N. By adding 1,4-benzoquinone to the reaction, the catalyst could be recycled four times without any observable decrease in the activity. The selective arylation of indoles at the C-2 position using Pd-AmP-MCF and symmetric diaryliodonium salts is presented in the third part. These studies revealed that Pd0-AmP-MCF was more effective than PdII-AmP-MCF for this transformation. Variously substituted indoles as well as diaryliodonium salts were tolerated, giving arylated indoles in high yields within 15 h at 20 - 50 oC in H2O. Only very small amounts of Pd leaching were observed and in this case the catalyst exhibited moderate recyclability. The final part of the thesis describes the selective hydrogenation of the C=C in different α,β-unsaturated systems. The double bond was efficiently hydrogenated in high yields both under batch and continuous-flow conditions. High recyclability and low metal leaching were observed in both cases.

Using Surface Spectroscopy to Help Interpret STM Images of Chemisorbed Molecules: Application to the Study of the Hydrogenation of Ketones and a-Ketoesters on Pt

Depuis que la haute énantiopureté est nécessaire dans l’industrie pharmaceutique, les études visant à découvrir les mécanismes pour l’hydrogénation énantiosélective de cétones ou céto-esters sur les surfaces, et à rechercher de nouveaux et plus performants catalyseurs asymétriques, sont d’une grande importance. La microscopie à effet tunnel (STM), la spectroscopie infrarouge de réflexion-absorption, la spectroscopie de désorption à température programmée et la spectrométrie de photoélectrons induits par rayons X sont des méthodes performantes facilitant la compréhension des mécanismes de réaction. En plus de nous permettre de comprendre les mécanismes réactionnels, les études peuvent fournir des informations sur la dynamique des réactions en catalyse hétérogène ainsi que sur le développement de la théorie de la fonctionnelle de la densité (DFT) afin de calculer des interactions faibles dans les processus de surface. D’autres parts, les calculs DFT fournissent une aide essentielle à l’interprétation des données de STM et spectroscopie de surface. Dans cette thèse, certains cétones et céto-esters sur la surface de platine sont étudiées par les techniques sophistiquées mentionnées ci-dessus. Mes études démontrent que la combinaison de l’utilisation de la spectroscopie de routine, des nanotechnologies et de nombreux calculs élaborés, est une méthode efficace pour étudier les réactions à la surface car ces techniques explorent les différents aspects de la surface ainsi que s’entraident mutuellement lors de certaines interprétations.

Catalytic CO2 hydrogenation: study at the molecular scale using field emission techniques

An accurate characterization of the rhodium specimen was obtained via FIM experiments. Reaction behaviors between H2 and CO2 were observed in FEM mode at 700 K. At this temperature, CO desorption occurs, preventing CO+H2 reaction. Surface is mainly recovered by oxygen; reaction with hydrogen occurs. Finally, we can identify the reaction as the Reverse Water Gas Shift.

Selective hydrogenation by novel composite supported Pd egg-shell catalysts

Two organic–inorganic mixed phase supports were prepared, comprising an alumina filler and polymers of different chemical nature. Four low loaded Pd catalysts were prepared. Good activities and selectivities were obtained during the hydrogenations of styrene, 1-heptyne and 2,3-butanedione. The catalysts were found to have excellent mechanical properties and could be used in applications needing high attrition resistance and crushing strength. In this sense, processes for fine chemicals using slurry reactors or processes for commodities using long packed beds could advantageously use them.

Catalytic asymmetric transfer hydrogenation of ketones: recent advances

In this review, we consider the main processes for the asymmetric transfer hydrogenation of ketones from 2008 up today. The most effective organometallic compounds (derived from Ru, Rh, Ir, Fe, Os, Ni, Co, and Re) and chiral ligands (derived from amino alcohols, diamines, sulfur- and phosphorus-containing compounds, as well as heterocyclic systems) will be shown paying special attention to functionalized substrates, tandem reactions, processes under non-conventional conditions, supported catalysts, dynamic kinetic resolutions, the use of water as a green solvent, theoretical and experimental studies on reaction mechanisms, enzymatic processes, and finally applications to the total synthesis of biologically active organic molecules.

Catalytic Asymmetric Transfer Hydrogenation of Imines: Recent Advances

In this review article recent developments in the asymmetric transfer hydrogenation of imines from 2008 up to today are presented. The main methodology involves either metal-catalyzed procedures in the presence of a chiral ligand or organocatalyzed technologies using a Hantzsch ester and a chiral BINOL-derived phosphoric acid. The most important procedures are collected, paying special attention to the application of this methodology in synthetic organic chemistry.

Hydrogen spillover mechanism on a pd-doped mg surface as revealed by ab initio density functional calculation

The hydrogenation kinetics of Mg is slow, impeding its application for mobile hydrogen storage. We demonstrate by ab initio density functional theory (DFT) calculations that the reaction path can be greatly modified by adding transition metal catalysts. Contrasting with Ti doping, a Pd dopant will result in a very small activation barrier for both dissociation of molecular hydrogen and diffusion of atomic H on the Mg surface. This new computational finding supports for the first time by ab initio simulationthe proposed hydrogen spillover mechanism for rationalizing experimentally observed fast hydrogenation kinetics for Pd-capped Mg materials.