Päivi Mäki-Arvela

Asymmetric Heterogeneous Catalysis: Science and Engineering

Asymmetric heterogeneous catalysis is a vivid branch of catalysis, remaining, however, largely a domain of organic chemists. The view towards asymmetric heterogeneous catalysis adopted in this review is mainly from catalytic science and engineering. Not only reaction mechanisms, but also catalytic properties, kinetic regularities, as well as chemical engineering aspects, are covered with the main focus on recent developments.

Recent Progress in Synthesis of Fine and Specialty Chemicals from Wood and Other Biomass by Heterogeneous Catalytic Processes

Synthesis of fine and specialty chemicals involving heterogeneous catalysts is discussed according to the type of reactions (e.g., hydrogenation, oxidation, isomerization, etc.) for various biomass derived feedstocks (carbohydrates, lignans, phenols, flavonoids, tannins, and stilbenes, tall oil, and fatty acids).

Transforming Triglycerides and Fatty Acids into Biofuels

Fuels derived from biobased materials are attracting attention for their potential in securing the energy supply and protecting the environment. In this Minireview, we evaluate the use of biobased sources, particularly fatty acids and triglycerides from seed oils and animal fats, as fuels. The physical and chemical properties of these fatty acids and triglycerides are discussed, including the link to their sources and current availability to meet fuel demands. The current technologies, also known as the first-generation ones, for converting triglycerides into fuels are covered, including conventional methods such as transesterification, pyrolysis, cracking, and emulsions. Recent, second-generation technological developments that lead to more commercially viable biofuels based on diesel-like hydrocarbons are also discussed.

Ruthenium-modified MCM-41 mesoporous molecular sieve and Y zeolite catalysts for selective hydrogenation of cinnamaldehyde

Abstract Ru-modified MCM-41 mesoporous molecular sieve and Y zeolite catalysts were synthesised and characterised using XRD, electrochemical voltammetry, ESCA (XPS), nitrogen adsorption and H2-TPD. Selective liquid-phase hydrogenation of cinnamaldehyde to cinnamyl alcohol was investigated over these catalysts and compared to hydrogenation on a commercial Ru/C catalyst. The effect of support (MCM-41, Y and C), solvent (cyclohexane, hexane and 2-propanol) and catalyst pre-treatment (calcination) on the conversion of cinnamaldehyde and selectivity to cinnamyl alcohol was studied. The zeolite structure, pore size, acidity, catalyst pre-treatment as well as the solvent influenced the activity and selectivity. Non-calcined Ru/Y exhibited the highest selectivity to cinnamyl alcohol. The activity of Ru/Y was highest with 2-propanol as a solvent.

Solvent effects in enantioselective hydrogenation of 1-phenyl-1,2-propanedione

Abstract Solvent effects in enantioselective hydrogenation of 1-phenyl-1,2-propanedione ( A ) were investigated in a batch reactor over a cinchonidine modified Pt/Al 2 O 3 catalyst. The effect of different solvents, binary solvent mixtures and solvent dielectric constant on regio- and enantioselectivity as well as on the hydrogenation rate were studied. The hydrogen solubility in different solvents and the dielectic constants of solvent mixtures were measured. The highest enantiomeric excesses (ee) of ( R )-1-hydroxy-1-phenylpropanone ( B ) (65%) were obtained in toluene. The ee decreased non-linearly with an increasing solvent dielectric constant being close to zero in methanol. The role of the reactant conformation in different solvents was evaluated by quantum chemical calculations and the role of the Open(3) conformer of the modifier, cinchonidine was discussed. The dependence of ee on the dielectric constant could not solely be attributed to the abundance of the Open(3) conformer of cinchonidine in the liquid phase. A possible involvement of additional factors was proposed and discussed. The non-linear dependence of the ee on the dielectric constant was included in a kinetic model to describe quantitatively the variation of the ee in different solvents.

Switchable Ionic liquids (SILs) based on glycerol and acid gases

New types of switchable ionic liquids (SILs), containing 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), glycerol and an acid gas (CO2, SO2), were synthesized and characterized in this study. [DBU][Carbonate] or [sulfonate] were easily synthesized from a non-ionic mixture of molecular organic polyol and amidine base upon bubbling of an acid gas (CO2, SO2). Moreover, they were switched back to the original molecular solvents by flushing out the acid gas (CO2, SO2) by heating and/or bubbling an inert gas such as N2 through it. The structures of the SILs were confirmed by NMR and FTIR. The change from low polarity (molecular solvent) to high polarity (Switchable Ionic Liquid, SIL) was also indicated by the changes in properties, such as viscosity and miscibility with different organic solvents. The decomposition temperatures of the SILs were determined by means of Thermo Gravimetric Analysis (TGA) and gave values in the range of 50 °C and 120 °C for DBU-glycerol-CO2 (SIL1) and DBU-glycerol-SO2 (SIL2), respectively. Due to the reasonable decomposition temperatures, these novel SILs can be employed in multiple applications.

Xylose hydrogenation: kinetic and NMR studies of the reaction mechanisms

Abstract Hydrogenation of xylose over Raney nickel was studied in a batch reactor. A pseudo-homogeneous kinetic model was able to prognose the xylose and xylitol concentrations rather well. The obtained fit for the activation energies suggests that external diffusion limitations are absent in our experimental conditions. The sugar equilibria studies gave new information about the temperature dependence of the α–β-pyranose equilibria. It was found that the equilibria in D2O follows an S-shaped curve, the equilibria being shifted towards the α-form at higher temperatures.

Imidazolium‐Based Poly(ionic liquid)s as New Alternatives for CO2 Capture

Solid imidazolium-based poly(ionic liquid)s with variable molecular weights that contain the poly[2-(1-butylimidazolium-3-yl)ethyl methacrylate] (BIEMA) cation and different counter anions were evaluated in terms of CO2 capture and compared with classical ionic liquids with similar counter anions. In addition to poly(ionic liquid)s with often-applied ions such as BF4 (-) , PF6 (-) , NTf2 (-) , trifluoromethanesulfonate (OTf(-) ) and Br(-) , for the first time [BIEMA][acetate] was synthesised, which revealed a remarkably high CO2 sorption performance that exceeded the poly(ionic liquid)s studied previously on average by a factor of four (12.46 mg gPIL (-1) ). This study provides an understanding of the factors that affect CO2 sorption and a comparison of the CO2 capture efficiency with the frequently used sorbents. Moreover, all the studied sorbents were reusable if regenerated under carefully selected conditions and can be considered as suitable candidates for CO2 sorption.

Liquid-phase hydrogenation of citral over an immobile silica fibre catalyst

A new knitted silica fibre catalyst was introduced into liquid-phase hydrogenation of organic compounds. The fibre catalyst combines the advantages of catalyst slurries and large catalyst particles: diffusional limitations are suppressed and the catalyst is immobile. Nickel-impregnated silica fibres were used in the hydrogenation of citral to citronellal and citronellol in a tubular glass reactor where the catalyst was packed in two layers. The liquid phase was recirculated while the gas phase was flowing concurrently through the reactor to the vent. The highest selectivities to the desired product, citronellol, exceeded 90%. The catalyst performance was competitive with a conventional crushed nickel catalyst.

Overview of catalytic methods for production of next generation biodiesel from natural oils and fats

Production of biodiesel from natural oils and fats can be achieved using various technologies briefly discussed in this review. A particular appealing concept for production of green diesel is selective catalytic deoxygenation of renewables leading to diesel fuel products. This reaction can be performed over Pd on active carbon supports with saturated and unsaturated fatty acids and their derivatives.