Sustainable Catalytic Conversions of Renewable Substrates
Catalysis Science & Technology
is organising a one day Symposium
Sustainable Catalytic Conversions of Renewable Substrates (SuBiCat II) Monday 2nd March 2015 Upper/Lower College Hall North Street St Andrews.
The symposium is free of charge but we request that you register before 15th February 2015 see tab registration form.
- Piet van Leeuwen, ICIQ Tarragona
- Javier Perez Ramirez, ETH Zurich
- Ding Ma, Peking University
- Christian Bruneau, University of Rennes
- David Jackson, Glasgow University
- Pieter Bruijnincx, Utrecht University
- Carsten Bolm, RWTH Aachen
- Kristiina Hilden, University of Helsinki
- John T. S. Irvine, University of St Andrews
Program Symposium on ‘Sustainable Catalytic Conversions of Renewable Substrates’ (SuBiCat II) Monday 2nd March 2015 University of St Andrews, Upper/Lower College Hall, St Salvator’s Quad, North Street St Andrews
Monday 2nd March 2013
- 8.50 Welcome – Prof Paul Kamer, University of St Andrews, Associate Editor Catalysis Science & Technology
Session 1 - Chair Prof Paul Kamer
Session 2 - Chair Prof Andy Smith
Session 3 - Chair Prof Nick Westwood
Session 4 - Chair Prof Bob Tooze
- 9.00 - Prof. Piet van Leeuwen , ICIQ, Tarrgona, Spain
Ligand effects in nanoparticle catalysis
- 9.45 Dr Pieter Bruijnincx, University of Utrecht, The Netherlands
Catalyst Development for New and ‘Drop-in’ Chemicals from the Carbohydrate and Lignin Fractions of Biomass
- 10.30 Prof. Ding Ma Peking University, China
Insight into Iron-based Fischer-Tropsch Synthesis Reaction
- 11.15 Coffee break
- 11.45 Prof. Carsten Bolm, RWTH Aachen University, Germany
Lignin degradation by mechanochemistry and catalysis
- 12.30 Prof. David Jackson, University of Glasgow, Scotland, UK
Conversion of Lignin to Functionalised Alkylphenols over Heterogeneous Catalysts
- 13.15 Lunch
- 14.15 Dr Kristiina Hilden, University of Helsinki, Finland
Plant biomass degradation by the white rot basidiomycete fungi
- 15.00 Prof. Christian Bruneau, University of Rennes, France
Metal catalysts equipped with a bifunctional phosphinesulfonate ligand: applications in catalytic reactions involving hydrogen transfer
- 15.45 Tea break
- 16.15 Prof. John Irvine, University of St Andrews, Scotland, UK
Direct Carbon Fuel Cells
- 17.00 Prof. Dr. Pérez-Ramírez, Institute for Chemical and Bioengineering, Zurich, Switzerland
Treasure hunting in catalysis by hierarchical zeolite design
- 17.45 Wine reception and symposium end
Ligand Effects Metal Nanoparticles Catalysis
In this contribution we describe the effects that ligands can have in the catalysis by MNPs, thus applying the methods of homogeneous catalysis in heterogeneous catalysis. Mainly two metals will be discussed, ruthenium and gold. Ruthenium nanoparticles (MNPs) are of great interest as catalysts. Their properties are controlled by stabilizers present during their synthesis. A mild and controlled method for obtaining MNPs is the decomposition of organometallic precursors by dihydrogen as developed by Chaudret and co-workers. Small Ru-NPs (1–3 nm) are stabilized by concave, large organic molecules that cover part of the vertices and apices, thereby controlling the size and the shape, leaving edges next to the molecular wings and uncovered surface available for interactions leading to catalysis. Some of these Ru-NPs showed very good activities in the hydrogenation of aromatic compounds. A detailed HRMAS-NMR characterization of the Ru-NPs showed that the ligand nature and not only the size of the RuNP is decisive for catalytic activity.
The synthesis, thorough identification, and unique catalytic properties of small gold nanoparticles ligated by secondary phosphine oxides will be presented. The gold nanoparticles containing on average 50 gold atoms and 30 SPO ligands are easy to make in a reproducible manner. The AuNP@SPO nanoparticles have been fully identified. They are very selective catalysts for the hydrogenation of aldehydes in the presence of any functional group. The ligands play a crucial triple role as stabilizers for the nanoparticles, as modifying ligands, and as functional ligands supplying the oxygen function that participates in the heterolytic cleavage of dihydrogen. We have proven that the secondary phosphine is present as the R2P=O anionic species, similar to thiolates in AuNPs, coordinating to gold with the phosphorus. We suggest that the oxygen atom of the secondary phosphine oxide plays a role similar to the one of oxygen atoms of oxide supports in the heterolytic cleavage and hydrogenation.
1. Philippot, K.; Chaudret, B., C. R. Chimie 2003, 6, 1019. Gonzalez-Galvez, D.; Lara, P.; Rivada-Wheelaghan, O.; Conejero, S.; Chaudret, B.; Philippot, K.; van Leeuwen, P. W. N. M Catal. Sci. Technol. 2013, 3, 99–105. Gonzalez-Galvez, D.; Nolis, P.; Philippot, K.; Chaudret, B.; van Leeuwen, P. W. N. M. ACS Catal. 2012, 2, 317–321.
2. Cano, I.; Chapman, A. M.; Urakawa, A.; van Leeuwen, P. W. N. M. J. Am. Chem. Soc. 2014, 136, 2520–2528. Rafter, E.; Gutmann, T.; Low, F.; Buntkowsky, G.; Philippot, K.; Chaudret, B.; van Leeuwen, P. W. N. M. Catal. Sci. Technol. 2013, 3, 595.
Catalyst Development for New and ‘Drop-in’ Chemicals from the Carbohydrate and Lignin fractions of Biomass
Efficient second generation biorefinery operations require the valorization of all fractions of lignocellulosic biomass, i.e. outlets need to be sought for both the carbohydrate as well as the lignin components. The production of value-added, renewable chemicals from lignocellulosic biomass typically entails the depolymerization/conversion of the (hemi)cellulose or lignin biopolymers to versatile and easy-to-obtain platform molecules, which can in turn be further converted by (chemo)catalytic means to the desired end products. These value-added, biomass-derived chemicals can either be new or ‘drop-in’, i.e. molecularly-identical to an existing (petro)chemical. The former have the advantage of holding the promise of improved performance. The latter have the advantage of serving already existing markets and using current infrastructure, but can only compete on price. Here, some of the recent efforts from our group on the valorization of lignocellulosic biomass to both new and drop-in renewable chemicals will be discussed, with a particular emphasis on the valorization of the sugar fraction. Topics covered will include the unexpected benefits that the use of a real, crude biorefinery feed brings to the production of 5-hydroxymethylfurfural (HMF) and the structural characterization and catalytic conversion of humins, an important waste product formed during hydrothermal carbohydrate conversion processes, such as the production of HMF. As an example of both new and drop-in chemicals production, turther catalytic valorization of platform molecules that can be obtained from the carbohydrate fraction will also be discussed. The development of highly active and stable bimetallic catalysts for the hydrogenation of levulinic acid to valerolactone will be reported, as well as an alternative route for the production of aromatics from sugar-derived furans.
Insight into Iron-based Fischer-Tropsch Synthesis Reaction
As one of the oldest and most complicated heterogeneous catalytic reaction, the basic understand regarding the Fischer-Tropsch synthesis (FTS) in term of the catalyst active phase and reaction mechanism remain unclear and even in debates. In this report, pure phase iron-based catalysts including α-Fe, Fe5C2, Fe7C3 and Fe2C were prepared and used to identify their intrinsic activity. It was found that Fe5C2 is the most active catalyst while α-Fe underwent a gradual increase in activity in the induction period due to the structural transformation toward iron carbide. A transient experiment named high-pressure stepwise temperature programming surface reaction (STPSR), in-situ XRD and X-ray absorption fine structure (XAFS) experiments were conducted to follow the reaction dynamics over these catalysts and structural evolution under FTS condition. Coping with comprehensive density functional theory calculations, a vivid image about how the FTS processes are for the first time disclosed. It was found that though α-Fe was highly active for CO activation, the too strong binding with dissociated atomic carbon prevented subsequent C-C coupling and methanation. α-Fe catalyst, whose intrinsic activity for FTS was therefore rather low, tends to be carburized and transformed into thermodynamically more favorable iron carbide under FTS condition. For iron carbide, CO activation remained facile, but dissociated atomic carbon was largely destabilized. This facilitated greatly the formation of monomers and C-C coupling with preference of unsaturated hydrocarbon. Importantly, the effective barrier for C-C coupling was even lower than that of CO activation. The insights revealed are valuable for rationale of design for iron-based FTS catalysts.
Lignin degradation by mechanochemistry and catalysis
After optimizing the synthetic access of lignin model compounds1 and revealing mechanistic details by DFT calculations,2 we have now been focusing our attention of degradation studies. First, a mechanochemical approach was investigated.3 Currently, we emphasize on oxidative cleavage reactions4 and transformations in dimethyl carbonate as solvent.5
1. J. Buendia, J. Mottweiler, C. Bolm, Chem. Eur. J. 2011, 17, 13877 - 13882.
2. A. J. Johansson, E. Zuidema, C. Bolm, Chem. Eur. J. 2010, 16, 13487 - 13499.
3. T. Kleine, J. Buendia, C. Bolm, Green Chem. 2013, 15, 160 - 166.
4. J. Mottweiler, M. Puche, C. Räuber, T. Schmidt, P. Concepión, A. Corma, C. Bolm, submitted for publication.
5. S. Dabral, J. Mottweiler, T. Rinisch, C. Bolm, submitted for publication.
Conversion of Lignin into Functionalised Alkylphenols over Heterogeneous Catalysts
Lignin is the most recalcitrant part of woody biomass yet is one of the few natural aromatic resources available in abundance. There is huge potential for this material to be used as a key feedstock in future applications however a conversion route to fine chemicals must be first be established. In this lecture we report on a methodology to convert the high purity lignin, extracted from raw wood sawdust, into value added products by hydrogenolysis.
It was found that lignin isolated using an ammonia pre-treatment from Poplar wood gave an uncondensed structure that was more reactive to catalytic depolymerisation compared to the condensed lignin produced using an organosolv or dilute sulphuric acid pre-treatment .
Fig. 1. Alkylphenol motif.
The lignin was converted to aromatic monomers over a series of supported metal catalysts in a batch reactor at 250 – 300C with 20 barg hydrogen in a water/methanol solvent . The monomers produced were based on a simple substituted alkyl phenol motif shown in Fig. 1, where R1 = H, C1 – C3, R2 = H, OMe and R3 = H, OMe. By changing the water to methanol ratio in the solvent it was possible to direct the selectivity, with methanol favouring R1 as a C3 unit and water favouring R1 as H.
The mechanism of the reaction was probed using deuterium and deuterated water and methanol. Interestingly an inverse kinetic isotope effect was observed when a deuterated reaction was performed instead of a protiated reaction. Hence by using mixtures of deuterated and protiated solvents and gas a picture of the surface chemistry has been developed and will be presented.
 Florent P. Bouxin, Michael C. Jarvis, S David Jackson, Bioresource Technology, 162, 236-242 (2014)
 Florent P. Bouxin, Ashley McVeigh, Fanny Tran, Nicholas J. Westwood, Michael C. Jarvis and S. David Jackson, Green Chemistry, Advance article, (2015), DOI: 10.1039/C4GC01678E
Plant biomass degradation by white-rot basidiomycete fungi
White-rot fungi are major decomposers of wood and the only microbes capable of completely degrading lignin. Therefore they play a central role in the global carbon cycle. In addition to the ability to mineralize aromatic lignin polymer, white-rot fungi produce enzymes that degrade plant cell wall polysaccharides into oligosaccharides and monomeric sugars which can be used as a carbon source. Genome sequencing projects have revealed that white-rot fungi not only have an array of lignin-modifying peroxidase encoding genes together with various H2O2-generating enzymes encoding genes but also the most extensive arsenal of genes encoding hydrolytic and oxidative carbohydrate active enzymes. All these enzymes have potential as tools for biotechnology, as the products of their catalysis can be used as precursors of bio-based fuels and chemicals. This work focuses on the ability of the white rot fungus Dichomitus squalens to degrade various plant-derived biomasses. The influence of different types of plant biomasses on mechanisms behind the white-rot fungal plant cell wall degradation process will be discussed.
"Metal catalysts equipped with a bifunctional phosphinesulfonate ligand: applications in catalytic reactions involving hydrogen transfer"
Meta-and para-phosphinesulfonates are well known monodentate ligands that have been used for a long time to generate water-soluble catalysts. Ortho-phosphinesulfonates provide bidentate, and even tridentate ligands, that have been coordinated to transition metals (palladium, nickel) with the main initial applications in the field of polymers and copolymers.
Their coordination to ruthenium and iridium centers will be described. Their recent application in catalysis for fine chemistry in our laboratory will be discussed and their efficiency in hydrogen transfer reactions will be highlighted. Tandem reactions involving hydrogen transfer associated with C-C coupling reactions will be presented.
Nucleophilic allylic substitution directly from allylic alcohols catalyzed by Cp*Ru catalysts will illustrate an example of proton shuttle assisted by a phosphinesulfonate ligand. Then N-alkylation of amines by alcohols and functionalization at C(3) position of saturated cyclic amines will reveal the excellent properties of ruthenium and iridium catalysts to dehydrogenate alcohols into aldehydes and amines into enamines, and to achieve hydrogen borrowing processes. We will show that (phosphinesulfonate)ruthenium catalysts are also effective in enantioselective hydrogenation of non-functionalized aromatic ketones.
Direct Carbon Fuel Cells
Hybrid Direct Carbon Fuel Cells merge Solid Oxide Fuel Cell (SOFC) and MCFC technologies, using a solid oxide electrolyte to separate the cathode and anode compartments, while a molten carbonate electrolyte is utilised to extend the anode/electrolyte region. Oxygen is reduced to O2- ions at the cathode and transported across the solid electrolyte membrane to the anode compartment, where carbon is oxidised to CO2. Molten carbonate could enhance the carbon oxidation in two ways as a fuel carrier or as an electrochemical mediator. The maximum energy density can be achieved by fully oxidising carbon to CO2 offering very high efficiencies. This concept has been demonstrated using a wide range of carbons and carbon-rich fuels such as coal, plastics, carbon colloids, activated carbons and charcoals.
The underlying chemical processes are complex involving a series of catalytic and electrochemical reactions of a complex fuel. Coal and biochars are quite far from pure carbon comprising of high hydrogen content and often significant oxygen, sulphur and nitrogen contents as well as inorganic, ash components. Here we report on the pyrolysis and oxidation reactions and processes that occur in situ and in DCFC relevant conditions. Of key importance is interplay between carbon and its oxides as direct oxidation of carbon to carbon dioxide delivers the ultimate efficiency. There is a change in process above 750oC where the reverse Boudouard reaction becomes dominant and our focus is on understanding the lower temperature electrochemical processes.
NEW PROCESSES FOR GLYCEROL VALORIZATION TO COMMODITIES
Recently, the sustainable production of commodity chemicals and polymers from bio-derived feedstocks has received increasing attention. In this respect, many research efforts have been directed toward polylactic acid, whose scope of application is rapidly expanding in view of its versatile plastic properties and biodegradability. Since the current manufacture of lactic acid, sugar fermentation, suffers from limited productivity and scalability, it has been envisaged to alternative prepare this monomer from glycerol, an abundant byproduct of the biodiesel production, through a cascade process. Following an established biocatalytic oxidation step, the dihydroxyacetone intermediate can be transformed into the desired product via a chemocatalytic isomerization. We show that Lewis-acid tin-containing zeolites prepared by a facile and scalable post-synthetic strategy are very active, selective, and recyclable for this latter reaction. Thereafter, we demonstrate through life cycle analysis that the alternative route to lactic acid is environmentally and economically more advantageous than the conventional enzymatic technology in view of the use of a waste feedstock and of the outstanding performance of the heterogeneous catalyst. Still, the results of our assessment point out that an even more attractive process could be achieved if the first transformation was accomplished by a more productive method than fermentation. Following up this direction, we report the design of iron-containing zeolites, featuring mild acidity and small iron clusters, which are able to convert glycerol into the ketonic product with high selectivity in the gas phase. This achievement is not only relevant in the context of lactic acid production but also opens the door to a wider exploitation of dihydroxyacetone as an emerging building block to manufacture green copolymers with unprecedented functions.
P.Y. Dapsens, C. Mondelli, J. Pérez-Ramírez, ACS Catal. 2012, 2, 1487-1499.
P.Y. Dapsens, C. Mondelli, B.T. Kusema, R. Verel, J. Pérez-Ramírez, Green Chem. 2014, 16, 1176-1186.
M. Morales, P.Y. Dapsens, I. Giovinazzo, J. Witte, C. Mondelli, S. Papadokonstantakis, K. Hungerbühler, J. Pérez-Ramírez, Energy Environ. Sci., 2015, 8, 558-567.
G. M. Lari, C. Mondelli, J. Pérez-Ramírez, ACS Catal. 2015, 5, 1453-1461.