Final Report Summary - NANOCAT (Tailored nanosized metal catalysts for improving activity and selectivity via engineering of their structure and local environment)
Special emphasis within NANOCAT project was put on the deeper understanding of the nanometal particle environment, i.e. the different local metal particle environments were compared with the same metal particle sizes in different partial oxidations, hydrogenation, chemoselective hydrogenations as well as in isomerisation reactions. The work was divided in nine different subtasks: catalyst synthesis, testing, characterisation, kinetic and quantum chemical modelling, creating and disseminating of the new knowledge, prototype catalyst preparation, characterisation and testing, economical evaluation of the prototype catalyst as well as the project management.
The technical aim was to develop selective catalysts for producing fine and specialty chemicals, like fragrances, drugs and anticarcinogenic compounds with high purity as well as to investigate the possibility of preventing metal leaching. Another important topic was catalyst deactivation which was investigated by reusing the same catalyst in consecutive experiments.
The NANOCAT project had the following milestones: delivery of catalysts and database from catalyst characterisation, from catalyst screening and from kinetic tests, description of reaction mechanisms via kinetic and quantum chemical modelling, establishment of the fundamental knowledge on nanosized catalysts and dissemination of it, delivery of prototype catalysts including economical evaluation of these catalysts as well as arranging project meetings, mid-term assessment and final assessment.
The interrelation of different workpackages in NANOCAT project is presented below.
WP 1 - Catalyst synthesis. The objective was to prepare catalysts incorporated with nanosized metal particles (1-10 nm). Catalyst support materials, such as zeolites, mesoporous inorganic matrices, polymer matrices and carbon nanofibres, were utilised to obtain metal particles of nanosize. Palladium, platinum, gold, and ruthenium were incorporated into the organic and inorganic matrices, since these metals are commonly used in the synthesis of fine chemicals. Also bi-metallic catalysts were synthesized in order to further improve the activity and selectivity to the desired products. The objective, the milestone (M1), and the deliverables D1-D4 were all fulfilled, meaning that WP 1 has been successfully accomplished.
WP 2 - Testing of the catalysts. The objective of WP 2 was to test the catalysts synthesized in work package 1 in several reactions. The aim was to correlate the catalytic behaviour to the catalyst properties. An additional aim was to investigate the possible metal leaching from the nanosized supported metal catalysts. The most promising materials were further used in kinetic study. The hydrogenolysis and dehydrogenation of hydroxymatairesinol, oxidation of lactose, L-sorbose, D-glucose, and piperonyl alcohol, as well as hydrogenation of crotonaldehyde and cinnamaldehyde were performed. The two milestones, a database from catalyst screening results relating catalytic activity in a variety of reactions (M2) and kinetic results from comparison between one metal of the same metal particle size (1- 2 nm) supported on inorganic/organic matrix and the correlation of the solvent nature to the catalyst performance (M3), together with the two deliverables D5 and D6 were all fullfilled. The results from WP 2 served as input to WP 4, WP 5 and WP 6.
WP 3 - Catalyst characterisation. The objective of WP 3 was the characterisation of the micro-mesoporous matrices, carbon nanofibres and polymer matrices as well as the nanosized metal supported catalysts synthesized in WP 1. Moreover, to characterise the solution properties and swelling behaviour of the linear and cross-linked polymers respectively, before the formation of the metal nanoparticles and to investigate the changes in the micelle and gel characteristics after the metal incorporation and the metal nanoparticle formation. The materials were characterized using N2-physisorption (surface area), CO- and H2- chemisorption (dispersion, metal surface area), direct current plasma atomic emission spectrometry (DCP, metal content), inductively coupled plasma emission mass-spectrometry (ICP-MS, metal content), Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR, pyridine adsorption for determination of concentration of acid sites), titrations using NaOH for determination of acid sites, X-ray powder diffraction (XRPD), X-ray fluorescence analysis (XFA), Atomic force microscopy (AFM), ASAXS, UV-Visible spectroscopy (UV/Vis), dynamic light scattering (DLS), proton nuclear magnetic resonance spectroscopy (1H NMR), and Electron paramagnetic resonance (EPR). The two milestones, M 4 with delivery of the micro-mesoporous materials and carbon nanofibres without and with metal incorporation provided with structural data and M 5 with delivery of the polymer matrices without and with metal incorporation provided with structural data, together with the two deliverables, D7 and D8 database from structural characterisation of micro-mesoporous matrices and carbon nanofibres without and with metal incorporation and database from structural characterisation of polymer matrices without and with metal incorporation. Input into WP 4, WP 5 and WP 6.
WP 4 - Modelling. The objective of WP 4 was to perform Monte Carlo simulations and quantum chemistry calculations based on catalyst characterisation from WP 3 as well as kinetic modelling based on the kinetic data from WP 2. The description of the reaction mechanism for these reactions using Monte Carlo simulations and quantum chemistry calculations in combination with the input data from catalyst characterisation from WP 3 as well as on kinetic modelling with the input data from the reaction tests from WP 2 was performed. The modelling provided interrelation with WP 5, creation of fundamental knowledge from the local metal environment of the metal particle size. The deliverables D9 and D10, description of the reaction mechanisms based on the catalyst characterisation results from WP 3 and D the kinetic data from WP 4 were delivered. Hereby, WP 4 has successfully been completed.
WP 5 - Creation of fundamental knowledge. The objective of WP 5 was to create fundamental knowledge from the relation between the metal particle size and its local environment and the catalytic performance in the test reactions carried out in WP 2. The knowledge developed in WP 2 (testing), WP 3 (characterisation) and WP 4 (modelling) was used as input data. The milestone M7 establishing of correlation between the metal particle size and the local environment of metals with the catalytic performance and the establishing of the surface reaction mechanisms together with the deliverables, D11 and D12 (patent and scientific manuscripts) were all fulfilled.
WP 6 - Prototype catalyst. The objective of WP 6 was prototype catalyst preparation, characterisation and testing. The fundamental knowledge served as basis for the preparation, characterisation and testing of prototype catalysts in the test reaction in WP 2. Scale-up of preparation recipes was studied.
The development of preparation routes for heterogeneous (powder) catalysts aimed at reliable recipes capable of producing catalysts with reproducible performance.
WP 7 - Dissemination of knowledge. The objective of WP 7 was to disseminate the fundamental knowledge from the metal particle size and environment as well as its relation to the catalyst activity / selectivity in forms of summer schools and workshops.
WP 8 - Project management. The objective of WP 8 was to arrange project management and mid-term assessment as well as final project assessment. Two meetings per year were arranged within the NANOCAT project.
WP 9 - Economic evaluation of catalysts. The objective of WP 9 was the economical evaluation. Based on results of prototype and scale-up study economic potential of catalysts and processes using respective catalysts was evaluated.