Transcript
Page 1: Novel materials and sustainable chemistry

Novel materials and sustainable chemistry

A decade of EU-funded research

su

cc

es

s s

to

ries

Page 2: Novel materials and sustainable chemistry

Interested in European research?

Research*eu is our monthly magazine keeping you in touch with main developments (results, programmes, events, etc.). It is available in English, French, German and Spanish. A free sample copy or free subscription can be obtained from:

European Commission Directorate-General for ResearchCommunication UnitB-1049 BrusselsFax (32-2) 29-58220E-mail: [email protected]: http://ec.europa.eu/research/research-eu

EUROPEAN COMMISSION

Directorate-General for ResearchDirectorate G – Industrial technologiesUnit G3 ‘Value – added materials’E-mail: [email protected]: http://ec.europa.eu/research/industrial_technologies/

Page 3: Novel materials and sustainable chemistry

EUROPEAN COMMISSION

Directorate - General for Research, Industrial technologies2008 Unit G3 ‘Value – added materials’ EUR 23585 EN

Novel materials and sustainable chemistryA decade of EU-funded research

G. Hernández, S. Bøwadt and J.L. Vallés

Page 4: Novel materials and sustainable chemistry

LEGAL NOTICE

Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of the following information.

The views expressed in this publication are the sole responsibility of the author and do not necessarily reflect the views of the European Commission.

A great deal of additional information on the European Union is available on the Internet.It can be accessed through the Europa server (http://europa.eu).

Cataloguing data can be found at the end of this publication.

Luxembourg: Office for Official Publications of the European Communities, 2008

ISBN 978-92-79-09721-8DOI 10.2777/99099

© European Communities, 2008Reproduction is authorised provided the source is acknowledged.

Printed in Belgium

PRINTED ON WHITE CHLORINE-FREE PAPER

EUROPE DIRECT is a service to help you find answers to your questions about the European Union

Freephone number (*):

00 800 6 7 8 9 10 11(*) Certain mobile telephone operators do not allow access to 00 800 numbers

or these calls may be billed

Page 5: Novel materials and sustainable chemistry

3

Table of contents

4 Mastering the building blocks essential for our daily lives

6 Materials and Chemistry in FP5

8 Clean route to precious metal catalyst recovery (2002-2005)

9 Catalyst system cuts eco-impact of pharmaceuticals manufacture (2002-2005)

10 On-the-spot hydrogen peroxide synthesis reduces processing risks (2002-2005)

11 Low-cost asthma sensor set to replace expensive hospital systems (2001-2004)

12 Cleaning up car exhausts (2001-2004)

13 Widespread application for anti-bacterial and anti-fouling

functionalised polymers (2001-2004)

14 Materials and Chemistry in FP6

16 ‘Solid smoke’ from cellulose (2004-2006)

17 Designer materials enhance pharmaceuticals purification (2004-2008)

18 Nanotechnology-based gas separation membranes exemplify

clean technology (2004-2007)

19 Bioprocessing improves on natural materials (2004-2007)

20 Network integrates EU catalysis research (2005-2010)

21 Better, safer lithium batteries for everyday applications (2007-2009)

22 Virtual laboratory unites European nanopore researchers (2004-2008)

23 Ligand bank cuts process development times (2004-2006)

24 Materials developments enhance nanocatalyst performance (2005-2008)

25 High-performance nanocomposites mimic nature (2005-2008)

26 European Membrane House coordinates key domain (2004-2009)

27 Polysaccharides to replace oils as source of tomorrow’s polymers? (2005-2009)

Page 6: Novel materials and sustainable chemistry

4 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Mastering the building blocks essential for our

Chemistry is the science of the atomic and molecular constituents of the real world: everything we see, smell, touch and taste is shaped through chemistry.

Chemicals are the building blocks of all the materials we use, the air we breathe, the food we consume – and even of our bodies themselves. Given this ubiquitous nature, the industrial manipulation of basic chemicals, frequently relying on new functionalised materials such as catalysts or membranes, impacts on virtually every aspect of our existence. Materials developments can therefore result in chemical process innovations capable of reducing costs, improving product performance and enhancing the quality of life. Chemistry is capable, on the other hand, of selectively modifying existing materials to tailor them for specific applications, for example by reshap-ing a polymeric structure or by adding functional groups to a surface.

Purpose-designed chemical products are essential to our power generating and storage systems, our transport infrastructure, our computers and mobile phones, our healthcare and security devices, our leisure and sporting accessories. Man-made chemical compounds fulfil vital roles in medical treatments, in food production and pro-tection, in paints and dyestuffs, in hygiene and cosmetic products… The list is endless.

Chemical industry transformation essentialIn the past, much of the chemical industry has been char-acterised by an exploitive use of natural resources, often taking insufficient account of the environmental conse-quences. Today, however, there is widespread recognition of the need to adopt cleaner, sustainable practices by switching from a resource-intensive to a knowledge-based approach.

The goal of sustainable chemistry is to meet the needs of the present without compromising the ability of future generations to meet their own needs. Using and building on our accumulated chemical knowledge and expertise can help to provide a solution to the challenge of climate change. By developing sound biological and eco-efficient processes, reducing the environmental impact of industrial processes and products, optimising the use of finite resources and minimising waste, know-ledge-based chemistry can also contribute greatly to ‘doing more with less’.

Prime examples can be seen in the use of silicon and pol-ymers to produce the sub-micron-sized components of modern information and communications technologies, the miniaturised, powerful and long-lasting batteries, which

EU funding on Novel materials and sustainablechemistry under FP5 and FP6

FP6€145 million58 projects

FP5€57.3 million36 projects

Page 7: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 5

control of the materials essential for the design of advanced chemical processes. Nanotechnologies and molecular mod-elling strategies provide the tools for a more precise handling of the chemical reactions leading, for instance, to materials functionalisation.

Crossing new technological frontiers involves under-standing and optimising material combinations and their synergistic functions in multi-material devices. Exciting products are also likely to arise from the integration of traditional and nano-structured materials.

This is why the EU is a strong supporter of research for the development of such innovative materials, in partic-ular of those for use in sustainable chemical technologies or produced thanks to them. In the following, a few ex -amples are shown of successful projects funded within this research area by the NMP Theme during FP5 and FP6.

have revolutionized our use of electronic gadgets during the last decade, and in the nanotechnology enhanced sensors and instruments that now form an integral part of today’s medical diagnosis and intervention.

Materials innovation leading to sustainable chemical tech-nologies is key to protecting and expanding employment in Europe by ensuring the continuing competitiveness of the EU chemical industry. Materials development obtained through chemical processes also creates opportunities for new enterprises in the materials and chemicals sectors.

Directions for changeThe requirements of tomorrow’s technology translate directly into increasingly stringent demands on the chem-icals: their intrinsic properties, their cost, their processing and fabrication, and their recyclability. This leads indirect-ly to demands on the tailor-made materials involved in their transformation and processing. The focus on eco-efficiency requires complete life cycle analysis to be conducted on newly developed products, considering both the ecological and economic aspects.

A variety of new technologies and approaches is emerg-ing to answer these needs by offering more rapid paths to the discovery, characterisation and direct molecular-level

Total number of projects in FP6 per subarea (€145 million)

Chemistry for energy

Chemical processing of materials

Polymer chemistry

Catalysis and chemical technologies

Hybrid materials

Total number of projects in FP5 per subarea (€57.3 million)

Hybrid materials

Polymer chemistry

Catalysis and chemicaltechnologies

Chemical processing of materials

daily lives

4

14

12

12

13

6

17

9

7

Page 8: Novel materials and sustainable chemistry
Page 9: Novel materials and sustainable chemistry

❉ Materials and Chemistry in FP5

Types Number of EC funding contracts CR 1 €0.5 millionRS 35 €56.8 million Grand Total 36 €57.3 million

CR = Cooperative Research (CRAFT) ProjectsRS = Research Projects

Page 10: Novel materials and sustainable chemistry

8 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Strategic precious metals (SPMs) are important as catalysts for chemical and pharmaceutical manufacture, as well as for fuel cells and automotive exhaust systems. As demand increases, the price of SPMs is rising – and the commercial and technical need for cost-effective recycling becomes more pressing.

Current recycling techniques use concentrated and/or aggres-sive chemicals, are energy-intensive and generally inefficient. For example, only around 6 % of the SPMs in car catalysts are recovered. Considerable economic advantage could thus be gained by developing simpler, higher-yielding processes for extracting these valuable catalysts from waste.

The three-year BIO-CAT project set out to produce improved catalysts from recovered SPMs by combining two biotech-nologies into a single process, permitting clean recovery and bulk synthesis into novel bionanocrystalline material forms. The partners also developed biotemplates comprising whole cells and proteins for Pd nanocluster preparation, involving controlled adsorption of Pd ions and reduction of the Pd clusters using hydrogen.

To demonstrate the benefits of this approach, the perform-ance of biologically-produced palladium – ’Bio-Pd0’ – as a chemical catalyst was compared with that of chemically-produced Pd catalysts.

❉ Project successes

Four biosystems have been developed: crystalline bacte-rial cell surface layer (S-layer) proteins and hydrogenase were synthesised in vitro; while in vivo processes delivered a range of hydrogenase-containing bacteria and an S-layer protein incorporating the bacterium bacillus sphaericus.

New nanocatalysts resulted from controlled adsorption of Pd ions from metal-salt solutions on the biotemplates, followed by reduction of the Pd clusters with an external hydrogen source.

Laboratory-scale systems for biological Pd-nanocluster preparation have been designed, built, demonstrated and evaluated. Bionanocrystals of Pd0 with good catalytic activity have been produced in the laboratory. Although their catalytic efficiency is not yet markedly superior to that of commercial products for reactions such as the reduc-tion of hexavalent chromium, oxidation of itaconic acid and the hydrogenation of various double-bonded com-pounds, it is still a very exciting result considering that the catalysts are made out of recycled materials.

One system is the ‘flow-through electroporous cell’: a tubular cell comprising a number of cylindrical sections, one of which contains a carbon support for immobilisa-tion of biomaterial from the flowing Pd-salt solution. The second is a column bioreactor, which is an adsorption tower with an external hydrogen source. Biomaterial, either immobilised on carriers or as free-floating powders, can be coated with metal in the presence of the salt solution.

Until the processes have been fully developed and opti-mised for commercial production, the project’s SPM recov-ery methods will be used to treat liquid processing waste provided by a precious metal catalyst producer.

A European patent filed on ‘Use of bacterium strains for the preparation of bimetallic biocatalysts, in particular for the preparation of palladium biocatalysts’, secures the essential IPR of the initiative.

G5RD-CT-2002-00750 – BIO-CAT Novel precious-metal-based bionanocatalysts from scrapTotal cost: €2 362 274 | EC contribution: €1 555 478Project duration: May 2002 – April 2005 (36 months) Coordinator: Wolfgang Skibar – C-Tech Innovation Limited, Chester, United Kingdom

Clean route to precious metal catalyst recovery (2002-2005)

8 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Palladised biomass of

D. desulfuricans, cells harvested

at the middle of exponential

phase. High catalytic activity.

A single cell of Desulfovibrio desulfuricans (a) (TEM, negative staining)

palladised D. desulfuricans cells (b) (SEM).

Bio-inspired processes eliminate aggressive chemicals in catalyst production.

Page 11: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 9

❉ Project successes

Small-scale production of controlled meso- and micro-porous carbon with controlled surface chemistry and particle size was accomplished. A patent has been granted.

A Pt based catalyst suitable for pharmaceutical manufac-ture applications was developed – although work on fine chemicals was abandoned due to technical problems.

Early demonstrations showed that a range of pharmaceuti-cally important reagents can be converted at rates better than 95 %, and isolated with yields higher than 90 %.

An optimised micro-channel reactor was constructed in accordance with the design specification, as well as a spherical mesoporous carbon catalyst support system. Measurements showed that control of the mesoporosity is crucial to the achievement of high conversion rates.

Results from the catalytic oxidation experiments proved that the optimised multichannel reactor is suitable for three-phase catalytic reactions. Conversions rates up to 75 % per 10 cm bed length were obtained.

This significant achievement in performance is due largely to a method used to integrate heat transfer, mixing and reaction functionality into a single reactor, as well as to the choice of reaction channel sizes.

Based on the results of the study, a 2kg/hour (isolated prod-uct yield) reactor has been designed and manufactured to demonstrate the viability of multichannel multifunctional compact reactor technology for the manufacture of fine chemicals and pharmaceutical intermediates.

In conclusion, it is shown that the developed compact multi-channel reactor shows considerable promise for the catalytic oxidation of organic feedstocks to produce pharmaceutical intermediates and products. From the obtained results it seems plausible that the reactor concept can be extended to other gas/liquid/solid catalytic systems.

Catalyst system cuts eco-impact of pharmaceuticals manufacture (2002-2005)

G5RD-CT-2002-00724 – CREATION Compact reactor and carbon supported catalyst system for multiphase air oxidation Total cost: €2 302 698 | EC contribution: €1 370 574Project duration: April 2002 – September 2005 (42 months) Coordinator: Pawel Plucinski – University of Bath, Bath, United Kingdom

A D E C A D E O F E U - F U N D E D R E S E A R C H 9

Existing processes for the oxidation of oxygenated mole-cules, as required for the manufacture of pharmaceuticals and fine chemicals, tend to use either stoichiometric amounts of nitric acid or inorganic oxidants, notably Cr 4+, both of which have significant environmental impacts.

The CREATION project aimed to overcome this problem by using air oxidation with heterogeneous catalysts in an aqueous environment, whereby water would be the only reaction by-product – thus reducing both gaseous and liquid effluents. The achievement of high purity, high yield production directly from this reaction would require both high conversion and high selectivity.

The proposal envisaged the development of a compact microchannel reactor system suitable for use in three-phase catalytic air oxidation reactions. The intention was to provide precise control of oxygen concentration along the reaction pathway, enhanced gas-liquid-solid mixing and improved heat transfer.

In order to optimise catalyst performance in the confines of the microchannel geometry, a carbon catalyst support system with precisely tailored nano/micro/mesopore struc-ture was also required, together with a suitable bimetallic catalyst system.

Micro-channel reactor pilot plant

assembly using mesoporous carbon

bead supported catalysts.

Indirect fired rotary kiln for

conversion of polymer beads.

Catalysed microchannel oxidation allows effluent-free pharmaceuticals production.

Page 12: Novel materials and sustainable chemistry

10 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Hydrogen peroxide, H2O2, is a clean oxidant with a high active oxygen content, which gives water as its sole by-product. It is used as a ‘green’ reagent in the bleaching of paper, cellulose and textiles, as well as in environ-mental applications such as water purification and the manufacture of chemicals.

Development of an economically viable process for in situ H2O2 manufacture would provide Europe’s chemical indus-try with a leading-edge technology for oxidation applica-tions. It could help to eliminate risks associated with the large-scale transport and storage of this highly active substance, while also facilitating its use in a wider range of reactions.

The initial goal of the three-year NEOPS project was to develop an effective, selective and reliable catalytic mem-brane reactor for the synthesis of H2O2 from hydrogen and water. The next step would be to prove the concept of an integrated technology employing H2O2 produced in situ for eco-efficient reactions based on selective oxidation for small- and large-scale market applications, such as phenol synthesis and the epoxidation/hydroxylation of chemicals of interest for fine chemicals production.

❉ Project successes

Carbon ceramic-coated membranes adaptable to multi-phase reactions have been prepared.

A prototype tubular catalytic membrane reactor has been developed, and good results achieved in the syn-thesis of H2O2.

Optimal catalysts and reaction conditions for the direct selective oxidation of benzene to phenol, alkene epoxi-dation and phenol hydroxylation using the H2O2 solution produced by direct H2O2 synthesis have been identified.

Significant progress was made in selective oxidation reactions, but further research will be needed to improve the understanding of structure-activity relationships in the catalyst as the means to improve selectivity and perform-ance in line with relevant industrial needs. The project’s techno-economical feasibility study also indicates that the integrated process is not currently competitive enough. Additional work will be required to prove whether in situ production and use of H2O2 in selective oxidation can become fully viable.

A German patent application has been lodged on ‘Opti-mized reactant concentration profiles in the catalytic layer in the membrane assisted direct synthesis of hydrogen peroxide as a key to high selectivity’.

On-the-spot hydrogen peroxide synthesisreduces processing risks (2002-2005)

G5RD-CT-2002-00678 – NEOPSNovel Eco-efficient oxidation processes based on H2O2 synthesis on catalytic membranesTotal cost: €3 487 550 | EC contribution: €1 891 128Project duration: May 2002 – July 2005 (36 months) Coordinator: Gabriele Centi – Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, Firenze, Italy

Interaction of

benzene with TS-1

catalyst sites for its

hydroxylation

to phenol.

New direct process of

benzene hydroxylation

to phenol using H2O2

in comparison with

the commercial process

via cumene.

In situ oxidant production shows promise for clean, hazard-free manufacture.

Page 13: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 11

Around 25 million Europeans are afflicted by asthma. The prevalence of the condition has risen over the past 20 years, especially among children, where it is now approaching 15 % in Western Europe.

A useful way to measure the degree to which this disease causes inflammation of sufferers’ airways is to measure the concentration of nitric oxide (NO) in the exhaled air. However, current inflammation measurement techniques are time-consuming, expensive and sometimes invasive. Although newly developed technologies enable some non-invasive pulmonary tests to be performed easily and repeatedly, the equipment currently costs approximately $25 000, and is neither mobile nor cheap to operate.

The SENTIMATS project targeted the introduction of inex-pensive, sensitive and reliable NO tests for patient diag-nosis and monitoring. The objective was to develop the principle and a prototype of a selective but low-cost type of hybrid organic/inorganic sensor for this purpose. This would be based on the seemingly simple concept of replac-ing the logic gate in a transistor-like device by sensor mol-ecules that react with the compound of interest, causing changes in the current passing through the transistor.

The aim was to produce a chip-based sensor that would cost less than €1 to make, and could be embedded in a device that could become commonplace in clinics, doctors’ surgeries and homes.

❉ Project successes

A new type of hybrid organic/inorganic sensor based on GaAs/AlGaAs or silicon-oxide-coated GaAs/AlGaAs devices has been developed and patented. This has been shown to be extremely sensitive to the electrical potential on its surface, which is measurably affected by the adsorp-tion of NO on the chemical sensing molecules attached on the surface. The sensor can detect NO at 1 ppb concentra-tion, and has a selectivity of about 1:108 against various gases like water, oxygen, CO2 and CO.

The partners have devised a procedure to prepare the GaAs surface for adsorption.

Negotiations are now underway regarding commercial production.

Low-cost asthma sensor set to replace expensivehospital systems (2001-2004)

G5RD-CT-2001-00569 – SENTIMATSDevelopment of a sensor for NO based on a hybrid organic-semiconductor device for detection of asthmaTotal cost: €1 961 758 | EC contribution: €1 159 190Project duration: December 2001 – November 2004 (36 months) Coordinator: Ron Naaman – Weizmann Institute of Science, Rehovot, Israel

Sensor for asthma.

Molecular controlled semiconductor resistor (MOCSER).

NOx-sensing device costing €1 slashes cost of monitoring lung patients.

Page 14: Novel materials and sustainable chemistry

12 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Nitrogen oxides (NOx) from vehicle exhaust emissions contribute to both the ‘greenhouse gas’ content of the atmosphere and the generation of acid rain.

The SMART project studied the application of advanced materials with self-tuneable and adaptive activity as novel catalytic devices for the removal of NOx from the exhaust output of lean-burn and diesel engines, which contains oxygen concentrations of up to 20 %. It also explored highly sensitive NOx sensors, able to operate with these oxygen concentrations.

The aims were to reduce NOx emissions by more than 50 % in the presence of oxygen, and to develop sensors able to detect NOx at concentrations below 100 ppm. This involved demonstrating the techno-economical feasibility and advantages of combining and integrating NOx sensors and catalysts.

A further intention was to show the feasibility of de-veloping smart catalytic devices for a range of different applications.

❉ Project successes

A new monolithic-type electrochemically-promoted reactor (MEPR) was produced, the prototype of which functioned satisfactory in O2 concentrations lower than 2 %. Further development to achieve significant NOx con-version in a real lean exhaust environment, with O2 con-centrations in the region of 10 %, was not possible within the project period.

A patent was registered on ‘Method and apparatus for carrying out electrochemically promoted reactions’.

Four complete devices integrating a sensor and a cata-lyst with different numbers of sensor and catalyst plates were constructed and tested.

The concept of a constant current potentiometric NOx sensor (CCP sensor) was demonstrated, while the prin-ciples of a multilayer ceramic amperometric sensor (MCA) were also established. Work continued to validate and scale-up the latter to a commercial stage.

Both types of sensors were able to detect NOx at concen-trations lower than 100 ppm.

Cleaning up car exhausts (2002-2005)

G5RD-CT-2002-00710 – SMARTNOx abatement systems for next-generation environmental technologiesTotal cost: €4 166 090 | EC contribution: €2 480 384Project duration: April 2002 – March 2005 (36 months) Coordinator: Sabine Thiemann-Handler – Robert Bosch GmbH, Gerlingen, Germany

Assembling the MEPR

integrated device:

integration of sensor

and catalyst plates into

one single device.

Electrochemically promoted catalysis explored as route to reduce acidic emissions.

Page 15: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 13

There is an emerging market for antimicrobials and anti-fouling additives in plastics for pharmaceutical packaging, fishing nets and underwater constructions, as well as for textile yarns and fibres. Suitable active agents are often mentioned in the literature – but, prior to the SPAN project, only few compounds had yet been commercialised.

Two main factors determine the efficacy of an antimicrobial compound:• the ability to inhibit microbial growth (biostatic effect);• the tendency to bind to microorganisms and subsequently

kill them (biocide effect).

The partners in SPAN sought both to develop antimicro-bial oligomers for incorporation into conventional poly-mers, and to chemically modify polymeric materials bearing functional groups with suitable antimicrobial properties. Synthesising a novel antimicrobial polymeric material in a way that allowed controlled release of the antimicrobial effect over an extended period of time was seen as one viable method of providing protection against a broad spectrum of bacteria or fouling organisms, without creating hazard to the environment or end user.

The envisaged approach for creating polymers with anti-bacterial properties was a considerable advance on existing products. Their performance would no longer depend on small bacteriostatic molecules incorporated by simple mix-ing into polymeric matrices with little control over uniform-ity in dispersion, migration and leaching. The antibacterial action would rather derive from groups located on the backbone of the polymer chain, thus being part of the polymer itself.

Since no chlorine or heavy metals were involved in the proposed approach, and the final polymers would remain recyclable, they could be treated as commodity plastics without environmental restrictions.

❉ Project successes

Compounds from three different classes have proved to have antimicrobial or antifouling properties. End products including injection moulded containers and yarns were produced and successfully tested at pilot scale.

Protection of fibres either by oligomers with antibacterial or antifouling properties, or by silver microparticles, has been demonstrated.

A patent on ‘High density polyethylene (HDPE) with pro-nounced antimicrobial properties’ was granted in Greece and is pending at European level.

Following completion of the three-year project, one devel-opment line being pursued is yarn for outdoor use, with antifouling protection by antimicrobial oligomers. Another is antimicrobial filaments protected by silver nanoparticles, made using a process that increases fibre quality and decreases the amount of silver required. This makes them particularly suitable for use in medical wear, due to their low toxicity.

Widespread application for anti-bacterial andanti-fouling functionalised polymers (2001-2004)

G5RD-CT-2001-00568 – SPANSpecialty antimicrobial polymeric materials Total cost: €1 950 163 | EC contribution: €1 209 204Project duration: November 2001 – October 2004 (36 months) Coordinator: Alexis Stassinopoulos – Argo S.A., Koropi, Greece

SEM of composites

containing elementary

silver powder (JMAC).

SEM micrographs

showing the dispersion

of two silver powders in

a PA matrix.

Built-in functional groups improve polymers’ resistance to infective agents and algal growth.

Page 16: Novel materials and sustainable chemistry
Page 17: Novel materials and sustainable chemistry

❉ Materials and Chemistry in FP6

Types Number of EC funding contracts IP 3 €38.7 millionSTREP 55 €106.3 million Grand Total 58 €145.0 million

IP = Integrated ProjectsSTREP = Specific Targeted Research Projects

Page 18: Novel materials and sustainable chemistry

16 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Aerogels are ultra-light solids produced by extracting the liquid component of a gel by supercritical drying, which allows the liquid to be drawn off without causing the solid matrix to collapse. The resultant material has extremely low density and in the case of silica aerogels is semi-transparent, giving rise to the popular names ‘solid smoke’ or ‘blue smoke’.

The goal of the AEROCELL project was to produce aero-gels with nano- or submicron-sized pore structures from renewable natural polymers, especially cellulose. The po-tential of such materials, which have huge specific surface areas and are biodegradable, was seen to be enormous. Applications were envisaged in many different fields, in-cluding packaging, controlled release and delivery systems, electrochemistry, fuel cell hydrogen storage, chromato-graphy columns, thermal and acoustic insulation and plant growth supports.

At the time of the project launch, this was largely unex-plored territory. Nothing was known apart from a scien-tific paper reporting an attempt to prepare an aerogel from a cellulose-derivative solution, and a first successful pre-liminary test made at the end of 2002 to prepare a pure ultra-light cellulose structure. The development of aerocel-lulose depended upon bringing together multidisciplinary teams to acquire basic new knowledge and exploit the synergy between the different scientific areas.

❉ Project successes

Aerocellulose was successfully obtained from cellulose/NaOH/water solutions. A production path via N-methyl-morpholine-N-oxide (NMMO)-route was optimised and streamlined.

A new family of aerogels, made by urethane cross-linking of cellulose acetate, showed promise for applications in thermal insulation. Highly porous aerocellulose material developed via a cellulose carbamate route appeared inter-esting for loading with non-aqueous liquids. Working with different cellulose solutions revealed that cellulose was generally suited for the production of spherical particles with diameters in the range of 300-1 200 μm using a so called jetcutter technology.

Four supercritical drying procedures were developed at pilot and full scale, and a pilot plant with a drying volume of 20 litres was designed. A feasibility study considered a plant with drying volumes of 1-5 m3.

A wide range of carbon aerogels (CA) was produced by pyrolysis for subsequent evaluation. Their use for super-capacitor purposes proved problematic, but most could yield better results with further future development. The utilisation of CA from cellulose in industrial batteries was shown to be possible, with minor modification of the assembly process.

The best aerocellulose samples were also characterised and tested for various applications. They unfortunately proved to be unsuitable for packaging or cosmetics use, but were found to be interesting as a carrier for the solidification of non-aqueous liquid surfactants and oils. However, the cost remains a barrier to commercial exploitation.

‘Solid smoke’ from cellulose (2004-2006)

NMP3-CT-2003-505888 – AEROCELL Aerocellulose and its carbon counterparts – porous, multifunctional nanomaterials from renewable resourcesTotal cost: €4 250 745 | EC contribution: €2 299 376Project duration: January 2004 – December 2006 (36 months)Coordinator: Hedda Weber – Lenzing Aktiengesellschaft, Research and Development, Lenzing, Austria

Areocellulose beads

from the early stages

of the project.

Aerocellulose was

produced in different

shapes, e.g. beads

or cylinders.

Renewable solid aerogels poised for widespread application when costs become more competitive.

Page 19: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 17

Current development of new pharmaceutical products such as fermentation-based antibodies, recombinant pro-teins and monoclonal antibodies (MAB) creates an urgent need for improved production technologies.

The market for MABs is growing at an annual rate of 20 %; more than 120 are now being developed and tested. They could theoretically be used for successful treatment of various illnesses, including cancer and Alzheimer’s, but production capacities will not meet the demand when they are commercially launched.

To bridge this gap, the Integrated Project AIMs is target-ing significant enhancements in the downstream process-ing of such biopharmaceuticals. This entails the design of new interactive materials for the purification of MABs, and the development of new, high capacity purification technologies.

Experimentally validated molecular modelling strategies are being used to improve the understanding of material/product interactions, while the integration of materials and process design should greatly increase process effi-ciency at an early development stage. The intention is to establish reliable, highly flexible computer-aided design strategies.

❉ Project successes

At the time of publication, new chromatographic beads with tuneable properties and enhanced mechanical stabil-ity (chromatographic resin FractoAIMs) had been developed and produced, as had affinity membranes (SartoAIMs protein A affinity membrane) with an open pore structure that significantly increases capacity.

The validated molecular modelling allowed prediction of the interaction between support, ligand and product for various types of system.

Development of a continuous chromatographic unit for the purification of MABs with ion-exchange materials is complete. In addition, a multi-stage aqueous two-phase extraction unit has been developed and scaled-up.

Detailed process models have been produced for chro-matography, membrane separation and extraction, together with software interfaces that allow for an easy exchange of data between the detailed unit operation models and a generic process model.

Designer materials enhance pharmaceuticalspurification (2004-2008)

NMP3-CT-2004-500160 – AIMs Advanced interactive materials by designTotal cost: €19 712 232 | EC contribution: €11 400 547Project duration: April 2004 – September 2008 (54 months) Coordinator: Andrzej Górak – Dortmund University of Technology, Dept of Bio- and Chemical Engineering, Laboratory of Fluid Separations, Dortmund, Germany

SEM image of an affinity membrane with open pore structure. Final structure of the system IgG (green), ligand

(orange), linker (yellow), and support (blue).

New materials and systems unblock production bottleneck for urgently-needed drugs.

© SA

RTORIO

US A

G

© PO

LITECN

ICO

DI M

ILAN

O

Page 20: Novel materials and sustainable chemistry

18 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Membrane technologies are model examples of sustain-able development: they generally function at moderate temperatures, and do not involve energy-consuming phase changes or chemical additives. They are simple in concept and operation, modular, easy to scale-up – and have great potential for more rational utilisation, recovery and re-use of chemicals.

With a 10-20 % annual growth rate, the world market for membranes with industrial and medical applications is expected to exceed €2.7 billion in a decade. With the exception of membranes for medical therapy, however, European industry remains relatively underdeveloped in this area.

The EU nevertheless enjoys a strong position in the na-nosciences, which opens new avenues to the design of complex high-performance multifunctional membranes. Combining polymers with inorganic nanoparticles gives rise to porous materials with selectivities far better than those of pure polymers for the separation of liquids and gas mixtures such as O2/N2, CO2/CH4 and butane/methane.

The COMPOSE project investigated a series of nano-structured organic/inorganic hybrid materials for this pur-pose. It also conducted research into the self-assembly of supra molecular structures (the building principle behind biological membranes) in order to establish the technical feasibility of employing such an approach to manufacture new membranes. Further studies explored the application of these developments in the chemicals and pharmaceuticals industries.

❉ Project successes

A novel poly(4-methyl-2-pentyne)/TiO2 nanocomposite membrane for butane/methane separation was incor-porated into a module that is now being tested as a means of natural gas purification.

Another new membrane based on a cellulose polymer modified with a nano-sized filler has been shown to offer excellent properties for oxygen enrichment, and is now being tested by an industrial user.

A layer-by-layer process for the preparation of aligned flakes in a matrix of poly(dimethylisoloxane) rubber was developed. With this, it was possible to achieve a remarka-bly high selectivity in separating helium and hydrogen from nitrogen.

Prototype membranes resistant to organic solvents have been prepared, characterised and incorporated into a bench-scale nanofiltration test unit.

Thin films of self-organising block copolymers on con-ventional microporous supports were made. On dense substrates, it proved possible to grow thin films with hexagonally ordered pores orientated perpendicularly to the film plane. This structure is extremely interesting for membrane manufacture.

A combination of the well-established non-solvent-induced phase separation method of membrane formation with the self-assembly of a block copolymer has been demonstrated in a straightforward and very rapid one-step proce-dure for producing an asymmetric membrane of block copo lymer with a highly ordered layer on top of a non-ordered sponge-like layer.

A patent application has been entered for ‘New mem-brane formation method by simultaneous self-assembly and non-solvent induced phase separation’.

Nanotechnology-based gas separation membranes exemplifyclean technology (2004-2007)

NMP3-CT-2003-505633 – COMPOSE Multicomponent nanostructured materials for separation membranes Total cost: €2 864 839 | EC contribution: €1 829 719Project duration: March 2004 – July 2007 (42 months)Coordinator: Klaus-Viktor Peinemann – GKSS Forschungszentrum Geesthacht GmBH, Institute of Chemistry, Department of Membrane Development, Geesthacht, Germany

SEM photo of block copolymer membrane with a very regular

porous structure. The membrane has been prepared by simultaneous

self-assembly and non-solvent induced phase separation. A patent

for this totally new membrane formation method is pending.

PMP/TiO2 membrane, which

was developed in Compose.

The membrane has been

produced into a module and

is now being tested for

natural gas purification.

European nanoscience is improving polymer membrane performance for industry and medicine.

Page 21: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 19

Over millions of years, nature has evolved fibrous materi-als such as wool, silk, leather and feather, with unique physical and chemical structures giving rise to remarkable combinations of surface and bulk properties. The HIPER-MAX project team sought to build on these matrices through bioprocess engineering, introducing innovative enzymatic technologies to modify and improve the estab-lished materials with a view to their exploitation in various industrial sectors.

The project covered four main areas:• analysis and definition of the accessibility of useful tar-

gets in natural proteins e.g. amino, hydroxyl, sulfhydryl, carboxyl or carboxamide groups;

• screening for novel enzymes to catalyse the modification of surface and bulk properties of the protein matrices, fol-lowed by production of those enzymes at pilot scale;

• mechanistic investigations of the enzymatic reactions on modelled and real substrates;

• exploitation of enzymes for surface and bulk modification of the protein matrices in order to develop engineered materials.

❉ Project successes

Novel sulfhydriloxidases (SOXs) were screened and charac-terised, with the aim of incorporating molecules with desired functionalities into proteinaceous fibres by means of enzymatic grafting. The potential of fungal tyro-sinase to catalyse grafting of functionalities onto wood and silk was also assessed.

New transglutaminase (TGase) genes have been identified. Screening of large culture collections and isolates identi-fied six novel microbes as suitable TGase sources.

Modelling of TGase-catalysed grafting and cross-linking of amines to protein substrates was confirmed via mass spectrometry.

Tyrosinase-catalysed grafting of phenolic and thiol com-pounds into wool and silk fibres was verified.

TGase and tyrosinase were applied to improve the ten-sile strength and shrink resistance of untreated and air-plasma-treated wool. The chemical reactivity and accessibility of target residues in wool and silk have been analysed and a database set up.

Tyrosinase-catalysed production of protein-polysaccha-ride bioconjugates and surface functionalisation of protein materials was demonstrated.

The production of moulded products and paper from feathers is undergoing further evaluation. In all, 30 com-mercially feasible feather- and wool-based products were made on a semi-industrial scale.

An important outcome of the project is the efficient uti-lisation of waste poultry feathers in the manufacture of mixed paper/feather products. The project has realised a unique manufacturing process whereby substituting enzyme-treated feathers for pulp and paper in innova-tive non-woven packaging products seems to be com-mercially competitive. Considering that in the UK alone some 2 000 tonnes of feathers are produced per week, which previously could only be disposed of in landfills or by burning, this is a truly important result for society.

Functionalised protein matrices of interest for tissue engineering and medical devices such as scaffolds have been produced from blends of silk fibroin/gelatine and hydroxyapatite/collagen sponges. Enzyme-catalysed treat-ment of hide powder and leather were also shown to impart anti-odour properties and improve dyeing.

Melt-extruded guides for peripheral nerve repair have been manufactured from blends between poly(ε-caprolactone) and gelatine, with inner surfaces function-alised by poly(L-lysine).

Two patent applications have been submitted, respec-tively on ‘Production of hollow conduits based on natural and synthetic polymers for applications in peripheral nerve regeneration’ and ‘Use of thiol groups in tyrosinase-catalysed grafting’.

Bioprocessing improves on natural materials (2004-2007)

SEM image of chicken

feather paper: flat cellulose

(wood pulp) fibres

and individual chicken

feather fibres.

Reel of chicken feather paper

made at the University

of Manchester.

NMP3-CT-2003-505790 – HIPERMAX High performance industrial protein matrices through bioprocessingTotal cost: €4 257 412 | EC contribution: €2 997 283Project duration: March 2004 – May 2007 (39 months) Coordinator: Elisabeth Heine – DWI an der Rwth Aachen e.V., Aachen, Germany

Functionalisation by enzyme grafting creates new uses for wool, hide and feather.

Page 22: Novel materials and sustainable chemistry

20 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

The development of high-performance and conceptually innovative catalytic nanomaterials is crucial for industry and for Europe’s competitiveness and sustainability. EU research in this field has been fragmented, due to the lack of a strong thematic identity and communication gaps between separate scientific communities dealing with heterogeneous, homogeneous and bio-catalysts.

The IDECAT network was therefore created to bring about a lasting integration between the main European institutions operating in all aspects of catalysis. This will create a critical mass and assemble the multidisciplinary competences necessary to design the next generation of catalysts and sustainable catalytic processes/technologies. In doing so, it can be expected to increase the cost-effec-tiveness of European research.

A prime objective is to bridge the gap between theory and modelling, surface science and kinetic\applied cataly-sis, as well as between heterogeneous, homogeneous and biocatalytic approaches. Actions include the development of frontier research initiatives on the synthesis and master-ing of nano-objects as the materials of the future for catalysis; integrating the design of catalytic nanomaterials to achieve breakthrough innovation; and incorporating concepts derived from other nanotechnologies.

A European Research Institute of Catalysis (ERIC) will be cre-ated, to offer companies and public sponsors the opportu-nity to realise top-level projects drawing on the extensive experience and competences afforded by the network. It will provide access to a pool of equipment, some unique, and expertise in associated laboratories operated as multi-site user facility for selected joint activities.

❉ Project successes

Two years on from the launch of the NoE, the legal basis for the establishment of ERIC as an independent jurid-ical structure in the form of AISBL under Belgian law was established by all the relevant parties.

Effective collaboration with industrial companies has started with the creation of an Industrial Council and an International Liaison Office.

The strengthening of collaborative projects – notably in the areas of supported catalysis, dendrimers, polymerisation, enzymes and ionic liquids – has been achieved through the launch of various joint PhD programmes.

A number of measures have been taken to increase researcher mobility and facilitate equipment sharing. Schemes favouring the exchange of PhD students, post-docs and young researches are being pursued. Upgrading of existing equipment by the purchase of new parts and software is also underway.

Dedicated workshops have been organised to define roadmaps in specific areas relevant to sustainability. Three macro-tasks have been defined: ‘Nanoporous materials as tailored reaction space’, ‘Nanofibrous materials as cat-alysts and supports’ and ‘Chemically nanostructured and functionalised materials’. The IDECAT research roadmap has been published.

Several joint research activities have been launched or continued on the themes of nanostructured electro-catalysts and photocatalysts, catalysts for the production of fine chemicals and polymeric materials, and catalysts for biofuels and biomass gasification.

A wide range of activities has been organised to pro-mote catalysis and disseminate information to the catalysis community. Still more are supporting the transfer of knowledge to industry.

A dozen academia-industry proposals for FP7 are being prepared; a patent databank is being set up; and a book-let ‘Inventory of IDECAT research’ has been published and distributed to the members of the Industrial Board.

Network integrates EU catalysis research (2005-2010)

NMP3-CT-2005-011730 – IDECAT Integrated design of catalytic nanomaterials for a sustainable production Total cost: €10 800 000 | EC contribution: €9 500 000Project duration: April 2005 – March 2010 (60 months)Coordinator: Gabriele Centi – Consorzio Interuniversitario per la Scienza e Tecnologia dei Materali (INSTM), Firenze, Italy

Bridging the gap between fundament

and application of catalysis is a major

objective of IDECAT for the development

of next generation catalytic materials.

Europe-wide institute pools equipment and expertise in search for next-generation sustainable catalysts.

Page 23: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 21

Lithium ion batteries are excellent power sources for both small- and large-scale applications, from mobile phones and laptop computers to electric vehicles. However, they suffer from some drawbacks, such as age-related capacity loss and a tendency to overheat under continuous charge.

The ILLIBATT project is seeking to develop safer, better per-forming and environmentally benign technology that makes use of solid-state electrolytes containing non-volatile and thermally stable ionic liquids, together with nano-structured anodes and advanced cathodes. Resulting new materials are expected to be useful across an extended range of cell sizes, from micro-batteries to very large delocalised storage units (10-20kWh) and vehicle battery packs rated at up 50kWh.

The proposal for the three-year initiative identifies four key objectives:• development of a green and safe solid-state electrolyte

chemistry based on ionic liquids; • use of novel nano-structured high capacity anodes pre-

pared with the help of novel ionic liquids;• investigation of the properties of the electrolytes and of

their specific interactions with advanced commercial and self-prepared anode and cathode materials;

• construction of rechargeable lithium cells with optimised electrode and electrolyte components.

This research could position Europe at the forefront of a de-veloping field of high performances batteries. This is a very important priority for European research considering the

approaching paradigm change in the automotive industry towards hybrid cars powered by batteries and traditional fuel engines. The combination of innovations should make it possible to realise true solid-state lithium batteries operating at room temperature, delivering specific en-ergy higher than 180 Wh/kg with respect to the overall weight of the cells. The coulombic efficiency is expected to average higher than 99 % during cycling; and life-times to reach 1 000 cycles with a 20 % maximum loss of capacity.

❉ Project successes

By the end of the first project year, polymer electrolytes and an anhydrous high-purity ionic liquid exhibiting conductivity higher than 1 mS cm-1 had been prepared. The synthesis and characterisation of polymeric ionic liquids were also completed, together with a small-scale prepara-tion of conducting composites containing suitable binder polymers and ionic liquids.

Electrochemical testing procedures and standardised conditions were defined, and samples of all the cathode materials have been tested.

In the remaining project period, work will continue with the design and fabrication of solvent-free, all-solid-state concept batteries, as well as evaluation of their electro-chemical and safety performance.

Better, safer lithium batteries for everyday applications (2007-2009)

NMP3-CT-2006-033181 – ILLIBAT Ionic liquid based lithium batteriesTotal cost: €2 667 513 | EC contribution: €1 848 396Project duration: January 2007 – December 2009 (36 months) Coordinator: Martin Winter – Westälische Wilhelms Universität Münster, Institute of Physical Chemistry, Münster, Germany (former Technische Universitaet Graz, Institute for Chemistry and Technology of Inorganic Materials (ICTAS), Graz, Austria)

The ILLIBAT polymer battery

concept: a vacuum-sealed,

laminated, solid-state cell and

its voltage profile at 40 °C and

different discharge rates.

Sub-ambient temperature ionic liquid (Tm = -18 °C).

Solid-state Li-ion batteries set to deliver more power, last longer in phones, computers and cars.

Page 24: Novel materials and sustainable chemistry

22 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Nano-porous materials can often serve in successful replacements for traditional polluting and energy- con-suming separation techniques employed for chemical processing. Nanomaterials are widely used as catalysts, catalyst supports and membranes, forming the basis of innovative technologies involved in energy storage, high-temperature molecular sieve separation (e.g. hydrogen purification) and low-temperature sorption separation (e.g. CO2 removal).

As in other technology areas, a fragmentation of resources and expertise is impeding European progress in this field. In response, the INSIDE-PORES NoE is creating a ‘laboratory without walls’, by developing innovative in situ and ex situ techniques that can be assembled into special case studies for investigation within a common infrastructure.

A further objective is to advance the nano-manipulation of porous materials from the current state of the art, i.e. method tailoring, to the bottom-up design, preparation and optimisation of material structures and their clean technology applications.

❉ Project successes

In its first three years of existence, the NoE assessed and clustered the disparate research into a more efficient and inspirational common research programme.

The participating academic partners have been integrated into an independent legal entity, established in the legal form of a Belgian International non-profit association (AISBL), and named the European Nanomaterials Institute of Excellence (ENMIX). This will implement an innovative strategy in order to address sustainability issues by adopt-ing beneficial technology transfer arrangements for both the academic and industrial collaborators.

Integration of human and material resources into the vir-tual laboratory has been realised by the creation of the ‘Supertool’ infrastructure for testing materials and optimising processes in a sophisticated and interactive collaborative environment. This is used to streamline the management process, monitor network progress and perform educational tasks. An INSIDE-PORES website (www.pores.gr) coordinates the activities of the partner laboratories.

A Supertool study regarding chemical vapour deposition (CVD) modification of membranes is already complete.

Several well-defined reference nanomaterials – carbon molecular sieves, spherical activated carbon, inorganic membranes, microporous silica (silicalite), etc. – were selected for testing using all of the proposed techniques. A prototype flow-controller system developed by the coordinating institute will assist in the performance of these experiments.

Many conferences, schools and workshops have been organised, including the first INSIDE-PORES workshop, the Seventh International Symposium on the Characterisation of Porous Solids, the ‘Diffusion Fundamentals I’ conference and the INSIDE-PORES South Africa workshop.

Promotional materials have also been compiled and distributed at numerous conferences and exhibitions. A spe-cial issue of the ‘Microporous and Mesoporous Materials’ journal (April 2008) included research presentations from the first workshop.

Virtual laboratory unites European nanopore researchers (2004-2008)

NMP3-CT-2004-500895 – INSIDE-PORES In situ study and development of processes involving nano-porous solids Total cost: €6 800 000 | EC contribution: €6 800 000Project duration: October 2004 – September 2008 (48 months) Coordinator: Nick Kanellopoulos – National Centre for Scientific research ‘Demokritos’, Attiki, Greece

Nanoporous catalytic membranes.

‘Lab without walls’ introduces Supertools in drive to replace polluting separation techniques.

Page 25: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 23

New metal-catalysed processes form a rapidly expanding sector of the global fine chemicals and pharmaceuticals markets, with a 10-15 % annual growth rate and already representing a value greater than €6 billion/year.

The key requirement in realising such processes is the identification of reaction additives, called ligands, which strongly promote the desired catalytic activity. Typically, the route to a successful new process involves checking the efficacy of large numbers of ligands – often more than 100. Although the checking process is completed in less than one day, synthesis of the ligands themselves may require months of work. This is often the slowest step in new process discovery – and, to date, European endeavours in this area have tended to be fragmented.

The objective of the LIGBANK initiative was therefore to create a central bank of ligand molecules, pre-screened for their applicability to reactions of fundamental impor-tance in the relevant sectors. This would be realised as a readily accessible and highly interactive website allow-ing dynamic searching by interested researchers and pro-viding a forum for the exchange/sale of ligands, related additives and other information on catalysis.

❉ Project successes

The European Ligand Bank was duly set up at www.ligbank.com, and now boasts an ever-expanding number of users. Membership is open to all of the European cata-lytic chemistry community, including industrial enterprises.

By the end of the three-year project, some 600 structurally diverse samples of ligand additives had been identified and trialled in both existing and new chemical reactions.

A number of these were new discoveries displaying exceptional properties. One example is the trimethyl-aluminium analogue DABAL – which is an air-stable white powder, whereas its parent spontaneously combusts in air. DABAL has been commercialised for use in the prep-aration of secondary chiral alcohols, which are useful pharmaceutical building blocks.

Patent-protected in situ quench methods contributed by an SME member for the preparation of pyridyl amino-alcohol ligands allow their rapid synthesis in flow and carousel reactors.

Activities within the project led to the publication of three patents, 46 scientific papers and 63 oral presentations at world-wide industrial, academic and scientific meetings. A follow-up COST Action on innovative catalysis now encompasses over 20 EU countries.

Ligand bank cuts process development times (2004-2006)

NMP3-CT-2003-505267 – LIGBANK The European Ligand Bank: an innovation facilityTotal cost: €2 463 000 | EC contribution: €2 150 000Project duration: January 2004 – December 2006 (36 months) Coordinator: Simon Woodward – The University of Nottingham, School of Chemistry, University Park, Nottingham, United Kingdom

Central info-bank is a living, growing resource for Europe’s catalyst community.

Comparison of air-stable DABAL and its pyrophoric parent trimethylaluminium.

Page 26: Novel materials and sustainable chemistry

24 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Pharmaceuticals, healthy food ingredients, perfumes and many other fine chemicals play important roles in the lives of mankind. In many cases, improving the quality of such products is inhibited by the low selectivity of hetero-geneous catalysts based on nano-sized metallic particles, which are used in various synthesis processes.

To overcome this obstacle, the NANOCAT project ex-plored methods of enhancing catalytic performance by adjusting the size and environment of the nanoparticles. This began with the assembly of fundamental knowledge about the synthesis of catalysts on inorganic and organic support matrices, as a basis for the development of more effective new particle/matrix combinations.

Another essential step was to determine the link between the nanocatalysts’ properties and their performance in industrially important reactions, such as hydrogenation/oxidation and isomerisation, while also monitoring the rates of catalyst deactivation and risks of metal leaching.

Establishing correlations between the nanoparticle size-shape-environment and catalytic behaviour required the development of reaction mechanisms by means of diffusion and time-dependent kinetic modelling.

❉ Project successes

Ru, Pt, Au and Pd particles of 1-10 nm diameter were incorporated into organic and inorganic matrices. In a bid to further improve activity and selectivity, bi-metallic catalysts were also synthesised.

Specific metal-polymer nanoscale systems have been designed and prepared for in situ synthesis of nanoparticles at high metal concentrations.

An efficient method was developed for the formation of Pt metal nanoparticles with various structures and morphologies in a matrix of hyper-crosslinked polystyrene.

A number of hydrogenolysis, dehydrogenation and oxida-tion reactions were performed. A database of catalyst screening results relating catalytic activity in variety of reactions to kinetic results from comparison between met-als of constant particle size supported on inorganic and organic matrices has been prepared. A correlation of solvents with catalyst performance was also completed.

In an effort to integrate and thereby optimise the exper-imental performance, the partners performed quantum chemical calculations for several supported catalytic systems, aimed at investigating: • the structural and energetic characteristics of the support; • the relationships occurring between metal particle size,

shape and the 3D surrounding environment; • the influence of the above relationships on the kinetic

properties of the studied materials, with respect to the hydrogenation, isomerisation and dehydration processes.

Applications have been entered for two patents on ‘Evaluation of the performance profile of catalysts’.

Six prototypes were delivered: TEGMA stabilised Pd/C, DEAEMA stabilised Pd/C, PVP stabilised Pd/C, PVP stabilised Pt/C, PVP stabilised Pd/CNF, Pt/mesoporous alumosilicate.

Materials developments enhance nanocatalyst performance (2005-2008)

NMP3-CT-2005-506621 – NANOCAT Tailored nanosized metal catalysts for improving activity and selectivity via engineering of their structure and local environment Total cost: €2 515 800 | EC contribution: €2 054 699Project duration: February 2005 – January 2008 (36 months) Coordinator: Dmitry Murzin – Abo Akademi University Faculty of Chemical Engineering, Laboratory of Industrial Chemistry, Turku Suomi, Finland

Reactants inside

a mesoporous material.

3D high resolution TEM

of metal particles.

Better understanding of particle-matrix interactions boosts catalytic efficiency.

Page 27: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 25

Whereas most current nanocomposites rely mainly on physical bonding between a nanofiller and matrix, the NANOHYBRID project sought to learn from nature to pro-duce skeleton-like superstructures and hybrids built using a combination of chemical and physical bonding. The aim was to derive new melt-processable nanophase-separated hybrid materials from low cost petrochemical olefin feedstocks. With controlled architectures and prop-erties designed to permit easy processing, the novel materials are likely to be suitable for a variety of industrial applications, from packaging and low weight engineering materials to communications technology.

The adopted approach was intended to overcome a limita-tion of earlier polyolefin-based composites, which pose dif-ficulties in dispersing tectons (nanometer-scaled building blocks such as organophilic inorganic polyelectrolyte nano-particles, that induce self-assembly, functional silicates, organoclays, and carbon nanotubes) in the matrix. Solving this problem would open the door to a real breakthrough in material performance.

Progress depended upon the acquisition of new know-ledge related to macromolecular architecture design via

transition metal catalysis, and understanding the phenom-ena of nanocomposite formation by in situ polymerisation or during melt processing. Extensive evaluation and test-ing was also necessary to adapt the new materials to real industrial requirements.

❉ Project successes

A range of novel nanoparticles were produced – including doped and non-doped alumina, silica-alumina, hydrotalcites and specially developed carbon nanotubes.

New catalysts such as those based on rare-earth metal complexes and novel synthesis led to the creation of poly-mer architectures, random and block copolymers and other compositions for improved matrix/filler adhesion and nanofiller dispersion.

Catalysts supported on tectons for in situ polymerisation produced nanoparticles coated with polymer, used as inter-mediates to obtain nanohybrids with high inorganic content. Complex melt-processable polyolefin hybrids were also designed.

Nanocomposites containing very small amounts of nano-metre-scaled anisotropic tectons successfully combined chemical and physical bonding between nanofiller and matrix.

Investigation of the fundamental characteristics of the organic-inorganic interphase region and their relation-ship with nanocomposite properties by multi-scale analysis during in situ polymerisation and melt processing represents a frontier achievement in this field of research.

Tests showed extensive improvements in mechanical, thermal and electrical properties.

Application studies identified materials worthy of further development for automotive parts, ICT devices, high-performance elastomers and components for MEMS (micro-electro-mechanical systems).

High-performance nanocomposites mimic nature (2005-2008)

NMP3-CT-2005-516972 – NANOHYBRID Designed nanostructured hybrid polymers: polymerisation catalysis and tecton assemblyTotal cost: €2 761 394 | EC contribution: €2 070 000Project duration: March 2005 – February 2008 (36 months) Coordinator: Incoronata Tritto – Istituto per lo Studio delle Macromolecole-Consiglio Nazionale delle Ricerche (Ismac-CNR) Milano, Italy

Nanohybrid dielectric thin film (shutter).

Nanohybrid dielectric thin film (bond).

Skeleton-like superstructures and nanohybrids show new way to derive engineering plastics from low-cost feedstocks.

Page 28: Novel materials and sustainable chemistry

26 N O V E L M AT E R I A L S A N D S U S TA I N A B L E C H E M I S T RY

Membrane science is regarded as one of the main stra-tegic axes of innovative process research activities in all developed countries (a set of ‘dominant technologies’). With an annual market growth rate above 10 %, membranes now play a leading role in many industries – including water treatment, energy, electronics, healthcare and agro-business. They are used in processes and systems involving separations, reactions, sensing and actuation.

The importance of membrane technology is emphasised by the fact that one of the major challenges of this cen-tury is the provision of safe drinking water for a growing population. The shortages in water resources (e.g. in Africa and the Middle East, but also in regions of Europe) will soon require the availability of more efficient and cheaper processes, fed not only from surface waters or aquifers but also from sea, brackish or waste waters. The most promising solutions to this problem could come from new membranes tailored at the nano-scale level.

Fine-tuning membrane properties requires a multidisci-plinary approach combining solid-state chemistry, supra-molecular chemistry, polymer chemistry, organic synthesis, physico-chemistry of interfaces and solutions, modelling and chemical engineering. A particular demand is to syn-thesise nanostructured artificial membranes mimicking

the functions of naturally occurring cellular membranes that control many functions of life.

To coordinate EU effort in this domain, the NANOMEMPRO network is creating a European Membrane House to share research facilities, develop common procedures and protocols, foster professional mobility, and provide new opportunities for training and education in membrane engineering. It will forge strong links between industrial stakeholders via a ‘Club of Interest’ concentrating on four application areas: new production processes and system approaches, food quality and safer production methods, sustainable energy systems, and life support and health.

❉ Project successes

The statutes of the European Membrane House, in the form of a non-profit association under Belgian law, have already been adopted by the partners. As well as providing a plat-form to support industry-driven research projects, this will form a channel of communication between the EC and the European Membrane Research Area and a natural inter-face to prepare further collaborations with other similar organisations in the other world regions.

A roadmap has been drawn up and presented to the membrane community to initiate new collaboration in defining a strategic business and research agenda for membrane technologies in Europe.

The mobility plan covers masters, PhDs, postdocs and research staff, including those from industrial research and development centres. Available courses and poten-tial partners for common degrees (master/doctoral) have been identified, and additional collaborative programmes are being organised.

European Membrane House coordinates key domain (2004-2009)

NMP3-CT-2004-500623 – NANOMEMPRO Expanding membrane macroscale applications by exploring nanoscale material properties Total cost: €13 160 000 | EC contribution: €6 380 000 Project duration: September 2004 – February 2009 (54 months) Coordinator: Gilbert M. Rios – Centre National de la Recherche Scientifique, Paris, France

Polymer capillary membrane

for chromatography.

PVDF support with top polymeric dense layer.

Research collaboration strengthens EU competitiveness in membrane engineering.

Page 29: Novel materials and sustainable chemistry

A D E C A D E O F E U - F U N D E D R E S E A R C H 27

The use of renewable raw materials is one of the corner-stones of European policy, which has objectives to promote biodegradation and to double the share of renewable energy from 6 % in 1997 to 12 % in 2010.

In this context, polysaccharides such as starch and cellulose are extremely interesting. They are very abundant in nature, representing an almost inexhaustible source of natural raw materials. They are the sustainable polymeric materials of tomorrow. When synthetic polymers derived from oil become expensive and rare, renewables could replace oil-based materials with biodegradable and biocompatible products in sectors such as paper, textiles, packaging, healthcare, hygiene, construction and transport.

The mission of the POLYSACCHARIDE initiative is to or-ganise the EU scientific community around a network fostering the use of polysaccharide renewable industrial feedstocks for the development of advanced multifunc-tional materials. Its consortium includes leading research centres and top-ranked universities with expertise and state-of-the-art technologies in key polysaccharide-related disciplines, including chemistry, chemical engineering, enzymology, modelling, physics, processing, material science, life-cycle analysis and economics.

Building a single umbrella organisation, the European Polysaccharide Network of Excellence (EPNOE), will allow full integration of all these resources into a Europe-wide ‘super-laboratory’, conducting shared activities and inter-acting directly inside the partner organisations. Included in its remit will be the training of scientists in academia and industry; spreading of knowledge, results and best practices; and attracting the interest of citizens to science.

❉ Project successes

The network of 16 partners is conducting a very active col-laborative research which benefits both laboratories and students. The placement of 14 PhDs in several research projects adds further to the spreading of knowledge.

The constitution and registration of the EPNOE Asso-ciation is complete, and efforts are proceeding to attract industrial participants. A first meeting in Paris drew 56 com-panies, and a Business Industrial Club with six activity areas already counts more than 20 members.

An education roadmap and new research roadmap for 2010-2015 have been completed.

Formal links with related organisations, including the Euro-pean Bioplastics association, American Chemical Society and Polymer Processing Society, are broadening the exchange of information.

The first successful EC projects have been announced: a Marie Curie Initial Training Network (STEP) and a large-scale project (Surfuncell).

Two leading EPNOE scientists received prestigious awards. The ‘Personal Contribution to Bio-plastics’ prize went to Martin Patel, University of Utrecht, and Bjarne Holmbom, Aabo Academy, collected the Wallenberg prize for sustainability of renewable resources in forestry and technology of the forest products industry.

Polysaccharides to replace oils as source of tomorrow’s polymers? (2005-2009)

NMP3-CT-2005-500375 – POLYSACCARIDE The European Polysaccharide Network of ExcellenceTotal cost: €9 900 000 | EC contribution: €5 000 000Project duration: May 2005 – October 2009 (54 months) Coordinator: Patrick Navard – Centre for Material Forming (CEMEF), Paris, France

Novel Polysaccharide based nanoparticles for drug targeting.

Research community unites to explore the potential of an abundant natural resource.

Page 30: Novel materials and sustainable chemistry

How to obtain EU publications

Our priced publications are available from EU Bookshop (http://bookshop.europa.eu), where you can place an order with the sales agent of your choice.

The Publications Office has a worldwide network of sales agents. You can obtain their contact details by sending a fax to (352) 29 29-42758.

European Commission

EUR 23585 – Success stories in the materials field – A decade of EU-funded research

Luxembourg: Office for Official Publications of the European Communities

2008 – 27 pp. – 21 x 29.7 cm

ISBN 978-92-79-09721-8DOI 10.2777/99099

Acknowledgements

The authors express their thanks for the contributions of the coordinators and the programe officers of the projects.Furthermore, the collaboration of Mike Parry, Michael Horgan, Charlotte Andersdotter and Bingen Urquijo Garay is acknowledged.

Page 31: Novel materials and sustainable chemistry

KI-N

A-2

35

85

-EN

-C

Chemicals are the building blocks of all the materials we use, the air we breathe, the food we consume, and even of our own bodies. Given their ubiquitous nature, the industrial manipulation of basic chemicals, frequently relying on new functionalised materials such as catalysts or membranes, impacts on virtually every aspect of our existence. Materials development can therefore result in chemical process innovation capable of reducing costs, improving product performance and enhancing the quality of life. Chemistry is capable, on the other hand, of selectively modifying existing materials to tailor them for specific applications, for example by reshaping a polymeric structure or by adding functional groups to a surface. This publication presents in a condensed form the objectives and main achievements of 18 selected projects from a group of nearly 100 projects funded under the 5th and 6th Framework Programmes in the fields of novel materials and sustainable chemistry.


Top Related