Symposium 2013

SuStainable catalyticconverSionS of

renewable SubStrateSSunday 24th until Tuesday 26th March

Plenary speakers:

Prof bert weckhuysen:utrecht university

Prof James Dumesic:university of wisconsin Madison

Prof Matthias beller:leibniz-institut fur Katalyse ros-tock

Prof walter leitner:rwtH aachen

Prof Graham Hutchings:cardiff university

SympoSium programme

Sunday March-24th

Session 1: Chair Paul Kamer: University of St Andrews17.00-18.00 Bert Weckhuysen: Utrecht University Catalytic Conversion of Lignin and Humins18.00-20.00 Poster session and drinks

Monday March-25th

Session 2: Chair David Cole-Hamilton: University of St Andrews9.00-9.40 Walter Leitner: Aachen University Catalytic Processes Utilizing CO2 as C-1 Building Block: Challenges and Opportu nities

9.40-10.20 Adisa Azapagic: University of Manchester Identifying Sustainable Industrial Options

10.20-11.00 Tim D.H. Bugg: University of Warwick Production of Aromatic Chemicals from Lignin using Bacterial Lignin-degrading Ezymes

11.00-11.30 Coffee break

Session 3: Chair Polly Arnold: University of Edinburgh11.30-12.10 Krijn P. de Jong: Utrecht University Nanostructured Catalysts for more Sustainable Production of Fuels and Chemicals

12.10-12.50 Matthew Davidson: University of Bath Robust and Benign Initiators for the Solvent-free, Stereoselective Polymerization of rac-Lactide

12.50-14.00 Lunch break

Session 4: Chair Nick Westwood: University of St Andrews14.00-14.40 Dieter Vogt: University of Edinburgh Ru-Catalyzed Direct Amination of (Bio)Alcohols

14.40-15.20 Nicholas J. Turner: University of Manchester Design and Evolution of New Biocatalysts for Organic Synthesis 15.20-16.00 Phil Dyer: University of Durham Moulding biomass with clays and mixed metal oxides

16.00-16.30 Tea break

Session 5: Chair Bob Tooze: Sasol UK16.30-17.10 Bert F. Sels: Universiteit Leuven Routes for Production of Value-added Chemicals from Cellulose by Liquid-phase Catalytic Processing

17.10-18.10 Graham J. Hutchings: Cardiff University Synthesis and Catalysis using Gold Nanoalloys for the Conversion of Renewable Substrates 19.30 Symposium Dinner: Golf Hotel St Andrews

Tuesday March-26th

Session 6: Chair Andrew Smith: University of St Andrews9.00-10.00 Matthias Beller: Universität Rostock Catalysis: A Key Enabling Technology for Sustainable Chemical Production and future Energy Technologies

10.00- 10.30 Thibault Cantat: Iramis Institute A Diagonal Approach to the Catalytic Chemical Recycling of CO2

10.30-11.00 Adam Harvey: Newcastle University A Continuous Screening and Process Development Platform for Solid-catalysed Liquid Phase Reactions

11.00-11.30 Coffee break

Session 7: Chair: Paul Kamer: University of St Andrews11.30-12.00 Ronan Bellabarba: SASOL/ University of St Andrews A Future Biobased Economy; Opportunities and Challenges from an Industrial Perspective 12.00-12.30 Claire Halpin: University of Dundee Manipulating Lignin Biosynthesis for Industrial Processes

12.30-13.30 James A. Dumesic: University of Wisconsin Strategies for Catalytic Conversion of Lignocellulosic Bio mass to Fuels and Chemicals

13.30-14.30 Lunch and closing symposium

Catalytic Conversion of Lignin and Humins

B.M. Weckhuysen

Utrecht University, Debye Institute for Nanomaterials Science, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands

E.mail: b.m.weckhuysen@uu.nl

Lignin is one the three major components of lignocellulosic biomass and holds great potential for the sus-tainable production of aromatics and phenolics. The catalytic valorization of the lignin fraction of biomass is highly challenging, however, and has met with limited success. The chemocatalytic conversion of the poly-saccharide components of lignocellulose to chemicals and fuels, on the other hand, has been better devel-

oped. Such conversions often involve a hydrothermal treatment under acidic conditions, such as is the case for the production of levulinic acid from cellulose. Such (acidic) hydrothermal treatments often result in the

formation of a new polymeric byproduct called humins, though, to which a large part of the biomass can be lost. Humins and lignin have in common that both these polymers are difficult to convert, but need to

be valorized to increase the economic viability of a biorefinery process. The recalcitrance of these renewable feedstocks is related to their limited (lignin) or complete (humins) insolubility and highly heterogeneous

nature. This lecture focuses on our recent efforts to solubilize and catalytically convert humins and lignin into value-added chemicals. Attention will be placed on quest for analytical methods to characterize the different properties of lignin and humins, as well as on the physicochemical stability of catalytic solids in the process-

ing media required for solubilizing this recalcitrant feedstock.

Catalytic Processes Utilizing CO2 as C-1 Building Block: Challenges and Opportunities

Walter Leitner

Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany;

e-mail: leitner@itmc.rwth-aachen.de

The anthropogenic emission of carbon dioxide (CO2) is a major concern of global importance. Howev-er, carbon dioxide is not only a problematic waste material, it can on the other hand find use in inno-

vative chemical processes. Given the difference in scale of the energetic and chemical use of our carbon resources (based on crude oil, it is approximately 93:7), the question arises how the chemical utilization of CO2 can be implemented into a general strategy for a global carbon balance. Thus, the question to be asked in this context is not only “How much can we reduce the CO2 emission?”, but more importantly

“What can we do with CO2”?

This presentation highlights the potential impact and scientific challenges associated with the use of CO2 as building block [1]. They will be illustrated for the production of polymers from CO2 and epox-

ides, the hydrogenation of CO2 to formic acid [2] and methanol [3], and the direct carboxylation of C-H bonds [4].

[1] Chemical Technologies for Exploiting and Recycling CO2 into the Value Chain M. Peters, B. Köhler, W. Kuckshinrichs, W. Leitner, P. Markewitz, T.E. Müller ChemSusChem. 2011, 4, 1216 - 1240.

[2] Continuous-Flow Hydrogenation of Carbon Dioxide to Pure Formic Acid using an Integrated scCO2 Process with Immobilised Catalyst and Base S. Wesselbaum, U. Hintermair, W. Leitner, Angew. Chem. Int. Ed. 2012, 51, 8585 - 8588.

[3] Hydrogenation of Carbon Dioxide to Methanol using a Homogeneous Ruthenium-Phosphine Catalyst S. Wesselbaum, T. vom Stein, J. Klankermayer, W. Leitner Angew. Chem. Int. Ed. 2012, 51, 7499 - 7502.

[4] Carboxylation of Arene C-H Bonds with CO2 – A DFT-Based Approach to Catalyst Design A. Uhe, M. Hölscher, W. Leitner Chem. Eur. J. 2012, 18, 170 - 177.

Identifying Sustainable Industrial Options

Adisa Azapagic

School of Chemical Engineering and Analytical Science, The University of Manchester, M13 9PL, UKadisa.azapagic@manchester.ac.uk

Achieving sustainability requires balancing economic, environmental and social aspects [1]. The awareness of and interest in sustainability are growing but the main question still remains unanswered: what indus-

trial activities and systems could be considered sustainable? This paper looks into the subject of measuring sustainability of industrial systems using a life cycle approach [2,3]. It demonstrates on a number of case

studies how sustainability assessment can be applied to help industry (and consumers) identify more sus-tainable options.

Figure 1. A life cycle approach to identifying sustainable options

References1. Azapagic, A. and S. Perdan (eds.) (2011). Sustainable Development in Practice: Case Studies for Engineers and Scientists. 2nd ed. John Wiley & Sons, Chichester, pp521.2. Azapagic, A. and H. Stichnothe (2009). A Life Cycle Approach to Measuring Sustainability. Chemistry Today. International Journal of Chemistry and Biotechnology. V27 (1) 44-46.3. Azapagic, A., R. Burkinshaw, S. Chahal, J. Leadbitter and M. Pitts (2011). Measuring Carbon Footprints, TCE, 24-26, March 2011.

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Production of Aromatic Chemicals from Lignin using Bacterial Lignin-degrading Enzymes

T.D.H. Bugg, E.M. Hardiman, P.D. Sainsbury, and C.R. Taylor

Department of Chemistry, University of Warwick, Coventry CV4 7ALE.mail T.D.Bugg@warwick.ac.uk

The lignin content of lignocellulose and lignin-containing wastes represents a possible resource for produc-tion of aromatic chemicals, if efficient biocatalytic routes for lignin degradation can be found. The enzymol-

ogy of fungal lignin degradation is well-studied, whereas the enzymology of bacterial lignin degradation is much less well known, but offers potential advantages for biotechnology [1]. Using a colorimetric assay for lignin degradation [2], we have identified that peroxidase DypB from Rhodococcus jostii RHA1 is a

lignin peroxidase that is activated by Mn2+, and shows activity with a b-aryl ether lignin model compound, with Kraft lignin, and with lignocellulose [3]. Stopped flow kinetic analysis establishes that DypB is able to

oxidise either Mn2+ or b-aryl ether, at similar rates [3]. Using the colorimetric assay, we have also identi-fied a number of novel lignin-degrading bacteria from soil samples, which show higher activity for lignin

degradation [4]. A number of low molecular weight metabolites have been identified from cultures of these bacteria with lignocellulose, which can be rationalised in terms of lignin breakdown pathways. The seminar will also describe gene deletion studies carried out on genes involved in vanillic acid breakdown, in which

we have observed much higher yields of aromatic breakdown products.

References1. T.D.H. Bugg, M. Ahmad, E.M. Hardiman, and R. Singh, Curr. Opin. Biotech., 22, 394-400 (2011).2. M. Ahmad, C.R. Taylor, D. Pink, K. Burton, D. Eastwood, G.D. Bending and T.D.H. Bugg, Mol. Biosys tems, 6, 815-821 (2010)3. M. Ahmad, J.N. Roberts, E.M. Hardiman, R. Singh, L.D. Eltis, and T.D.H. Bugg, Biochemistry, 50, 5096-5107 (2011)4. C.R. Taylor, E.M. Hardiman, M. Ahmad, P.D. Sainsbury, P.R. Norris, and T.D.H. Bugg, J. Appl. Micro biol., 113, 521-530 (2012).

Nanostructured catalysts for more sustainable production of fuels and chemicals

Krijn P. de Jong

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials ScienceUtrecht University, The Netherlands; k.p.dejong@uu.nl

Synthesis gas, a mixture of CO and H2, can be produced from any carbon-containing feedstock such as natural gas, coal or biomass as well as from hydrogenation of CO2. Supported metal catalysts are used for

synthesis gas conversion to alternative fuels and chemicals. With the advent of nanotechnology in catalysis even more emphasis is put on the effects of size and shape of metal nanoparticles on their performance in synthesis gas conversion [1]. Here we focus on the effects of size and distribution of nanoparticles in sup-

ported Co, Cu and Fe catalysts on their performance.

For supported cobalt catalysts we report the effects of particle size and distribution to arrive at high activ-ity and stability for conversion of synthesis gas to higher alkanes [2]. For copper catalysts large effects of

nanoparticle distribution on stability in methanol synthesis are apparent [3]. Favorable effects of a uniform distribution of Fe nanoparticles on an alpha-alumina or carbon nanofiber support for FTO (Fischer Tropsch to lower Olefins) performance are presented [4]. For the latter catalysts effects of iron particle size and pro-

moters (Na+S) are also discussed.

References1. R.A. van Santen, Acc. Chem. Res., 2009, 42, 57–66; G.A. Somorjai et al., Topics in Catal., 2008, 49 , 126-135. 2. G.L. Bezemer et al., J. Am. Chem. Soc. 128 (2006) 3956-3964; J.P. den Breejen et al., J. Am. Chem. Soc. 131 (2009) 7197-7203; T.M. Eggenhuisen et al., J. Am. Chem. Soc., 2010, 132, 18318–18325.3. G. Prieto, J. Zecevic, H. Friedrich, K.P. de Jong and P.E. de Jongh, Nature Mater. (2012) DOI: 10.1038/ NMAT3471.4. H.M. Torres, J.H. Bitter, C.B. Khare, M. Ruitenbeek, A. Iulian Dugulan and K.P. de Jong, Science, 2012, 335, 835-838.

Robust and Benign Initiators for the Solvent-free, Stereoselective Polymerization of rac-Lactide

Matthew G. Davidson, S.D. Bull, Amanda J. Chmura, Christopher J. Chuck, Catherine J. Frankis, Matthew D. Jones and Lois B. Manton

University of Bath, Centre for Sustainable Chemical Technologies, Bath BA2 7AY UK.m.g.davidson@bath.ac.uk

Polylactide (PLA) is an environmentally and economically viable alternative to traditional oil-based plastics. Industrial processes to form PLA currently use Sn-based initiators which operate with no stereocontrol. For PLA to fulfil its true potential in commodity plastic applications, non-toxic initiators are required that are active and stereoselective for the production of PLA in the melt with enhanced mechanical and physical properties

We have developed a series of C3-symmetric Group 4 metal complexes which are able to produce almost pure heterotactic PLA in the melt. The mechanism of the polymerization has been probed by the preparation of enantiopure C3-symmetric catalysts and comparison of polymerization kinetics with those of racemic analogues. Investigation of these initiators under laboratory and industrial conditions has identified some promising alternatives to current Sn-based initiators for the stereoselective polymerization of rac-lactide to yield PLA with enhanced physical properties.

Figure: A Hf(IV) complex supported by a C3-symmetric amine tris(phenolate) utilized in this work and an in situ FTIR

spectrum of a polymerization under industrial conditions

Ru-Catalyzed Direct Amination of (Bio)Alcohols

D.L.L. Pingen1, C. Müller2 and D. Vogt1

1) University of Edinburgh, School of Chemistry, EaStChem, Edinburgh EH9 3JJ, UK. d.vogt@ed.ac.uk2) Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Germany. c.mueller@

fu-berlin.de

The recently developed direct amination of alcohols with ammonia opens new possibilities for the transfor-mation of renewable feedstocks for building-block synthesis.[1-4]

A range of biomass-derived alcohols was converted into primary amines in high to excellent selectivity, deriving interesting potential building blocks for polymers, intermediates and fine chemicals. The catalysts

proved to be stable in a couple of consecutive runs without product removal. In order to improve the catalyst performance, mechanistic insight has to be gained. The RuHCl(CO)(PPh3)3/Xantphos system shows excel-lent activity in this reaction[4]. Varying the Ru-precursor and the ligands, and the use of various additives

provided new insight on the reaction mechanism. Catalytically active and inactive intermediates have been identified by NMR studies. It was shown how inactive dihydrido species formed during the reaction can be

reactivated.Additives like bases or ketones have a profound effect, which can lead to total deactivation or increase in

reaction rate. Based on these insights, a possible mechanism for the direct amination of alcohols will be sug-gested.

Figure: Hydrogen shuttling concept (left), the RuHCl(CO)(PPh3)(Xantphos) catalyst structure in the crystal (middle), and repeti-tive batch conversion of cyclohexanol with a Ru3(CO)12/acridine-based diphosphine system (right).

References[1] C. Gunanathan, D. Milstein, Angew. Chem. Int. Ed. 2008, 47, 8661-8664.[2] S. Imm, S. Bähn, L. Neubert, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2010, 49, 8126-8129.[3] D. Pingen, C. Müller, D. Vogt, Angew. Chem. Int. Ed. 2010, 49, 8130-8133.[4] S. Imm, S. Bähn, M. Zhang, L. Neubert, H. Neumann, F. Klasovsky, J. Pfeffer, T. Haas, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 7599-7603.

Design and Evolution of New Biocatalysts for Organic Synthesis

Nicholas J. Turner

School of Chemistry, University of Manchester, Manchester Institute of Biotechnology, 131 Princess Street, Manchester, M1 7DN, UK

e-mail: Nicholas.turner@manchester.ac.uk

This lecture will describe recent work from our laboratory aimed at developing new biocatalysts for enan-tioselective organic synthesis.1 For example, monoamine oxidases (MAO-N) are a family of enzymes that catalyze the oxidation of amines to imines. MAO-N can be used as biocatalysts to obtain enantiomerically

pure chiral amines by deracemisation or desymmetrisation of substrates.2 Recently new variants of MAO-N (D5, D10, D11) have been developed via a combination of directed evolution and rational design in order to

broad the enzyme’s substrate specificity.

The new mutants have been used for the deracemisation of primary and secondary amines such as (R)-4-chlorobenzhydrylamine (building block for the synthesis of Levocetirizine), (S)-1-phenyl-1,2,3,4-tet-rahydroisoquinoline (building block for the synthesis of Solifenacin) and the two alkaloids (R)-Harmicine

and (R)-Eleagnine.

Levocetirizine Solifenacin (R)-Eleagnine (R)-Harmicine

The integration of several biocatalytic transformations into multi-enzyme cascade systems has also been a focus of recent work in our laboratories. In this context MAO-N has been used in combination with other biocatalysts and chemocatalysts in order to complete a cascade of enzymatic reactions. In particular, a bi-ocatalytic tandem reaction combining MAO-N and ATHase has been developed for the deracemisation of

1-methyl tetrahydroisoquinoline, nicotine and 2-substituted pyrrolidine3 and a combination of MAO-N and ω-transaminases was employed for a one-pot synthesis of enantiopure 2,5-disubstituted pyrrolidines starting

from different 1,4-diketones.

1 N.J. Turner, Nature Chem. Biol., 2009, 8, 567-573.2 R. Carr et al., Angew. Chem. Int. Ed., 2003, 42, 4807-4810.3 V. Koehler et al., Nature Chem., 2012, 4, in press.

Moulding biomass with clays and mixed metal oxides

Ben A. Coombs,a Matthew R. Gibbings,a Louise F. Gildea,a H. Christopher Greenwell,a,b Edward Leslie,a Li Li,a and Philip W. Dyera,*

a Centre for Sustainable Chemical Processes, Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK, (Email: p.w.dyer@durham.ac.uk)

Layered double hydroxides (LDHs), [(MII)1–x(MIII)x(OH)2]x+ [An–]x/n.yH2O, are an important class of readily

prepared synthetic anionic clay material, which comprise non-covalently bonded extended 2D cationic sheets with interlayer galleries filled by charge-balancing anions (An–) and water (Fig. 1). LDHs find widespread use as adsorbents, polymer stabilizers, anion exchangers, acid residue scavengers, and as acid/base catalysts.1,2 One of their most important roles is as precursors to the corresponding mixed metal oxides (MMOs), which are formed by calcination, and used extensively as catalysts/catalyst precursors in a range of industrial applications.3

Here, multipronged experimental and theoretical studies will be described, which probe the thermal behaviour of various Mg/Al LDH materials [e.g. Al2Mg6(OH)16CO3·4H2O] and their transformation into their corresponding MMO siblings.4 Recent investigations into the use of these oxide systems in mediating fatty acid transesterification and ketonic decarboxylation,5 two key transformations in processes for up-grading biomass to fuels and chemicals,6,7 will be outlined.

References1. V. Rives (Ed.), Layered Double Hydroxides: Present and Future, Nova Publishers, Hauppauge, NY, USA, 2011.2. D.P. Debecker, E.M. Gaigneaux, and G. Busca, Chemistry, 2009, 15, 3920.3. F. Figueras, Top. Catal., 2004, 29, 189.4. B.A. Coombs, J.C. Collings, D.L. Geatches, B. Grégoire, H.C. Greenwell, and P.W. Dyer, manuscript in preparation. 5. L.F. Gildea, L. Li, H.C. Greenwell, and P.W. Dyer, manuscript submitted. 6. A. Navajas, I. Campo, G. Arzamendi, W.Y. Hernandez, L.F. Bobadilla, M.A. Centeno, J.A. Odriozola, and L.M. Gandia, Applied Catalysis B: Environmental, 2010,100, 299.7. J.C. Serrano-Ruiz, A. Pineda, A.M. Balu, R. Luque, J.M. Campelo, A.A. Romero and J.M. Ramos-Fernández, Cat. Today, 2012, 195, 162.

Fig. 1. DFT-calculated structure of 3:1 Mg/Al carbonate LDH (left); observed and calculated powder X-ray diffraction patterns for 3:1 Mg/Al carbonate LDH (right).

Routes for production of value-added chemicals from cellulose by liquid-phase catalytic processing

Authors: Bert F. Sels

Address: Centre for Surface Chemistry and Catalysis, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Heverlee (Belgium), E.mail bert.sels@biw.kuleuven.be.

The selective conversion of cellulosic biomass and other carbohydrates by mono- and bifunctional catalysts is of major industrial importance, and improving its efficiency and selectivity towards value-added chemicals remains a prime

objective. Examples are the reductive splitting of cellulose to sorbitol and mannitol, sorbitans and isosorbide, precur-sors in the production of plastics and pharmaceuticals, and saccharification of cellulose to glucose, which amongst

others, offers a feedstock for bio-ethanol production, or conversion of cellulose to levulinic acid, which can for instance be used in the synthesis of bisphenol A substitutes [1]. Carbohydrates may also be a source towards new building likes like alfa-hydroxy esters [2]. We recently reviewed new advances in the catalytic conversion of cellulose [3], requiring the design of efficient, multifunctional systems with accessible acid and metal sites. This presentation overviews the

usefulness of chemocatalytic systems for the selective transformation of cellulose into chemicals. The reactivity of var-ious sources of cellulose towards chemical reaction is discussed first in relation to its crystallinity and chemical struc-ture using X-ray diffraction, FT-IR and 13C NMR. The impact of various cellulose mechanical, physical and chemical pre-treatment methods such as ball milling and atmospheric plasma will be systematically shown for a set of chemical reaction types such as hydrolysis and reductive splitting. The aspect of accessibility (with regard to active surface area) during hydrolysis and the importance (or not) of solid-solid phase interactions will be discussed in a series of catalytic systems using classic porous materials such as zeolites [4], porous carbon [5], carbon fibers [6], soluble branched poly-mers [7] and (in)soluble heteropolyacids [8]. (Dis)Advantages such as active site density, active site compartmentaliza-

tion and mobility and sorption aspects will be highlighted into more detail.

References1. a) Van De Vyver, S., Helsen, S., Geboers, J., Yu, F., Thomas, J., Smet, M., Dehaen, W., Román-Leshkov, Y., Hermans, I., Sels, B.F., ACS Catalysis, 2012, 2, 2700; b) Van De Vyver, S., Geboers, J., Helsen, S., Yu, F., Thomas, J., Smet, M. , Dehaen, W., Sels, B.F., Chem. Commun., 2012, 48, 3497. 2. F. de Clippel, M. Dusselier, R. Van Rompaey, P. Vanelderen, J. Dijkmans, E. Makshina, L. Giebeler, S. Oswald, G. V. Baron, J. F. M. Denayer, P. P. Pescarmona, P. A. Jacobs and B. F. Sels, J. Am. Chem. Soc., 2012, 134, 10089; L. Li, C. Stroobants, K. Lin, P. A. Jacobs, B. F. Sels and P. P. Pescarmona, Green Chem., 2011, 13, 1175; M. Dusselier, P. Van Wouwe, F. de Clippel, J. Dijkmans, D. W. Gammon and B. F. Sels, ChemCatChem, 2013, DOI: 10.1002/cctc.201200476.3. a) S. Van de Vyver, J. Geboers, P. A. Jacobs, B. F. Sels, ChemCatChem 2011, 3, 82; b) J. A. Geboers, S. Van de Vyver, R. Ooms, B. Op de Beeck, P. A. Jacobs, B. F. Sels, Catal. Sci. Technol. 2011, 1, 714.4. J. Geboers, S. Van de Vyver, K. Carpentier, P. Jacobs, B. Sels, Chem. Commun. 2011, 47, 5590.5. S., Van de Vyver; L., Peng; J., Geboers; H., Schepers; F., De Clippel; C. J., Gommes; B., Goderis; P. A., Jacobs; B. F., Sels, Green Chem-istry, 2010, 12, 1560.6. a) S., Van de Vyver; J., Geboers; M., Dusselier; H., Schepers; T., Vosch; L., Zhang; G., Van Tendeloo; P. A., Jacobs; B. F., Sels, Chem-SusChem, 2010, 3, 698. b) Stijn Van de Vyver, Jan Geboers, Wouter Schutyser, Michiel Dusselier, Pierre Eloy, Emmie Dornez, Jin Won Seo, Christophe M. Courtin, Eric M. Gaigneaux, Pierre A. Jacobs, Bert F. Sels, ChemSusChem, 2012, 5, 1549. c) B. Op de Beeck, J. Ge-boers, S. Van de Vyver, J. Van Lishout, J. Snelders, W. J. J. Huijgen, C. M. Courtin, P. A. Jacobs, B. F. Sels, ChemSusChem, 2013, DOI: 10.1002/cssc.201200610.7. S. Van de Vyver, J. Thomas, J. Geboers, S. Keyzer, M. Smet, W. Dehaen, P. A. Jacobs, B. F. Sels, Energy Environ. Sci 2011, 4, 3601.[8] a) J. Geboers, S. Van de Vyver, K. Carpentier, K. de Blochouse, P. Jacobs, B. Sels, Chem. Commun. 2010, 46, 3577; b) J. Geboers, S. Van de Vyver, K. Carpentier, P. Jacobs, B. Sels, Green Chem. 2011, 13, 2167.

Synthesis and catalysis using gold nanoalloys for the conversion of renewable substrates

Graham J. Hutchings

Cardiff Catalysis Institute, School of Chemistry, Cardiff University, CF10 3AT, UK

Catalysis and in particular selective oxidation and hydrogenation continues to play a key role in the manufac-ture of chemical intermediates and there is a continuing requirement to identify and design new effective re-dox catalysts. There have been a regular progression of new catalytic materials and one of these has been the

identification that gold in nanoparticulate form is exceptionally effective as a redox catalyst. This presentation will explore the latest developments using supported gold nanoalloys as heterogeneous catalysts. Alloying

gold with other metals can enhance the activity and these catalysts are effective for the oxidation of alcohols as well as the direct synthesis of hydrogen peroxide. The synthesis of active catalysts will be described as well as their characterization. Aspects of the latest research on these topics will be presented, in particular the use

of these catalysts for the oxidation of glycerol under mild reaction conditions.

Catalysis: A Key Enabling Technology for Sustainable Chemical Production and future Energy Technologies

Matthias Beller

Leibniz-Institut für Katalyse an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, matthias.beller@catalysis.de

Despite numerous important methodological advancements in all areas of chemistry, still most organic synthesis as well as the industrial production of chemicals can be improved. Currently, more than 80% of all products of the chemical industry are made via catalysis. In this regard, the development of new and more efficient catalysts constitutes a key factor for achieving a sustainable production of all kinds of chemi-cals today and in the future. Here, several major challenges will be presented in the talk. Furthermore, it will be shown that recently developed molecular-defined as well as nano-structured iron catalysts enable us to perform a multitude of redox processes with high yields and selectivity.[1-10] Specific examples which demonstrate the potential

of catalytic processes with bio-relevant metal complexes compared to more traditional catalytic reactions will include hydrogenations and dehydrogenations, as well as oxidation reactions.

References[1] S. Das, B. Wendt, K. Möller, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2012, 51, 1662.[2] M. Zhang, S. Imm, S. Bähn, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2012, 10.1002/ anie.201108599, in press.[3] M. Nielsen, A. Kammer, D. Cozzula, H. Junge, S. Gladiali, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 9593-9597.[4] M. Zhang, S. Imm, S. Bähn, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 11197-11201.[5] D. Hollmann, F. Gärtner, R. Ludwig, E. Barsch, H. Junge, M. Blug, S. Hoch, M. Beller, A. Brückner, An gew. Chem. Int. Ed. 2011, 50, 10246-10250.[6] S. Imm, S. Bähn, M. Zhang, L. Neubert, H. Neumann, F. Klasovsky, J. Pfeffer, T. Haas, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 7599-7603.[7] S. Das, D. Addis, L. R. Knöpke, U. Bentrup, A. Brückner, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 9180-9184.[8] G. Wienhöfer, I. Sorribes, A. Boddien, F. Westerhaus, K. Junge, H. Junge, R. Llusar, M. Beller, J. Am. Chem. Soc. 2011, 133, 12875-12879.[9] A. Boddien, D. Mellmann, F. Gärtner, R. Jackstell, H. Junge, P. J. Dyson, G. Laurenczy, R. Ludwig, M. Beller, Science 2011, 333, 1733-1736.[10] S. Fleischer, S. Zhou, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 5120-5124.

A Diagonal Approach to the Catalytic Chemical Recycling of CO2

T. Cantat

Atomic Energy and Alternative Energies Commission (CEA)Iramis Institute, SIS2M CEA/CNRS Research Unit

91191 Gif-sur-Yvette (France)thibault.cantat@cea.fr

While greenhouse gases emissions are reaching alarming levels, fossil fuels still represent 80% of the world energy portfolio and 95% of our chemical commodities rely on non-renewable resources, namely hydrocar-

bons. In this context, utilizing CO2 as a C1 building block to produce platform chemicals as an alternative to petrochemistry has a double advantage of reusing CO2 while sparing fossil resources and avoiding CO2 emissions from their use. We have developed a strategy relying on the simultaneous use of a functionaliz-ing reagent and a reductant that can be independently adjusted to perform the reductive functionalization of CO2. The so-called diagonal approach will be discussed and exemplified with novel catalytic processes to

convert CO2 to formamides, formamidines and N-heterocycles, using hydrosilanes and amines.1-3 These new organo-catalytic reactions circumvent the use of toxic and expensive metals for the formylation of a variety

N–H bonds (in amines, imines, hydrazines and N-heterocycles) and co-recycles CO2 with polymethylhydros-iloxane (PMHS), a by-product of the silicones industry.

References1. C. Das Neves Gomes, O. Jacquet, C. Villiers, P. Thuéry, M. Ephritikhine, T. Cantat, Angew. Chem. Int. Ed. 2012, 51, 187.2. O. Jacquet, C. Das Neves Gomes, M. Ephritikhine, T. Cantat, J. Am. Chem. Soc. 2012,134, 2934.3. O. Jacquet, C. Das Neves Gomes, M. Ephritikhine, T. Cantat, ChemCatChem 2013,5, 117.

A Continuous Screening and Process Development Platform for Solid-catalysed Liquid Phase Reactions

Authors: A.P.Harvey, A.N. Phan, V. Eze, F. Mohd Rasdi, R. AbernethyAddress: CEAM, Newcastle University, Newcastle upon Tyne NE1 7RU

Email: adam.harvey@ncl.ac.uk

It is often advantageous to optimise processes in the laboratory at the smallest scale possible, particularly when reagents or waste disposal are expensive. It is also advantageous to do this using continuous mode rath-er than batch, as it can, in principle, traverse the parameter space of interest for a given reaction much more efficiently and rapidly. This has led to designs of laboratory-scale screening reactor based on microchannels.

However, it is difficult to accommodate solids in such reactors. One way in which solids can be accommodated in laboratory-scale screening reactors is to use “mesoscale”

oscillatory baffled reactors (OBRs). In these reactors powders, granules or beads can be uniformly suspended to form a catalyst bed, whilst maintaining plug flow. A particularly useful feature is that solids suspension and plug flow can be maintained for long residence times, as the reactor is able to ensure plug flow at very low flow rates, thereby minimizing consumption of reagents. High degrees of plug flow allow rapid move-

ment between conditions and “dynamic Design of Experiments” (in which one or more input parameters are continually changing). A range of OBR designs have been developed at Newcastle over the last 5 years allow screening of reactions of a few hours residence time in a reactor a few tens of mL in volume at flowrates of a

few mL per hour.

Figure: An oscillatory baffled reactor

Various baffle designs of reactor were assessed to determine where desirable degrees of plug flow could be achieved, and different designs were used for different applications:

1. Multidimensional dynamic screening with online monitoring has been demonstrated for an imine synthesis reac-tion. The molar ratio and residence time of the reaction were continually altered, to scan the parameter space more rapidly (than one-at-a-time dynamic screening). Kinetic constants were calculated based on this data.

2. Investigation of a homogeneously catalysed biodiesel reaction revealed new sets of operating conditions that allow the reaction to be completed in under 2 minutes, rather than the conventional 1-2h, allowing a reduction in reactor size of a factor of between 30 and 60.Also, crystallization of L-glutamic acid has been investigated, and new crystal forms discovered, and heterogeneous catalysts for biodiesel production have been assessed in situ.

A Future Biobased economy; opportunities and challenges from an industrial perspective

Ronan Bellabarba

SASOL UK Technology Ltd, School of Chemistry, University of St Andrews, KY16 9ST, UKRonan.Bellabarba@eu.sasol.com

The exploitation of renewable resources is becoming an increasingly accepted part of future chemical and energy scenarios. New feedstocks and new technologies offer both new products and new routes to existing

products. Realising this potential will depend on the successful balancing of factors such as cost, market demand and acceptance, technology, timescales and demonstrable sustainability benefits. This talk will aim to

provide an industrial perspective on this complex and evolving landscape.

Manipulating lignin biosynthesis for industrial processes

Authors: Claire Halpin

Address: Division of Plant Sciences, College of Life Sciences, University of Dundee at the JHI, Invergowrie, Dundee DD2 5HN, UK.

E.mail c.halpin@dundee.ac.uk

Plant biomass is a major renewable feedstock for bioenergy generation, biofuel production and industrial biotechnology. Such biomass is mainly composed of cell walls made of lignocellulose – a composite struc-

ture of sugar polymers (cellulose and hemicellulose) and the phenolic polymer, lignin. The hydrophobicity of lignin helps to waterproof and confer structural rigidity to cells, particularly in the vascular system of plants.

By encrusting the other wall polymers, lignin significantly influences the ease with which biomass can be ‘deconstructed’, both chemically and biochemically, for use in industrial processes. Lignin is the product of a

10 enzyme biochemical pathway within plants which has been intensively studies over the past 20 years. Each of the genes on the pathway has been identified and can be manipulated genetically to modify the content, composition, and/or structure of lignin, often without adverse effects on plant growth. This opens the door

for the production of ‘designer’ biomass with lignin structures or deconstruction properties suited to specific industries.

Major bonds in lignin:

References1. P. Daly, M. Maluk, M. Zwirek, C. Halpin, ‘Lignin Biosynthesis and Lignin manipulation’. In: Stability of Complex Carbohydrate Structures: Biofuels, Foods, Vaccines and Shipwrecks. S. Harding Ed. RSC Publishing 2013.

Strategies for Catalytic Conversion of Lignocellulosic Biomass to Fuels and Chemicals

James A. DumesicDepartment of Chemical and Biological Engineering

University of Wisconsin – Madison

Environmental and political issues created by our dependence on fossil fuels, such as global warming and na-tional security, combined with diminishing petroleum resources are causing society to search for new renew-

able sources of energy and chemicals, and an important sustainable source of organic fuels, chemicals and materials is plant biomass. We will show how H2 and CO2 can be produced by aqueous-phase reforming of

oxygenated hydrocarbons derived from carbohydrates at low temperatures (e.g., 500 K) over supported metal catalysts, and we will address how the aqueous-phase reforming process can be carried out over bimetallic

catalysts (e.g, PtRe) to produce C5 and C6 mono-functional hydrocarbons, such as carboxylic acids, alcohols, and ketones. We will show that the active sites on these bimetallic catalysts are bi-functional in nature, where

the more reducible metal (Pt) catalyzes hydrogenation/dehydrogenation processes, and the more oxophilic metal (Re) provides hydroxyl groups that facilitate acid-catalyzed reactions. We will then present strategies for the catalytic conversion of the C5 and C6 sugars present in hemi-cellulose and cellulose, respectively. We will address how the hemi-cellulose fraction of lignocellulosic biomass can be converted to furfural, furfuryl

alcohol, and levulinic acid; and we will address how cellulose can be converted to hydroxymethylfurfural (HMF) and levulinic acid. Finally, we will present results for the catalytic conversion of levulinic acid to

gamma-valerolactone (GVL). We will show how GVL can be converted to gasoline and jet fuel by catalytic decarboxylation to produce 1-butene, combined with alkene oligomerization, and we will show how GVL can

be used as a solvent for biomass processing.

Poster sessions

Authors:

P1 C. S. Lancefield and N. J. WestwoodP2 Byron J Truscott, George C Fortman, Alexandra M. Z. Slawin, Steven P. NolanP3 L. Obrecht, P. J. Deuss, W. Laan and P. C. J. KamerP4 Adrián Gómez-Suárez, Ruben S. Ramón, Stéphanie Dupuy, Yoshihiro Oonishi, Sebastien Meiries, Alexandra M. Z. Slawin, Steven P. NolanP5 Stephanie Dupuy and Steven P. NolanP6 Roberto Caporali Prof. Chris Hardacre, Dr. Alex Gouget, Dr. Dave ThompsettP7 R. Ben-Giat, D. R. Carbery, M. G. Davidson, F. Dunn, P. K. Ivanova-Mitseva, B. J. Jeffery and A. W. ThomasP8 C. Finn, J. B. LoveP9 D. Minett, J O’Byrne, M. Jones, P. Plucinski, D.MattiaP10 David J. Lunn, Jamie Clifton, Paul G. Pringle and Ian MannersP11 Isobel H. Marra, Z. R. Turnera, A. I. Germerotha, R. M. Bellabarbab, R. P. Toozeb and P. L. ArnoldaP12 Panagiota Pelekanaki1, Luis-Gómez Hortigüela, Furio Corà1, C. Richard A. CatlowP13 D. L.L. Pingen, Prof. Dr. C. Müller,2 Prof. Dr.D. VogtP14 William J. Kerr and Richard J. MuddP15 Dorota D. Plaza, Andrew Clark, Alexei A. LapkinP16 Li Li, Philip Midgley, Hugh Christopher Greenwell , Philip Dyer P17 William J. Kerr, Marc Reid, and T. TuttleP18 R. E. Owen, J. P. O’Byrne, M. D. Jones, D. Mattia, P. Plucinski and S. I. PascuP19 J. S. Rowbothama, P. W. Dyera, H. C. Greenwellb, L. Lia,b and M. K. Theodorouc,dP20 M.E. Potter and R. RajaP21 Thomas R. Forder, Matthew D. Jones, Matthew G. DavidsonP22 Louis C. Morrill and Prof. Andrew D. SmithP23 F. Tran, D. M. U. K. Somisara, T. Lebl, N.J. Westwood and P. C. J. KamerP24 Alberto Cavalieri, Dieter Vogt, Christian MüllerP25 Christopher J. Chuck, Matthew G. Davidson, Gerrit Gobius du Sart, Petya K. Ivanova-Mitseva, Gabriele I. Kociok-Köhn and Lois B. Manton.

P26 Evert Boymans, Peter Witte, Dieter Vogt

P1: Isolation and Characterization of Lignin from Local Brewer’s Spent Grain

C. S. Lancefield and N. J. Westwood*

University of St. Andrews, School of Chemistry, EaStChem, St. Andrews, Fife, KY16 9ST, UK.njw3@st-andrews.ac.uk

Worldwide production of brewer’s spent grain, a co-product of the brewing process, has been estimated to be 30x109 Kg per annum.1 Traditionally this material has been discarded or used as animal feed but attention is increasingly turning towards finding novel, more profitably and/or more energy efficient uses of this waste stream.2 One way to achieve this goal may be the development processes capable of delivering valuable aro-matic chemicals from the lignin constituent of brewer’s spent grain. As such we have undertaken the extrac-tion and characterization of lignin derived from the spent grain of a local Scottish whisky distillery3 and have started initial investigations into the chemistry needed for lignin valorization.

References1. D. Cook, (2011, November/December), Brewer’s Guardian,60-63.2. a) A. L. McCarthy, Y. C. O’Callaghan, C. O. Piggott, R. J. FitzGerald and N. M. O’Brien, Proceedings of the Nutrition Society, 2013, 72, 117-125. b) S. Aliyu, M. Bala, African Journal Of Biotechnology, 2011, 10, 324-331.3. We would like to thank Francis Cuthbert of Daftmill Distillery, Cupar for his kind donation of the brewer’s spent grain used in this research.

P2: Well-defined monomeric Rh(I)-(NHC)-hydroxides: Design, Synthesis and Catalytic Po-tential

Byron J Truscott, George C Fortman, Alexandra M. Z. Slawin, Steven P. Nolan

Address: University of St. Andrews, School of Chemistry, EaStChem, St. Andrews, Fife, KY16 9ST, UK.E.mail: bt222@st-andrews.ac.uk

Herein, we report the design and synthesis of well-defined monomeric Rh(I)-hydroxide complexes bearing a series of N-heterocyclic carbene (NHC) ligands. [Rh(cod)(NHC)(OH)] complexes are prepared in a one-pot procedure from commercial [Rh(cod)Cl]2. The series of [Rh(cod)(NHC)(OH)] complexes proved successful promoters of 1,4-conjugate addition between arylboronic acids and α,β-unsaturated ketones with TON’s and TOF’s of 100,000 and 6,600 h-1,respectively.1 In addition, the [Rh(cod)(NHC)(OH)] complexes were found to successfully promote both hydrosilylation and dehydrogenative silylation of terminal alkenes with somewhat tuneable selectivity. Catalytic activity within the series of [Rh(cod)(NHC)OH] complexes is inversely proportional to the steric demand exerted by the NHC ligand on the metal. A discussion of the steric and electronic characteristics and differences is presented.2

As part of our investigations into Rh(I)-hydroxides, we report synthetic variations to complexes of the gen-eral type [Rh(cod)(NHC)OH] and chemistry associated therein. Our efforts are currently on-going in this regard and will be elucidated in more detail.

1. B. J. Truscott, G. C. Fortman, A. M. Z. Slawin and S. P. Nolan, J. Org. Biomol. Chem., 2011, 9, 7038- 7041.2. B. J. Truscott, A. M. Z. Slawin and S. P. Nolan, Dalton Trans., 2013, 42, 270-276.

P3: Artificial metalloenzymes in biphasic aqueous hydroformylation of long chain 1-alkenes

Authors: L. Obrecht, P. J. Deuss, W. Laan and P. C. J. Kamer

Address: University of St. Andrews, School of Chemistry, EaStChem, St. Andrews, Fife, KY16 9ST, UK.E.mail: pcjk@st-andrews.ac.uk

A general, easy and efficient method for site selective covalent introduction of phosphine ligands in pro-teins was used to synthesise artificial metalloenzymes.1 In this method the thiol of an introduced amino acid cysteine is selectively and stepwise modified to obtain an artificial metalloenzyme (see Fig. 1). The protein SCP-2 (Sterol Carrier Protein-2) exhibits a tunnel which is known to bind various aliphatic mol-ecules such as fatty acids and sterols.2 We mutated and modified an analogue of this protein: The SCP-2 like domain of human multifunctional enzyme type 2 (see Fig. 2).3 Using this protein as a template two artificial metalloenzymes were obtained, each of them having a catalytic phosphine-rhodium complex at the different end of the tunnel.While the aqueous biphasic hydroformylation is successful for short chain alkenes it remains problematic for long chain alkenes as the solubility of linear alkenes in water decreases logarithmically with their chain length.4 These artificial metalloenzymes are active catalysts for the biphasic hydroformylation of water insol-uble higher alkenes with chain lengths up to C18 . These mono ligated Rh-complexes show remarkably high selectivity with a linear to branched ratio close to 4 (see. Table 1)

References1. P. J. Deuss, G. Popa, C. H. Botting, W. Laan, P. C. J. Kamer, Angew. Chem. Int. Ed., 2010, 49, 5315.2. Adalberto et al., Prog. Lipid. Res., 2001, 40, 498.3. Haapalainen et al., J. Mol. Biol., 2001, 313, 1127.4. B. Cornils, W. A. Herrmann, 2004, Aqueous-Phase Organometallic Catalysis, Wiley-VCH.

P4: Synthesis and Reactivity of Digold-hydroxide Species

Adrián Gómez-Suárez, Ruben S. Ramón, Stéphanie Dupuy, Yoshihiro Oonishi, Sebastien Meiries, Alexandra M. Z. Slawin, Steven P. Nolan*

University of St. Andrews, School of Chemistry, EaStChem, St. Andrews, Fife, KY16 9ST, UK.E.mail: sn17@st-andrews.ac.uk

Despite once being considered as an inert metal, over the past decade gold has emerged as one of the most powerful synthetic tools in chemists’ toolkit. Gold complexes can catalyse a wide range of organic transformations, from C-C and C-heteroatom bond formation to rearrangement reactions. All these processes were thought to be based on the well-documented ability of a monomeric gold centre to interact with one substrate molecule, typically a C-C multiple bond, thus activating it towards nucleophilic attack. Although there is enough experimental evidence supporting the hypothesis that some gold-catalysed reactions follow this path, such as the isolation and characterisation of reaction intermediates presenting Au-C s or π-bonds, very recently the chemistry community has begun to question these assumptions for other reactions. This new trend puts forward another hypothesis, namely that not only one, but two gold centres could interact with one or more substrate molecules, thus generating a synergistic effect that has the potential to enhance the catalytic activity.1 During our investigations dealing with Late Transition Metal (LTM) hydroxide complexes, we developed the first cationic digold hydroxide species [{Au(IPr)}2(µ-OH)][BF4] (1) in 2010.2 Complex 1 has proven to be a valuable synthon for the synthesis of gem-diaurated and s,p-acetylide complexes and also an effective precatalyst for silver- and acid-free gold-catalysed transformations.3 Of particular interest are results from gold-catalysed nitrile hydration. In this study, a first glimpse at a synergistic effect due to the use of digold hydroxide species vs. monomeric gold complexes was observed.4 This greatly improved the yield for some of the tested nitriles and paved the way to a more scalable and cost-effective process.

XOH

[Au][Au]B(OH)2

ArAr [Au]

[Au] X

[Au]

[Au]X

Ph

OPh

Ph Bu

OPh NH2

O

Ph

OAc

Alkyne Hydration

Nitrile Hydration

Meyer-Schuster

[3,3]-rearrangement

H2O

H2O

H2O

H+

Catalysis Mechanistic Studies

[Au] = [Au(NHC)]X = BF4, NTf2, OTf, OTs, etc.

(1)

References(1) Gómez-Suárez, A.; Nolan, S. P. Angew. Chem., Int. Ed. 2012, 51, 8156-8159.(2) Gaillard, S.; Bosson, J.; Ramón, R. S.; Nun, P.; Slawin, A. M. Z.; Nolan, S. P. Chem. Eur. J. 2010, 16, 13729- 13740.(3) (a) Gómez-Suárez, A.; Dupuy, S.; Slawin, A. M. Z.; Nolan, S. P. Angew. Chem., Int. Ed. 2013, 52, 938-942; (b) Gómez-Suárez, A.; Oonishi, Y.; Meiries, S.; Nolan, S. P. Organometallics 2013, 32, 1106-1111.(4) Ramón, R. S.; Gaillard, S.; Poater, A.; Cavallo, L.; Slawin, A. M. Z.; Nolan, S. P. Chem. Eur. J. 2011, 17, 1238- 1246.

P5: The Fluoride-Free Transmetalation of Organosilanes to Gold

Stephanie Dupuy and Steven P. Nolan*

University of St. Andrews, School of Chemistry, EaStChem, St. Andrews, Fife, KY16 9ST, UK.E.mail: sd53@st-andrews.ac.uk; sn17@st-andrews.ac.uk

Because of their low cost, low toxicity, and high chemical stability, organosilanes have emerged as viable alternatives to the conventional reagents used in cross-coupling reactions in recent years.1 However, unlike the tin- and zinc-based reactions, which require no activation, or the boron-based reactions, which require only heating with mild bases, silicon-based cross-coupling reactions often require heating in the presence of a fluoride source; this has significantly hampered he widespread acceptance of organosilanes. Over the past few years, Denmark et al. have developed a variety a fluoride-free Hiyama-type couplings employing organo-silanols.2 A feature of this process is the formation of a covalently linked palladium silanolate Si-O-Pd species that facilitates the critical transmetalation step.3

Reaction of gold with a wide variety of aryl-, vinyl-, allyl- and alkylsiloxanes permitted room temperature access to a new class of gold silanolate, (Si-O-Au), complexes while, under heating, a selective and straight-forward transmetalation reaction could be achieved to provide diverse aryl-, vinyl- and allylgold(I) complex-es. Interestingly, further experiments confirmed the gold silanolate species to be a key intermediate in this transmetalation reaction. This discovery has revealed new reactivity for gold(I).4

References1. Hiyama, T. Organosilicon Compounds in Cross-coupling Reactions. In Metal-Catalyzed Cross-Cou pling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinheim, Germany, 1998; Chapter 10. 2. (a) Denmark, S. E.; Smith, R. C.; Chang, W. T. T.; Muhuhi, J. M., J. Am. Chem. Soc. 2009, 131, 3104; (b) Denmark, S. E.; Ober, M. H.; Aldrichimica Acta, 2003, 36, 75; (c) Denmark, S. E.; Ober, M. H. Adv. Synth. Catal. 2004, 346; (d) Denmark, S. E.; Butler, C. R. J. Am. Chem. Soc. 2008, 130, 3690.3. Denmark, S. E.; Smith, R. C. J. Am. Chem. Soc. 2010, 132, 12434. Dupuy, S.; Slawin, A. M. Z; Nolan, S. P. Chem. Eur. J. 2012, 18, 14923.

P6: Critical role of water in the direct oxidation of CO and Hydrocarbons in Diesel Exhaust Aftertreatment Catalysis

Roberto Caporali Prof. Chris Hardacre, Dr. Alex Gouget, Dr. Dave Thompsett

Queen’s University Belfast, Belfast, Northern Ireland, BT9 5AG, UKrcaporali01@qub.ac.uk

With increasing demands for increased fuel efficiency the interest in diesel engines for passenger vehicles has grown. Diesel engines have, in general, a better fuel economy than standard stoichiometric-burn gasoline vehicles, and emit less CO2. However, there are emission control issues, specifically associated with NOx, hydrocarbons, CO, and particulate matter (PM). In addition to these components, the exhaust gas is also composed of H2, O2, CO2 and SO2. In addition, in the exhaust gas composition, water is found to levels up to 10 vol.% and this plays an important role as an oxidant to convert CO and HCs by the water–gas shift and the steam reforming reactions, respectively, especially at high temperatures. The role of water at low temperature for the enhancement of the CO oxidation activity has been generally recognized as a modification of the cata-lyst surface and/or the reduction of the self-poisoning of CO [1].In the present study the promoting water effect on CO, and simultaneous CO, C3H6 oxidation activities, all during lean conditions was investigated. Understanding such improvement is important to clarify what actu-ally occurs over a diesel oxidation catalyst (DOC) in application.CO and C3H6 oxidation have been carried out in the absence and presence of water over a 2%Pd/Al2O3 catalyst. The results show that the promoting effect of water on CO and C3H6 oxidation is not simply due to changes in surface concentration of the reacting species, i.e. modulating the competitive adsorption effects. Using isotopically labelled dioxygen, the mechanism by which CO2 is formed in the presence of water has been elucidated and demonstrates that oxidation of CO and propene predominantly occurs via reaction with a water de-rived species and not with dioxygen. This is likely to occur as a result of water/OH activation process of CO and C3H6. These results are important as they indicate that at low temperatures, such as found under cold start conditions, the major pathways for CO and hydrocarbon oxidation in exhaust gases, where water is ubiquitous, involves reaction with water, or a water-related species such as –OH and, consequently, oxygen may play a secondary role.

References1. H.J. Kwon, Chem. Eng. J. 141 2008 194.

P7: Synthesis of Optically Active Polymandelic Acid via Metal-free Catalysis

R. Ben-Giat, D. R. Carbery, M. G. Davidson, F. Dunn, P. K. Ivanova-Mitseva, B. J. Jeffery and A. W. Thomas

Department of Chemistry, University of Bath, Bath, BA2 7AY, UKbjj21@bath.ac.uk

Modern society depends heavily on plastics in applications ranging from food packaging to engineering materials and medicines. One of the most widely used polymers is polystyrene (PS), a plastic produced on a huge scale in different forms (foams, sheets etc.), each with multiple uses. Despite its commonplace occurrence, polystyrene does not degrade for hundreds of years and its monomer is derived from the pet-ro-chemical industry. Polymandelic acid or polymandelide (PMA) can be regarded as the polyester analogue of polystyrene. PMA has been shown to mimic many of the physical properties of PS by virtue of its phenyl substitution but has the benefits of being synthesised from a natural, renewable source and being biodegrad-able.1 One ring-opening polymerisation (ROP) route to PMA is from mandelic acid ortho-carboxyanhydride (mandelic OCA), a cyclic monomer which can be synthesised in high yield under mild conditions. To date, only oligomers of mandelic OCA have been prepared using pyridine catalyst and initiated by adventitious moisture.2 We have re-examined the ROP of mandelic OCA under anhydrous conditions with the goal of producing high molecular weight polymer in a controlled fashion.

For this purpose a range of pyridine bases were assessed as catalysts for polymerisation of R-mandelic OCA and S-mandelic OCA. The tacticity of the polymers was investigated with 1H NMR and the polymer molecu-lar weight was analysed with GPC. We have observed that the pKaH of the pyridine bases influences both the rate of polymerisation as well the molecular weight control and tacticity. Whilst pyridines with a higher pKaH allowed for molecular weight control, the stereochemistry was uncontrolled, giving atactic polymer. Decreas-ing the pKaH of the pyridine base also decreased the rate of polymerisation but, importantly, retained the stereochemistry giving access to isotactically enriched PMA.

PMA synthesised via metal-free catalysis is potentially a useful material for biomedical applications such as tissue engineering and degradable implants. Isotactically enriched PMA could provide a material with me-chanical properties suitable for high-performance applications.

1. T. Liu, T. L. Simmons, D. A. Bohnsack, M. E. Mackay, M. R. Smith and G. L. Baker, Macromolecules, 2007, 40, 6040-60472. I. J. Smith, B. J. Tighe, Macromol. Chem. Phys. 1981, 182, 313-324.

P8: SMALL MOLECULE ACTIVATION BY PACMAN COMPLEXES: THE ELECTROCAT-ALYTIC REDUCTION OF CO2

C. Finn, J. B. Love*

EaStCHEM School of Chemistry, University of Edinburgh, West Mains Road Edinburgh, EH9 3JJ, U. K.

With increasing levels of CO2 contributing to global warming there is an ever-present need to reduce levels of this gas while attempting to find renewable energy sources for the future. CO2 represents an important, non-toxic, abundant and cheap carbon feedstock. The preparation of value-added compounds from CO2 has advantages in terms of mitigating environmental impact as well as generating new revenue streams. The Pacman Schiff-base calixpyrrole ligands used within the Love group have two N4 donor sets and fold to form a well-defined, rigid molecular cleft upon metalation. Complexes of this type show precedence for small mol-ecule activation, for example in the catalytic reduction of oxygen to water.1 We introduce here investigations into the use of these platforms in the activation of CO2 and its related catalytic chemistry. The syntheses of a number of mono- and bimetallic complexes are reported as well as variations of the ligand architecture to facilitate the approach of small molecules. The ability of these compounds to activate CO2 has been assessed under chemical and electrochemically reducing conditions in the presence of various proton sources.

References

1. Askarizadeh, E.; Bani Yaghoob, S.; Boghaei, D. M.; Slawin, A. M. Z.; Love, J. B.; Chem. Commun., 2010, 46, 710 2. Leeland, J.W.; Finn, C.; Escuyer, B.; Kawaguch, H.; Nichol, G.S.; Slawin, A. M. Z.; Love, J. B.; Dalton Trans., 2012, 41, 138153. Finn, C.;.Schnittger, S.; Yellowlees, L. J.; Love, J.B.; Chem. Commun., 2012, 48, 1392

P9: Carbon Dioxide conversion to hydrocarbons using structured carbon nanotube supports

Authors: D. Minett, J O’Byrne, M. Jones, P. Plucinski, D.Mattia

Address: University of Bath, Centre for Sustainable Chemical Technologies, BathE.mail: D.R.Minett@bath.ac.uk

www.bath.ac.uk/nanotech

Dealing with carbon dioxide waste is an ongoing societal and technological challenge. One attractive prop-osition is to chemically convert waste carbon dioxide into useful chemical products. One possible route is to combine two well-known chemical processes, reverse water gas shift and Fischer-Tropsch synthesis, to make a catalyst capable of converting carbon dioxide directly into hydrocarbons.Iron nanoparticles supported on carbon nanofibres have shown promise in the Fischer-Tropsch process.1 We have shown that iron nanoparticles supported on carbon nanotubes (Fe@CNT) are also effective catalysts for the coupled reverse water gas shift and Fischer-Tropsch reactions.2 Using an oxidation process the iron nano-particles embedded in the carbon nanotubes from the synthesis process can be regenerated to act as catalysts for the Fischer-Tropsch reaction (see figure 1a).2

Carbon nanotube powders generated in this way are difficult to handle, and could be difficult to scale-up. We have, therefore, developed a method to grow long, aligned carbon nanotubes on a commercial cord-ierite monolith support (see figure 1b.3 Using the same oxidation method we have now activated these Fe@CNTs-monoliths to act as catalysts for carbon dioxide conversion. Here we report on the first promising results.

References1. Torres Galvis, H. M.; Bitter, J. H.; Khare, C. B.; Ruitenbeek, M.; Dugulan, A. I.; de Jong, K. P., Science 2012, 335 (6070), 835-838.2. O’Byrne, J. P.; Owen, R. E.; Minett, D. R.; Pascu, S. I.; Plucinski, P. K.; Jones, M. D.; Mattia, D., High Catalysis Science & Technology 2013.3. Minett, D. R.; O’Byrne, J. P.; Jones, M. D.; Ting, V. P.; Mays, T. J.; Mattia, D., Carbon 2013, 51 (0), 327- 334.1.

P10: Transition metal catalysts immobilized on functional polymers

Authors: David J. Lunn,* Jamie Clifton, Paul G. Pringle and Ian MannersAddress: School of Chemistry, University of Bristol, Bristol, BS8 1TS, United Kingdom.

david.lunn@bristol.ac.uk

Polymer immobilization has been widely used as a method to facilitate the separation of products and ho-mogeneous catalysts in a given process. The polymeric network in these systems is generally considered to be an inert backbone to which an ‘important’ catalytic moiety is bound. However recent work has shown that the polymer itself can have a significant effect on the activity, stability and even selectivity of the immobilized catalysts.1

Preliminary research will be presented into the use of functional polymers and block copolymers to improve the activity and selectivity of catalytic transformations. In block selective solvents, crystalline-coil block copolymers (e.g. polyferrocenyldimethylsilane-block-polymethylvinylsiloxane (PFDMS-b-PMVS)) have been shown to undergo crystallisation-driven self-assembly (CDSA) to afford well-defined and colloidally stable cylindrical micelles.2 These inorganic polymers, prepared from cheap, sustainable and readily available start-ing materials, can be selectively functionalized to incorporate phosphine based ligands and immobilize and spatially isolate a variety of transition metal catalysts.

References1. B. Altava, M. I. Burguete, E. Garcia-Verdugo, S. V. Luis, M. J. Vicent, J. A. Mayoral, React. Funct. Polym. 2001, 48, 25.2. X. Wang, G. Guerin, H. Wang, Y. Wang, I. Manners, M. A. Winnik, Science, 2007, 317, 644.

P11: Small molecule activation by Rare-Earth Metal N-heterocyclic Carbene Complexes

Isobel H. Marra, Z. R. Turnera, A. I. Germerotha, R. M. Bellabarbab, R. P. Toozeb and P. L. Arnolda*a EaStCHEM School of Chemistry,

The University of Edinburgh, West Mains Road,

Edinburgh, EH9 3JJ, UK.

polly.arnold@ed.ac.uk

b Sasol Technology, Purdie Building , North Haugh, St. Andrews, KY16 9ST, UK

A select group of organometallic rare-earth complexes are known to activate small molecules such as meth-ane.1 However, as these rare-earth complexes are redox inactive, further chemistry is limited. In recent years our group has synthesised bidentate, saturated N-heterocyclic carbene (NHC) ligands bearing anionic alkox-ide tethers. These allow the hemilabile carbene donors to be retained in the coordination sphere of the elec-tropositive metal.2 We have demonstrated that in organo rare-earth complexes this hemilabile NHC can act as a reactive donor ligand and allow these redox inactive metals to partake in further chemistry.3

Two functional groups can be delivered simultaneously to an organometallic rare-earth complex via the addi-tion of an E-X (E = SiR3, PR2, SnR3, X = halide) across the metal-carbene bond to form a zwitterionic imida-zolinium metal complex with E adding to the carbene and X to the metal. Upon warming to room tempera-ture functionalised hydrocarbyl compounds (ER) are spontaneously eliminated from the complex reforming the metal-carbene bonds.4

We will present the synthesis and reactivity of a number of rare-earth metal NHC complexes in order to expand the scope of this addition-elimination chemistry and to look at the activation of small molecules such as CS2 and CO2.

References[1] P. L. Watson and G. W. Parshall, Acc. Chem. Res., 1985, 18, 51-56[2] P. L. Arnold, M. Rodden, K. M. Davis, Chem. Commun., 2004, 1612-1613[3] Z. R. Turner, R. Bellabarba, R. P. Tooze and P. L. Arnold, J. Am. Chem. Soc., 2010, 132, 4050-4051[4] P. L. Arnold, Z. R. Turner, R. Bellabarba and R. P. Tooze, J. Am. Chem. Soc, 2011, 133, 11744-11756

P12: Aerobic oxidation of hydrocarbons catalysed by Mn-doped nanoporous aluminophos-phate catalysts

Panagiota Pelekanaki1(*), Luis-Gómez Hortigüela1,Furio Corà1, C. Richard A. Catlow1

University College London, Department of Chemistry, 20 Gordon Street, LondonWC1H 0AJ, UK

(*) panagiota.pelekanaki.09@ucl.ac.uk

State of the art electronic structure techniques based on hybrid-exchange functionals in Density Functional Theory (DFT) and representing the extended nature of the catalyst using periodic boundary conditions have been recently applied in order to reveal the mechanism of the aerobic oxidation of ethane catalysed by Mn-doped AlPO-5 [1,2]. In the present work we extend previous results in order to discriminate the reactivity of primary and secondary carbon atoms to oxidation which is the most pressing open question in the literature. To achieve this goal we change the hydrocarbon substrate from ethane to propane. We study in detail two representative steps of the catalytic cycle discussed in [1,2]: the abstraction of H from ethane in the preacti-vation phase, which involves a reduction of the MnIII site to MnII, and one step of the propagation mechanism where Mn does not change oxidation state.Our results show that when the H-abstraction reaction takes place on the secondary carbon atom of propane in the preactivation phase, it requires lower activation barriers than on the primary C atoms. This result is consistent with the gas phase stability of primary and secondary C-based radicals. It indicates that the pore size on AlPO-5 is too large to impose structural constraints on the transition states and products formed, hence the propane oxidation is thermodynamically controlled.

The reaction profiles of ethane and propane as a functional of the reaction coordinate which is thedistance between H and O and the H transfer to the active site, yielding a MnII site and a propyl

radical.

References[1] L. Gomez-Hortigueela, F. Cora, G. Sankar, CM. Zicovich-Wilson, C..R.A. Catlow, Chem. Eur. J. 16, (13638-13645) 2010[2] F.Cora, L. Gomez-Hortigueela, C..R.A. Catlow, Proc. R. Soc. A, 2012

P13: DIRECT AMINATION OF BIO-ALCOHOLS USING AMMONIA†

D. L.L. Pingen,1 Prof. Dr. C. Müller,2 Prof. Dr.D. Vogt1

1 Industrial Chemistry, School of Chemistry, University of Edinburgh, Edinburgh, Scotland, United Kingdom2 Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Berlin, Germany

E.mail: dpingen@gmail.com, d.vogt@ed.ac.uk

Amines and especially primary amines are valuable building blocks for polymers, surfactants, corrosion inhibitors, and fine chemicals. The conventional production routes produce a lot of waste. In this project we aim at the direct amination of bio-based alcohols, preferably by ammonia, to give the primary amines. Previously, we showed that the combination of Ru3(CO)12 and a range of phosphine ligands, e.g. the CataCXium®PCy ligand gave primary amines in high selectivi-ty from alcohols and ammonia.[1] Now we de-veloped an improved system based on Ru3(-CO)12

and an acridine based di-phosphine ligand, which can be used in direct amination of bio-alcohols and bio-based diols.[2] Applying this improved catalytic system gave conversions generally over 80% with a typical selectivity of over 80% towards the primary amine. A wide range of cyclic and acyclic secondary and primary bio-based alcohols both saturated and unsaturated alcohols (geraniol, citronellol, isomannide, 1,4-cyclohex-anediol, borneol), were converted efficiently to their corresponding primary amines. Additionally, it has been shown that the catalyst can be used over multiple runs, without loss of activity or selectivity.

Further catalyst optimization and mechanistic work are in progress.

References1. Pingen, D.L.L., Müller, C., Vogt, D. Angew. Chem. Int. Ed. 2010, 49, 8130-8133. 2. Gunanathan, C., Milstein, D., Angew. Chem. Int. Ed. 2008, 47, 8661-8664.

† This research is funded by the private-public consortium CatchBio (http://www.catchbio.com).

P14: Highly Active Iridium(I) Catalysts for Mild Hydrogenation Processes.

William J. Kerr* and Richard J. Mudd

Department of Pure and Applied Chemistry, WestCHEM, University of Strathclyde,Glasgow, G1 1XL, UK.

richard.mudd@strath.ac.uk

Catalytic hydrogen of carbon-carbon multiple bonds is an essential tool in the repertoire of a synthetic chemist. As such, it remains a topic of intense research in organometallic chemistry. Having said this, many of these catalysts require elevated temperatures, pressures, or catalyst loading. Within our laboratory we have developed a range of iridium(I) complexes (2) bearing a phosphine and an N-heterocyclic carbene.1 These new species have proven to be highly active hydrogenation catalysts, allowing the use of reaction conditions that are mild and selective to olefin hydrogenation.2 More recently, we have been investigating the effect that changing the nature of the anionic counter ion (3) has upon the reactivity of the catalyst complex (Scheme 1). The full details of our endeavours in this area will be discussed as part of this poster presentation.

Scheme 1

References1. J. A. Brown, S. Irvine, A. R. Kennedy, W. J. Kerr, S. Andersson and G. N. Nilsson, Chem. Commun., 2008, 1115.2. L. S. Bennie, C. J. Fraser, S. Irvine, W. J. Kerr, S. Andersson and G. N. Nilsson, Chem. Commun., 2011, 47, 11653.

P15: EPOXIDATION OF TRIGLYCERIDE: FLOW vs BATCH

Dorota D. Plaza,1 Andrew Clark,2 Alexei A. Lapkin1

1 School of Engineering, University of Warwick, Coventry, CV4 7AL2 Department of Chemistry, University of Warwick, Coventry, CV4 7AL

d.d.plaza@warwick.ac.uk

The aim of this work is to develop an epoxidation process for bio-waste triglyceride found in cocoa butter (a waste product of chocolate production) using both batch and continuous phase transfer catalysis. A modified WVI/PV/H2O2/PTC complex was used as a catalyst, which had shown high selectivity and conversion towards the epoxidation reaction.

Epoxidation of cocoa butter under batch conditions was optimised in terms of reaction temperature and catalyst composition. Results shown in Fig. 1. The dependence of the rate of disappearance of double bond and selectivity to epoxide as a function of residence time (in the flow system) and reaction time (in the batch reactor).1 illustrate typical batch results (squares, CB = cocoa butter) with 100 % conversion and 85 % selectivity to the epoxide. The main byproduct is the ring opening di-ol, as determined by NMR and Raman.

Under flow conditions the reaction was run as a segmented flow in the presence of toluene to reduce viscosity. In this specific case reaction under flow conditions gives similar conversion and selectivity as batch reactions. However, other benefits, such as improved safety and reduced overall processing time due to elimination of batch cycle operations make the flow process attractive.

Acknowledgements: DP is grateful to University of Warwick for funding of PhD scholarschip

Fig. 1. The dependence of the rate of disappearance of double bond and selectivity to epoxide as a function of residence time (in the flow system) and reaction time (in the batch reactor).

P16: Sustainable Bio-Derived Ketones via Heterogeneous Catalysed Fatty Acid De-oxygenation Reactions

Li Li a, Philip Midgley a, Hugh Christopher Greenwell b,*, Philip Dyer a

a Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UKb Department of Earth Sciences, Durham University, South Road, DH1 3LE, Durham, UK

E.mail: li.li2@durham.ac.uk

Over the last decade, growing concerns for the depletion of petroleum reserves, combined with a growing awareness of greenhouse gas emissions have stimulated research on the potential conversions of renewable biomass to establish processes that transform different biomass and biomass derived products into liquid fuels and chemicals. Biomass can be fractionated into the traditional groupings of carbohydrate, protein and lipids. A defining characteristic of fresh bio-derived material, when contrasted to petroleum, is the high level of oxygen. For biofuel applications, this oxygen needs removing as it leads to lower energy density and increased polarity, which gives rise to adverse corrosion, hygroscopic and cold-flow properties [1, 2]. Conversely, there are large-scale chemical processes presently requiring the oxidation of petroleum based feedstocks, and one of the main products using hydrocarbon oxidation is the production of ketones [3, 4]. Biologically-derived aliphatic (fatty) acids from the lipid fractions of oil bearing alga, seeds or plants can be readily converted into useful ketones for platform chemicals by ketonic decarboxylation process, which has long been known as ketonization [5].

Layered double hydroxides (LDHs) have been recognized as useful solid base catalysts. We investigated the effect of metal type by comparing Mg-Al and Mg-Fe LDHs intercalated with CO3

2- and prepared by co-precipitation methods. We employed decanoic acid as the substrate for testing catalytic ketonic decarboxylation performance and investigated the effect of reaction temperature, reaction pressure and catalyst loading. It clearly showed that high reaction temperature (300 °C) and low reaction pressure favour this reaction, while ketone yield increased firstly, and then decreased with increasing LDH loading. Overall, Mg/Fe LDHs are more active than Mg/Al LDHs. Each Mg/Fe LDH gave more than 80% of ketone yield.

Figure 1. Ketonic decarboxylation reaction of decanoic acid

References1. M.N. Islam and M.R.A. Beg, Bioresource Technology, 2004. 92(2): p. 181-186.2. S. Zhang, Y. Yan, T. Li and Z. Ren, Bioresource Technology, 2005. 96(5): p. 545-550.3. M. G. Clerici, Applied Catalysis, 1991. 68(1): p. 249-261.4. K.E. Djernes, M. Padilla, M. Mettry, M.C. Young and R.J. Hooley, Chemical Communications, 2012. 48(94): p. 11576-11578.5. A.D. Murkute, J.E. Jackson and D.J. Miller, Journal of Catalysis, 2011. 278(2): p. 189-199.

P17: Emerging Iridium Complexes for Further Applications in Hydrogen Isotope Exchange

Authors: William J. Kerr,* Marc Reid, and T. Tuttle*

Address: Department of Pure and Applied Chemistry, WestCHEM, University of Strathclyde, Glasgow, G1 1XL, UK

E-mail: marc.reid@strath.ac.uk

Isotopic labelling with heavy hydrogen isotopes (D2 and T2) is widely used as a means to monitor the biolog-ical fate of a potential drug molecule.1 To circumvent additional synthetic steps in the drug design process, more direct, flexible, and selective means of introducing hydrogen isotopes continues to be the focus of considerable research attention. In relation to this, preliminary studies from our laboratory have allowed ex-pedient access to a series of novel iridium complexes, many of which were previously inaccessible. By careful manipulation of the ligands supporting the iridium centre, these new catalysts can be applied under extreme-ly mild reaction conditions and have now emerged to become some of the most active and, indeed, selective species known in this area of labelling chemistry.2

In a further extension to this overall programme of work, we are now using experimental and computational methods in parallel to optimise the design of our most successful catalysts. As a first step, investigations into the effect of changing the anionic portion of these complexes have been initiated to deliver complexes such as 2 (Scheme 1). This seemingly subtle adjustment of altering the catalyst counterion is now delivering unprec-edented catalyst efficiency and, crucially, longevity. All studies to date will be delineated within this poster presentation.

References1. E. M. Isin, C. S. Elmore, G. N. Nilsson, R. A. Thompson, L. Weidolf, Chem. Res. Toxicol., 2012, 25, 532.2. J. A. Brown, S. Irvine, A. R. Kennedy, W. J. Kerr, S. Andersson, G. N. Nilsson, Chem. Commun., 2008, 1115.

P18: Promoted Iron-Silica Nano-Catalysts for the Formation of Hydrocarbons from Carbon Dioxide

R. E. Owen1, J. P. O’Byrne2, M. D. Jones1, D. Mattia2, P. Plucinski2 and S. I. Pascu1

1Department of Chemistry, University of Bath, BATH, BA2 7AY, UK. 2Department of Chemical Engineering, University of Bath, BATH, BA2 7AY, UK

E.mail:reo20@bath.ac.uk

With over 85% of the world’s energy dependent on fossil fuels1 the increasing price and dwindling supply is likely to have a large impact on society. When combined with the long timescale and large cost associated with the substitution of fossil fuels for alternatives it becomes obvious that a new route for their production is essential. The widely noted negative consequences related to the release of CO2 into the atmosphere along with its low cost and renewable nature has resulted in it gaining attention as a possible feedstock for hydrocarbon formation. This can be achieved through a two-step process, the reduction of CO2 to CO via the reverse water gas shift (RWGS) reaction followed by the formation of hydrocarbons from CO by the Fischer-Tropsch (FT) process. Our work focuses on the development of nano-catalysts that are active for both steps simultaneously, under the same reaction conditions. Iron and cobalt have received the majority of attention in this area with iron’s RWGS activity proving important in its improved activity over cobalt systems. When used alone, in the absence of promoters, iron based catalyst systems can possess problems with deactivation and high selectivity to undesirable products such as methane.2 In order to counteract this problem we have investigated a range of novel promoters and their effects on iron-silica nano-catalysts. Our work has shown that through the addition of only small amounts of various metals a large effect on both conversion and selectivity can be obtained. The catalyst systems investigated have been analysed using a range of characterisation techniques such as TEM, SEM (see Figure 1), EDS, XPS and BET.

Figure 1. Example SEM (a) and TEM (b) images obtained for a 20wt%Fe/SiO2 catalyst.

References1. G. Centi, G. Iaquaniello and S. Perathoner, ChemSusChem, 2011, 4, 1265-1273.2. P. S. Sai Prasad, J. W. Bae, K.-W. Jun and K.-W. Lee, Catalysis Surveys from Asia, 2008, 12, 170-18

P19: Seaweed and sustainability: exploring the catalytic pyrolysis of macroalgae as a route to renewable fuels and chemicals

J. S. Rowbothama, P. W. Dyera, H. C. Greenwellb, L. Lia,b and M. K. Theodorouc,d

aCentre for Sustainable Process Chemistry, Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK

bDepartment of Earth Sciences, Durham University, South Road, Durham DH1 3LE, UK cSchool of Biological and Biomedical Sciences, Durham University, South Road, Durham DH1 3LE, UK

dCentre for Process Innovation, Wilton Centre, Wilton, Redcar TS10 4RF, UK

jack.rowbotham@durham.ac.uk

With demands on conventional sources of fuels and chemicals rapidly intensifying, there is growing interest in the development of new, sustainable methods for generating these commodities. In this respect, macroal-gae (seaweeds) have shown considerable potential as novel feedstocks for the production of chemicals via thermochemical processing methods (such as pyrolysis).1 However, the use of seaweeds in pyrolysis processes is relatively undeveloped and, as such, little is known about the fundamentals mechanisms by which thermal degradation occurs. One particular area of interest is the potentially catalytic role that metal ions (present naturally in the biomass) may have in the thermolysis process.2 This parameter is particularly interesting in the case of kelps owing to their extraordinarily high affinity for sequestering certain species of metal ion.3 In order to further eluci-date the influence exerted by these metal ions on the thermal behaviour of seaweed biomass, a novel, model compound approach has been developed. The method is based around the thermogravimetric analysis (TGA) and differential thermal analysis (DTG) of the algal polysaccharide alginic acid (and the corresponding metal alginate salts). This approach circumvents the inherent difficulties associated with using naturally heterogeneous biomass samples in order to reach widely applicable conclusions about the thermolysis behaviour of macroalgae (as exemplified by figure 1). Thus, the poster will introduce the concept of macroalgae pyroly-sis as well as exploring some of the fundamental results obtained from the model compound study to date. It is hoped that this work will lead to a greater understanding of how seaweed can be better exploited as a versatile bioresource.

References1) J. S. Rowbotham, P. W. Dyer, H. C. Greenwell and M. K. Theodorou, Biofuels, 2012, 3(4), 441-461. 2) M. S. Mettler, D. G. Vlachos and P. J. Dauenhauer, Energy Environ. Sci., 2013, 5, 7797-7809.3) T. A. Davis, B. Volesky and A. Mucci, Water Res., 2003, 37(18), 4311-4330.4) J. S. Rowbotham, P. W. Dyer, H. C. Greenwell, D. Selby and M. K. Theodorou, Interface Focus, 2013, 3(1).

P20: Transition-metal versus Heavy-metal Synergy in Nanoporous Frameworks for Selective Catalytic Oxidations

M.E. Potter and R. Raja*Address: School of Chemistry, University of Southampton, Southampton, SO17 1BJ.

E-mail: R.Raja@soton.ac.uk

The growing demand for sustainable technology, and advancements in structure-property correlations, has prompted a growth in the use of increasingly intricate multi-metallic catalytic species in a variety of systems.[1] Here-in we discuss the development of synthetic procedures designed to incorporate isolated catalyti-cally-active metal sites into nanoporous aluminophos-phate (AlPO) frameworks, and the adaption of these techniques to form novel bimetallic catalytic systems. Through such synthetic methods we demonstrate the ability to accurately tune the metal sites, allowing pre-cise control over both the coordination geometry of the individual sites and the relative proximity of the two species. Using a variety of characterization techniques it has been established that when two different species are placed sufficiently close to one another subtle chang-es occur in the precise nature of these species. Such modifications permit greater control over the design of catalytic species, allowing an optimization of the catalytic potential through this synergistic enhancement for a range of industrially significant hydrocarbon transformations.

In our previous work the choice of metal dopants has been lim-ited to the smaller transition metal ions such as cobalt and tita-nium given the distortion required to incorporate them directly into the microporous framework.[1] We then further this work by designing a range of novel aluminophosphate materials with the previously unexplored heavier metals dopants, ruthenium and tin. By incorporating these heavier metals we demonstrate both an improvement in catalytic activity over Co3+Ti4+AlPO-5 and also establish a synergistic enhancement between the two species in the novel bimetallic Ru3+Sn4+AlPO-5 system. In this work we will present our catalytic findings for both the tran-sition-metal and heavy-metal systems. We then combine the catalysis with a range of characterization techniques such as

EPR and UV/Vis to probe the exact nature of the active sites and the synergistic enhancements therein.

References1. J. Paterson, M.E. Potter, E. Gianotti, R. Raja, Chem. Commun., 2011, 47, 517-5192. M.E. Potter, J. Paterson, R. Raja, ACS Catal., 2012, 2, 2446-2452Figure 1: Schematic detailing metal incorporation in AlPO materials.Figure 2: Catalytic data for the epoxidation of cyclohexene with APB, data after 3 hrs at 66 oC

P21: Unsymmetrical Group 4 amine tris(phenolate) complexes as initiators for the controlled polymerisation of racemic-lactide

Authors: Thomas R. Forder, 1 Matthew D. Jones, 2 Matthew G. Davidson1

Address: 1Centre for Sustainable Chemical Technologies, University of Bath, Bath, UK2Department of Chemistry, University of Bath, Bath, UK

E.mail: T.R.Forder@bath.ac.uk

The controlled polymerisation of the renewable monomer lactide to give the degradable polyester polylactide (PLA) is an attractive area of research as efforts are made to move away from traditional petroleum-based plastics. A C3-symmetric Group 4 amine tris(phenolate) complex has previously been published exhibiting highly stereoselective polymerisation of racemic-lactide to yield heterotactic PLA.1

In this work a series of unsymmetrical amine tris(phenolate) ligands have been synthesised using a step-wise method. Subsequent reaction with Group 4 alkoxides generated a series of dimeric complexes, which have been characterised in the solid state by crystallography (Figure 1) and in the solution state by NMR spectroscopy.

We show that all complexes are active for the polymerisation of lactide and data is presented showing polymerisation kinetics and stereoselectivity (probability of racemic enchainment, Pr) for each complex. In the light of this data, we discuss the influence of sterics and complex symmetry on the polymerisation activity and selectivity.

Figure 1. Solid-state structure of Zirconium (VI) alkoxide complexed with an unsymmetrical amine tris(phenolate). Protons have been removed for clarity.

References1. A. J. Chmura, M. G. Davidson, C. J. Frankis, M. D. Jones and M. D. Lunn, Chem. Commun., 2008, 1293-1295.

P22: Organocatalytic Asymmetric Functionalisation of Carboxylic Acids using Isothioureas

Louis C. Morrill* and Prof. Andrew D. SmithSchool of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST

In recent years, isothioureas have found utility as organocatalysts through their ability to act as Lewis bases.1 Within the Smith group we have illustrated the ability of isothioureas to catalyse a range of reactions including the O- to C- carboxyl transfer of heterocyclic carbonate derivatives,2 and C-acylation of silyl ketene acetals.3 Recent research has shown that isothioureas promote the asymmetric intermolecular Michael addition-lactonisation reaction between carboxylic acids 1 and α-keto-β,γ-unsaturated esters 2 under open flask conditions with low catalyst loadings to give anti-dihydropyranones 3 with high diastero- and enantiocontrol (up to 98:2 dr, up to 99% ee)4 (Figure 1).

These results will be communicated, along with current research into related isothiourea catalysed Michael addition reactions involving trifluoromethyl enones 45 and N-aryl-N-aroyldiazenes 5.6 The value of these heterocyclic products will be illustrated through their subsequent derivatisation into useful synthetic building blocks such as α-substituted amino acid derivatives and those containing CF3-stereogenicity (Figure 2). Kinetic and mechanistic studies have allowed the determination of reaction orders for each component, with the observation of a primary kinetic isotope effect allowing the identification of a possible rate-determining step. Additionally, computational transition-state modelling has rationalised the factors leading to high stereocontrol in these processes.

References1 For a review see S. E. Denmark and G. L. Beutner, Angew. Chem. Int. Ed., 2008, 47, 1560.2 C. Joannesse, C. P. Johnston, C. Concellon, C. Simal, D. Philp and A. D. Smith, Angew. Chem. Int. Ed., 2009, 48, 8914.3 P. A. Woods, L. C. Morrill, T. Lebl, A. M. Z. Slawin, R. A. Bragg and A. D. Smith, Org. Lett., 2010, 12, 2660.4 D. Belmessieri, L. C. Morrill, C. Simal, A. M. Z. Slawin and A. D. Smith, J. Am. Chem. Soc., 2011, 133, 2714.5 L. C. Morrill, J. Douglas, T. Lebl, D. J. Fox, A. M. Z. Slawin and A. D. Smith Manuscript in preparation.6 L. C. Morrill, T. Lebl, A. M. Z. Slawin and A. D. Smith Chem. Sci., 2012, 3, 2088.

P23: A new NMR method to study Lignin depolymerisation and attempted cleavage of related model compounds

F. Tran, D. M. U. K. Somisara, T. Lebl, N.J. Westwood and P. C. J. KamerUniversity of St. Andrews, School of Chemistry, EaStChem, St. Andrews, Fife, KY16 9ST, UK.

njw3@st-andrews.ac.uk

With the availability of fossil fuels expected to become more and more scarce, the use of biomass as an alter-native sustainable source of bulk and fine chemicals appears attractive. In 2004, the pulp and paper industry produced 50 million tons of lignin of which only 2% were used commercially.1 Given its unique structure, a wide variety of aromatic compounds could be obtained from lignin.2 However lignin depolymerisation con-stitutes a significant barrier to exploit its full potential as a petroleum replacement. Pre-treatment of lignin delivers a series of aryl rings held together by various chemical linkages e.g. b-O-4, b-5, b-b (Figure 1a), that need to be broken down further for this particular type of biomass to be a sustainable source of chemicals.The development of a 2D HSQC NMR experiment to characterise these linkages3 (Figure 1b), the synthesis of model substrates and attempts to study their cleavage by mild catalytic degradation will be described.4.5

References1. Gosselink, R. J. A.; de Jong, E.; Guran, B. Abacherli, A. Ind. Crops Prod. 2004, 20, 1212. Zakzeski, J., Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen, B. M. Chem. Rev. 2010, 110, 35523. a. Liitia, T. M.; Maunu, S. L.; Hortling, B.; Toikka, M. Kiplenäinen, I. J. Agric. Food Chem. 2003, 51, 2136;b. Zhang, L.; Gellerstedt, G. Magn. Reson. Chem. 2007, 45, 37; c. Kleine, T.; Buendia, J.; Bolm, C. Green Chem. 2013, 15, 1604. a. Nichols, J. M.; Bishop, L. M.; Bergman, R. G.; Ellman, J. A. J. Am. Chem. Soc. 2010, 132, 12554; b. Wu, A.; Patrick, B. O.; Chung, E. James, B. R. Dalton Trans. 2012, 41, 110935. Zakzeski, J. Jongerius, A. L.; Bruijnincx, P. C. A.; Weckhuysen, B. M. ChemSusChem, 2012, 5, 1602

P24: Successful application of pyrroryl-based phosphoroamidite ligands in Nickel-catalyzed hydrocyanation of vinilarenes

Alberto Cavalieria,b, Dieter Vogt*b, Christian Müllerc

aSchuit Institute of Catalysis, Eindhoven University of Technology, Eindhoven, the Netherlands; E-mail: a.cavalieri@tue.nl;

bSchool of chemistry, University of Edinburgh, Edinburgh, Scotland, United Kingdom;cDepartment of Biology, Chemistry, and Pharmacy, Freie Universität Berlin, Berlin, Germany.

The rational design of improved ligands for the Ni-catalyzed hydrocyanation of alkenes (Figure1) has been an persistent goal. Rigid-backboned diphosphines [1] and diphosphonites[2] have been shown to be effective ligands for the hydrocyanation of butadiene to 3-PN. The hydrocyanation of other alkenes is also been a topic of continuing interest and all of these processes use the same classes of phosphorus ligands that are used for butadiene hydrocyanation.

R

HCN[Ni] R

NC+

R

CN

*

B L

Markovnikov anti-Markovnikov

Figure 1. Hydrocyanation of a 1-alkene

Our group has a continuing interest in the Ni-catalyzed hydrocyanation of alkenes.[3,4] The subtle interplay of bite angle, steric bulk, and π-acceptor properties of the ligands, in the presence of Lewis acids were demonstrated to be responsible for catalyst activity and stability. Hereby we report the catalytic hydrocyanation of vinilarenes with Pyrroryl-based phosphoroamidites Ni(0)-complexes. At the same time this is the first successful application of phosphoroamidite ligands in this catalysis. We investigated the coordination chemistry and the catalytic activities of a family of Pyrroryl-based phosphoroamidites in the presence of different Lewis acid co-catalysts. The bidentate tetra tetra-pyrrole-1,1’-binaphtol phosphoroamidite-Ni(0) complex (Figure2) appeared to be the most active catalyst of the family with activities comparable with the best performing phosphorus ligand-Nickel(0) systems.

O

O

P

P

N

N

N

N

Ni(cod)

Figure 2. Bidentate pyrrolyl-based phosphoroamidite Ni(0) complex

[1] Bini, L., Müller, C., Wilting, J., von Chrzanowski, L., Spek, A. L. and Vogt, D., J. Am. Chem. Soc. 129

(2007) 12622.[2] Van der Vlugt, J. I., Hewat, A. C., Neto, S., Sablong, R., Mills, A. M., Lutz, M., Spek, A. L., Müller, C. and Vogt, D., Adv. Synth. Catal. 346 (2004) 993- 1003.[3] Bini, L., Müller, C. and Vogt,D., ChemCatChem. 2 (2010) 590.[4] Bini, L., Müller, C. and Vogt,D., Chem. Commun. 46 (2010) 8325.

P25: Synthesis and Structural Characterization of Group 4 metal alkoxide complexes of N,N,N’,N’-tetrakis(2-hydroxyethyl)ethylenediamine and their use as initiators in the ring-opening polymerization

(ROP) of rac-lactide under industrially relevant conditions

Christopher J. Chuck, a Matthew G. Davidson, a,* Gerrit Gobius du Sart,b Petya K. Ivanova-Mitseva,a Gabriele I. Kociok-Köhn a and Lois B. Manton.a

aDepartment of Chemistry, University of Bath, Bath, BA2 7AY UK

bPurac Biochem B.V., Arkelsedijk 46, 4206 AC Gorinchem, The Netherlands

l.manton@bath.ac.uk

Degradable and biocompatible plastics are used in a variety of applications such as food packaging as well as medical stents and sutures. Polylactide (PLA) is a degradable and biocompatible aliphatic polyester that is derived from renewable resources such as corn starch and is a promising alternative to petrochemical-based commodity polymers.

A series of Group 4 metal complexes with N,N,N’,N’-tetrakis(2-hydroxyethyl)ethylenediamine (TOEEDH4) ligand was synthesized and investigated as new active, benign and controlled initiators for the synthesis of PLA. A range of complexes, varying the stoichiometry of ligand to metal, were synthesized and characterized by single crystal X-ray diffraction and the solution structures confirmed by NMR spectroscopy.

The ring-opening polymerization (ROP) of sublimed rac-lactide (rac-LA) was carried out under melt conditions at 135°C and 165°C to investigate the effect of temperature on the stereochemistry of the polymeric product. Polymerization kinetics were monitored in real time using FTIR spectroscopy with a diamond composite insertion probe. The degree of stereocontrol and the polymer microstructure imposed by the catalyst were investigated.

P26: Chemoselective hydrogenation of functionalized nitroarenes using supported Mo-promoted Pt NPs

Evert Boymansa,c*, Peter Witteb, Dieter Vogtc

aChemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The NetherlandsbBASF Nederland B.V., Process Catalysis Research, De Meern, The Netherlands

cSchool of Chemistry, University of Edinburgh, Edinburgh, Scotland*E-mail: e.h.boymans@tue.nl

Chemoselective reduction of a nitro-moiety in the presence of other reducible groups is challenging. Non-catalytic processes such as the Bechamp reduction (Fe/HCl) or the reduction using sulfide (H2S or NaSH) are economically not feasible due to the shear amount of by-products[1]. Catalytic hydrogenation of nitroarenes is typically the process of choice for the production of anilines. The challenge is to design a precious metal powder catalyst (PMPC) both active and (chemo)selective towards the aniline product. Common by-products produced in batch are related to the reaction intermediates (see reaction scheme below[2]), especially in the presence of electron withdrawing substituents on the aromatic ring and low reaction temperature[3].

Here we report on the chemoselective hydrogenation of functionalized nitroarenes to anilines using Mo-promoted supported Pt NPs (see Figure). The Pt nanoparticles are prepared via a commercialized route called the NanoSelect procedure[4], in which Pt(IV) is reduced in the presence of a cationic ammonium surfactant. This catalyst proofed extremely active and selective, even under mild hydrogenation conditions (30°C and 4 bar H2). For instance, nitroarenes containing reducible functional groups (CN, CO, C=C) are selectively reduced to anilines at high TOF.

ReferencesE. Boymans, S. Boland, P.T Witte, C. Müller, D. Vogt, ChemCatChem 2013, 5, 431- 434.[1] T. Kahl, K. Schröder, F. Lawrence, W. J. Marshall, H. Höke and R. JäckhBook: Ullmann’s Encyclopedia of Industrial Chemistry; aniline, 2000.[2] F. Z. Haber, Elektrochem. 1898, 22 506.[3] P. Baumeister, H. U. Blaser, M. Studer, Catal. Lett. 1997, 49 219-222.[4] P. T. Witte, WO patent 2009, 096783.

List of participants

1 Chris Adams Xef6 Consulting Chris@Xef6.Eu2 Polly Arnold Univ Of Edinburgh Polly.Arnold@Ed.Ac.Uk3 Nassilia Attaba University Of St Andrews Na27@St-Andrews.Ac.Uk 4 Adisa Azapagic University Of Manchester Adisa.Azapagic@Manchester.Ac.Uk5 Simon Beaumont Durham University Simon.Beaumont@Durham.Ac.Uk6 Ronan Bellabarba Sasol Ronan.Bellabarba@Eu.Sasol.Com7 Matthias Beller Universität Rostock Matthias.Beller@Catalysis.De8 Dorine Belmessieri University Of St Andrews Db445@St-Andrews.Ac.Uk9 Alexandra Berry EPSRC Alexandra.Berry@Epsrc.Ac.Uk10 Yannick Bidal University Of St Andrews Yb2@St-Andrews.Ac.Uk11 Florent Bouxin University Of Glasgow Flobou@Chem.Gla.Ac.Uk12 Evert Boymans University Of Edinburgh E.H.Boymans@Tue.Nl13 Michael Buehl University Of St Andrews Buehl@St-Andrews.Ac.Uk14 Timothy D. H. Bugg University Of Warwick T.D.Bugg@Warwick.Ac.Uk15 David Burns University Of Edinburgh D.Burns@Ed.Ac.Uk16 Thomas Cadenbach University Of Edinburgh Thomas.Cadenbach@Ed.Ac.Uk17 Thibault Cantat Cea Saclay DSM Thibault.Cantat[At]Cea.Fr18 Roberto Caporalli Queren’s University Belfast Rcaporali01@Qub.Ac.Uk19 John Casci J. M. Technology Centre John.Casci@Matthey.Com20 Ludovic Castro University Of St Andrews Lc214@St-Andrews.Ac.Uk21 Alberto Cavalieri Edinburgh University A.Cavalieri@Tue.Nl22 Ross Chisholm University Of St Andrews Rc73@St-Andrews.Ac.Uk23 Matt Clarke University Of St Andrews Mc28@St-Andrews.Ac.Uk24 David Cole-Hamilton University Of St Andrews Djc@St-Andrews.Ac.Uk25 Alba Collado-Martinez University Of St. Andrews Acm22@St-Andrews.Ac.Uk26 Chris Collett University Of St Andrews Cjc45@St-Andrews.Ac.Uk27 Rosalyne Cowie Wiley-Vch Rmcowie@Gmail.Com28 Luke Crawford University Of St. Andrews Lc437@St-Andrews.Ac.Uk29 David Daniels University Of St Andrews Dsbd@St-Andrews.Ac.Uk30 Pierre Y. Dapsens Eth Zurich Pierre-Yves.Dapsens@Chem.Ethz.Ch31 Matthew Davidson University Of Bath M.G.Davidson@Bath.Ac.Uk32 Alyn Davies University Of St Andrews Ad96@St-Andrews.Ac.Uk33 Krijn de Jong Utrecht University K.P.Dejong@Uu.Nl34 Alix De La Houpliere University Of St Andrews Adlh@St-Andrews.Ac.Uk35 Castagna Diana University Of Strathclyde Diana.Castagna@Strath.Ac.Uk36 Megan Doble University Of St Andrews Megandoble7389@Gmail.Com37 James Dumesic University Of Wisconsin Dumesic@Engr.Wisc.Edu38 Stephanie Dupuy University Of St Andrews Sd53@St-Andrews.Ac.Uk39 Philip Dyer Durham University P.W.Dyer@Durham.Ac.Uk40 Barthel Engendahl DSM Chemical Technology Barthel.Engendahl@Dsm.Com41 Charlene Fallan St Andrews University Cf52@St-Andrews.Ac.Uk42 Jose Fernandez Salas University Of St Andrews Jafs2@St-Andrews.Ac.Uk43 Colin Finn University Of Edinburgh C.Finn-2@Sms.Ed.Ac.Uk44 Tom Forder University Of Bath T.R.Forder@Bath.Ac.Uk45 Jose A. Fuentes St Andrews University Jaf14@St-Andrews.Ac.Uk46 Adrián Gómez-Suárez University Of St. Andrews Ags20@St-Andrews.Ac.Uk47 Aaron Gamboa University Of Edinburgh Aaron.Gamboa@Ed.Ac.Uk48 Roger Glã¤Ser University Of Leipzig Roger.Glaeser@Uni-Leipzig.De49 Alberto Gomez Herrera University Of St Andrews Agh6@St-Andrews.Ac.Uk50 Juan M.G. Carballo Sasol Technology Juanmaria.Gonzalezcarballo@Eu.Sasol. Com

51 Eoin Gould University Of St Andrews Eg255@St-Andrews.Ac.Uk52 Stefano Guidone University Of St Andrews Sg599@St-Andrews.Ac.Uk53 Clair Halpin University Of Dundee C.Halpin@Dundee.Ac.Uk54 Alan Harper Heriot-Watt University A.J.Harper@Hw.Ac.Uk55 Adam Harvey Newcastle University Adam.Harvey@Ncl.Ac.Uk56 Alan Healy University Of St Andrews Ah96@St-Andrews.Ac.Uk57 Frank Heutz University Of St Andrews Fjlh@St-Andrews.Ac.Uk58 Rebecca How University Of St Andrews Rh53@St-Andrews.Ac.Uk59 Graham Hutchings Cardiff University Hutch@Cardiff.Ac.Uk60 Ben Jeffery University Of Bath Bjj21@Bath.Ac.Uk61 Jennifer Julis St. Andrews University Jj34@St-Andrews.Ac.Uk62 Paul Kamer University Of St Andrews Pcjk@St-And.Ac.Uk63 Nina Kann Chalmers University Kann@Chalmers.Se64 Kevin Kasten University Of St Andrews Kk47@St-Andrews.Ac.Uk65 Bert Klein Gebbink Utrecht University R.J.M.Kleingebbink@Uu.Nl66 Christopher Lancefield University Of St Andrews Csl9@St-Andrews.Ac.Uk67 Rafael Larraz CEPSA Rafael.Larraz@Cepsa.Com68 Faima Lazreg University Of St Andrews Fl24@St-Andrews.Ac.Uk69 Stuart Leckie University Of St Andrews Sml3@St-Andrews.Ac.Uk70 Alistair Lees Binghamton University Alees@Binghamton.Edu71 Walter Leitner Aachen University Leitner@Itmc.Rwth-Aachen.De72 Mathieu Lesieur University Of St Andrews Ml63@St-Andrews.Ac.Uk73 Li Li Durham University Li.Li2@Durham.Ac.Uk74 Ian Little INEOS Technologies Ian.Little@Ineos.Com75 David Lunn University Of Bristol David.Lunn@Bristol.Ac.Uk76 Jarret Macdonald University Of Edinburgh Jarmacdonal0@Gmail.Com77 Lois Manton University Of Bath Lm422@Bath.Ac.Uk78 Isobel Marr University Of Edinburgh I.H.Marr@Sms.Ed.Ac.Uk79 Anthony Martin University Of St Andrews Am280@St-Andrews.Ac.Uk80 Julie Mayen St-Andrews University Jm276@St-Andrews.Ac.Uk81 Ashley Mcveigh University Of Glasgow Alexis.Stevenson@Glasgow.Ac.Uk82 Daniel Minett University Of Bath D.R.Minett@Bath.Ac.Uk83 Laura Mitchell University Of St Andrews Lm947@St-Andrews.Ac.Uk84 Louis Morrill University Of St Andrews Lcm56@St-Andrews.Ac.Uk85 Richard Mudd University Of Strathclyde Richard.Mudd@Strath.Ac.Uk86 David Nelson University Of St. Andrews Djn5@St-Andrews.Ac.Uk87 Lorenz Obrecht University Of St Andrews Lo89@St-Andrews.Ac.Uk88 Rhodri Owen University Of Bath Reo20@Bath.Ac.Uk89 Javier Pérez-Ramírez Institute For Chemical Jpr@Chem.Ethz.Ch And Bioengineering90 Scott Patrick University Of St Andrews Srp3@St-Andrews.Ac.Uk91 Panagiota Pelekanaki University College London Panagiota.Pelekanaki.09@Ucl.Ac.Uk92 Noemie Perret Sasol Technology Noemie.Perret@Eu.Sasol.Com93 Dennis Pingen University Of Edinburgh Dpingen@Gmail.Com94 Dorota Plaza Warwick University D.D.Plaza@Warwick.Ac.Uk95 Matthew Potter University Of Southampton Mep1c10@Soton.Ac.Uk96 Marc Reid University Of Strathclyde Marc.Reid@Strath.Ac.Uk97 Neville Richardson University Of St Andrews Nvr@St-Andrews.Ac.Uk98 Ed Richmond University Of St Andrews Er323@St-Andrews.Ac.Uk99 Emily Robinson University Of St Andrews Er36@St-Andrews.Ac.Uk100 Graeme Rogers St Andrews University Gwr5@St-Andrews.Ac.Uk101 Jack Rowbotham University Of Durham Jack.Rowbotham@Durham.Ac.Uk

102 Michiel Samuels University Of St Andrews Ms211@St-Andrews.Ac.Uk103 Orlando Santoro University Of St Andrews Os7@St-Andrews.Ac.Uk104 Karin Schmid University Of St. Andrews Ks92@St-Andrews.Ac.Uk105 Bert Sels Ku Leuven Bert.Sels@Biw.Kuleuven.Be106 Andrew Smith University Of St Andrews Ads10@St-Andrews.Ac.Uk107 Upulani Somisara University Of St Andrews Dmuks@St-Andrews.Ac.Uk108 Daniel Stark University Of St Andrews Dgs2@St-Andrews.Ac.Uk109 Derek Stewart The James Hutton Institute Derek.Stewart@Hutton.Ac.Uk110 Sergey Tin University Of St Andrews St298@St-Andrews.Ac.Uk111 Bob Tooze Sasol Technology Uk Ltd Bob.Tooze@Eu.Sasol.Com And St Andrews University112 Fanny Tran University Of St Andrews Ft5@St-Andrews.Ac.Uk113 Byron Truscott University Of St Andrews Bt222@St-Andrews.Ac.Uk114 Nicholas Turner University Of Manchester Nicholas.Turner@Manchester.Ac.Uk115 Piet van Leeuwen ICIQ Pvanleeuwen@Iciq.Es116 Dieter Vogt University Of Edinburgh D.Vogt@Ed.Ac.Uk117 Allan Watson University Of Strathclyde Allan.Watson.100@Strath.Ac.Uk118 Bert Weckhuysen Utrecht University B.M.Weckhuysen@Uu.Nl119 Thomas West University Of St Andrews Thw2@St-Andrews.Ac.Uk120 Nicholas Westwood University Of St Andrews Njw3@St-Andrews.Ac.Uk121 Ross Wilkie University Of St Andrews Rw259@St-Andrews.Ac.Uk122 Bo Yang Queen’s University Belfast Byang02@Qub.Ac.Uk123 Pei-Pei Yeh University Of St. Andrews Py1@St-Andrews.Ac.Uk

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