Technology
offers portfolio
CNRS
METAL-ORGANIC
FRAMEWORKS
03/03/2015Julien Brohan [email protected] V4
83 Bd Exelmans, 75016 PARIS Tel + 33 (0) 1 40 51 00 90 Fax + 33 (0) 1 40 51 78 58
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Table of content
Table of contents
Table of contents ... 1
Metal Organic Frameworks ... 2
Focus on Metal Organic Frameworks developed at Institut Lavoisier (ILV) UMR8180 ... 3
Part 1: BIOLOGICAL APPLICATIONS ... 5
Highly efficient hybrid solid functionalization with peptides for biosensor ... 6
Part 2: PETROCHEMICAL APPLICATIONS ... 8
Hydrocarbons separation ... 9
MOF application: sulfur compounds separation from mixture of gases ... 10
Part 3: Depollution ... 11
MOF application: deNOx catalysis ... 12
CNRS technology offers portfolio - appendix ... 13
Metal Organic Frameworks
Metal-organic frameworks (MOFs), also called “hybrid porous crystallized solids”, are coordination polymers with a hybrid inorganic-organic framework comprising metal ions and organic ligands coordinated to said metal ions.
These materials are organized as mono-, bi- or tri-dimensional networks wherein the metal clusters are linked to each other by spacing ligands periodically. These materials have a crystalline structure and are generally porous.
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Focus on Metal Organic Frameworks
developed at Institut Lavoisier (ILV)
UMR8180
Gérard Ferey - Christian Serre – Thierry Loiseau
For more than ten years, the team of Gerard Ferey has focused on the synthesis and the characterization of MOF type porous solids by developing several research directions.
Figure 1 Example of MOFs originating from the ILV and entitled ‘Matériau Institut Lavoisier’ aka MIL-xxx
Many patent applications have consequently been filled. Some are co-owned by the CNRS and other institutions as a result of intensive collaborations.
Many are directly managed by the CNRS and thus FIST SA
Figure 2 Number of patents filled per year and managed by the CNRS / FIST SA / Type of patent / Field of application / Specific application
You will find below short reviews of every patented technologies available for a transfer to the industry. 0 1 2 3 4 5 6
2007
2008
2009
2012
2014
Biological
Depollution
Petrochemical
Various
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Table of content
Part 1:
BIOLOGICAL
Highly
efficient
hybrid
solid
functionalization with peptides for
biosensor
CONTEXT
In order to be fully operative, biosensors such as peptides must be immobilized on solid support. Such immobilization is currently done by grafting said sensors on flat surface or in 3D gel. However, the result is not satisfying as said grafting comes out disordered and amorphous.
The ability to position entities used for detection in an orderly manner inside cavities of a solid is clearly still a technological challenge that needs to be overcome. Doing so would highly increase biosensors’ efficiency and selectivity. Current methods
There is definitely a demand for an improved grafting process which could lead to a better and faster peptides anchorage in cavities of solids.
TECHNICAL DESCRIPTION
In the present work, the inventors have developed a very efficient and fast process to functionalize hybrid porous solids with oligopeptides on their external surface or inside their pores. Said process comprises an amide coupling step through the reaction of an oligopeptide on the surface of an amine containing solid in presence of a coupling agent.
In particular, said porous solid used in the invention is a Metal Organic Framework (MOF).
MOF are coordination polymers consisting of a hybrid inorganic-organic framework comprising metal ions and organic ligands coordinated to the said metal ions.
DEVELOPMENT STAGE
Said functionalization has been successfully assessed on a laboratory scale Functionalized solids have eventually been characterized
The following MOF have been assessed so far:
Al-MIL-101-NH2; Al-MIL-101-NH2; In-MIL-68-NH2; In-MIL-68-NH2 and Zr-UiO-66-NH2 Reference 06657-01 Keywords Biosensor; MOF; Metal Organic Framework; functionalization. Status of Patent French priority patent application FR1454772 filed on May 27, 2014 and entitled “Méthode de greffage d'oligopeptides dans des matériaux hybrides poreux” Inventors Jérôme CANIVET Jonathan BONNEFOY Elsje QUADRELLI David FARRUSSENG Commercial Status Exclusive or non-exclusive license Laboratory Institut de recherches sur la catalyse et l’environnement de Lyon (IRECELYON, UMR5256), Lyon, France Chemistry, Catalysis, Polymers and Processes (C2P2, UMR5265), Lyon, France
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BENEFITS
Apart of being very fast and efficient, the current process allows higher loadings and densities of oligopeptide inside the cavities of the MOF than in the state of the art.
INDUSTRIAL APPLICATIONS
Biosensor is clearly the main targeted application.
However, one can cite the use of said functionalized solid for asymmetric catalysis, enantioselective separation.
Part 2:
PETROCHEMICAL
APPLICATIONS
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Hydrocarbons separation
In the present work, the research team has developed porous metal-organic frameworks for the separation of mixtures of molecules having different unsaturation degrees and / or a different number of unsaturations. One can cite olefin and paraffin mixtures.
The separation of mixtures of compounds in the gaseous or liquid phase is a major industrial problem concerning, in particular, the chemical, petrochemical and/or pharmaceutical industrial sectors.
Finding an absorbent making it possible to replace this expensive method while satisfying the required criteria (selectivity, diffusivity, regeneration...) would constitute a major advance in this field.
Among the disadvantages of the processes already known, the following can be cited as examples:
prohibitive implementation costs
lack of selectivity of the separation materials
insufficient diffusivity of the species to be separated in the separation materials
problems of lixiviation with the existing separation materials
Among compounds to be separated, there is a real need to develop systems making it possible to separate olefin/paraffin mixtures efficiently, as well as other mixtures of molecules having different unsaturation degrees and/or a different number of unsaturations.
The present invention aims at answering each of this need.
Development stage
Separation of propane and propylene as well as acetylene and ethylene has been sucessfully demonstrated on a laboratory scale
Pending patents
01904-01
Scope: metal-organic frameworks for separating hydrocarbons mixture
Priority application: french patent application FR0803245 filed on June 11, 2008 and entitled « Solide hybride cristallin poreux réductible pour la séparation de mélanges de molécules ayant des degrés et / ou un nombre d’insaturations différents »
Extensions in Europe, Japan, Canada and USA.
Reference 01904-01 Keywords Metal-organic framework, MOF, hydrocarbons, separation, purification, olefin, paraffin, refining, petrochemistry Inventors Christian SERRE Alexandre VIMONT Philip LLEWELLYN San CHANG JON Patricia HORCAJADA- CORTES Gérard FEREY Marco DATURI Kyu HWANG YOUNG Commercial Status Exclusive or non-exclusive license Laboratory Institut Lavoisier (ILV, UMR8180), Versailles, France
MOF application: sulfur compounds
separation from mixture of gases
In the present work, the research team has developed porous metal-organic frameworks for the separation of sulfur compounds from mixture of gases. Sulfur compounds may be naturally present in natural gas or biogas. Absorption techniques are known to remove the major part of such sulfur compounds, with amine treatments for example. However such processes do not entirely remove such sulfur compounds or provide a gas substantially free of sulfur compounds, i.e. with residual concentrations below 50 ppm mol.There is a need for improved and/or alternative sulfur adsorbents and processes for capturing sulfur compounds, in particular adsorbents which may have a high sulfur selectivity, a strong chemical resistance to the corrosive sulfur gases and preferably, which may be regenerated without high energetic regeneration costs.
The present invention aims at answering each of this need.
Development stage
Separation of hydrogen sulfide from methane has been successfully demonstrated on a laboratory scale.
Pending patents
02064-01
Scope: metal-organic frameworks for separating sulfur compounds from gas mixture
Priority application: Great-Britain patent application 0807299.3 and 0823514.5 filed on April 22, 2008 and Decembrer 24, 2008 and entitled « Gas adsorbent » Extensions in Europe Reference 02064-01 Keywords Metal-organic framework; MOF; sulfur compounds; separation; purification gas mixture Inventors Guy DE WEIRELD Lomig HAMON Christian SERRE Thomas DEVIC Gérard FEREY Thierry LOISEAU Commercial Status Exclusive or non-exclusive license Laboratory Institut Lavoisier (ILV, UMR8180), Versailles, France
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Part 3:
MOF application: deNOx catalysis
Metal-organic frameworks (MOFs), are coordination polymers with a hybrid inorganic-organic framework comprising metal ions and organic ligands coordinated to said metal ions.These materials are organized as mono-, bi- or tri-dimensional networks wherein the metal clusters are linked to each other by spacing ligands periodically. These materials have a crystalline structure and are generally porous.
In the present work, the research team has developed porous metal-organic framework as a nitrogen-oxide “deNOx” catalyst. This constitutes a major advance in this area as it offers the enormous advantage of removing and converting NOx from a liquid or gaseous effluent even at room temperature and in the absence of reducing species. This overcomes all the problems and drawbacks of the prior art.
The increased mobility throughout the world unfortunately has an impact on the environment and on health.
The main pollutants emitted are oxides of carbon (CO and CO2), volatile organic compounds (VOCs), unburnt hydrocarbons, and nitrogen oxides. This last term essentially comprises nitric oxide (NO) and nitrogen dioxide (NO2), together with smaller amounts of nitrous oxide (N20), dinitrogen trioxide (N203) and dinitrogen tetroxide (N204).
Although much effort has been expended for removing these pollutants, using systems for reduction of NOx at the sources of emission (vehicles, smokestacks, etc.), increasing concentrations of nitrogen oxides are being recorded in cities. Various strategies have been adopted for tackling these problems, but to date, no technology is able to offer a proper response to this problem.
The present invention aims at answering each of this problem.
Development stage
DeNox absorption and catalysis with invention’s MOF have been successfully demonstrated on a laboratory scale.
Pending patents
02582-01
Scope: metal-organic frameworks for deNOx catalysis
Priority application: French patent application FR0902587 filed on May 28, 2009 and entitled « Utilisation d'un solide hybride cristallin poreux comme catalyseur de réduction d'oxydes d'azote et dispositifs »
Extensions in United States, Canada, Europe, Japan, China, South Korea
Reference 02582-01 Keywords Metal-organic framework, MOF; separation; purification; depollution; deNOx; nitrogen oxide Inventors Marco DATURI Jong-San CHANG Christian SERRE Alexandre VIMONT Patricia HORCAJADA-CORTES
Young Kyu HWANG Ji Wooing YOON Gérard FEREY Commercial Status Exclusive or non-exclusive license Laboratory Institut Lavoisier (ILV, UMR8180), Versailles, France
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CNRS technology offers portfolio - appendix
Field of application Type of patent Reference number Maininventor UMR Priority date filling year Priority application number Priority patent
publication number Territories Granted patents Co-ownership
Biological Application 06657-01 Farrusseng UMR5256 27/05/2014 2014 FR1454772 CNRS -UCBL
Petrochemical Application 02064-01 Serre UMR8180 22/04/2008 2008 GB 0807299.3
GB 0823514.5 WO2009130251
US (abandoned), EP, (abandoned) JP
CNRS - UVSQ - UMONS
Petrochemical Application 01904-01 Serre UMR8180 11/06/2008 2008 FR0803245 FR2932397 US, CA, EP, JP
EP (FR, LU, CH, GB, DE), FR (priority)
CNRS - UCBN - UVSQ - KRICT Dépollution Application 02582-01 Serre UMR818
0
28/05/200 9
200
9 FR0902587 FR2945966
US, CA, EP, JP,
CN, KR JP
CNRS - UCBN - ENSICAEN - UVSQ - KRICT
Reference number
IP
manager Title Abstract Specific application Main claim Structure MOF
06657-01 CNRS
Méthode de greffage
d'oligopeptides dans des matériaux hybrides poreux
metal-organic framework with modified surface as
biosensor biosensor Process /
02064-01 CNRS Gas adsorbent metal-organic framework for separating sulfur compounds
from gas mixture Sulfur extraction Process MmOkXlLp
01904-01 CNRS
Solide hybride cristallin poreux réductible pour la séparation de mélanges de molécules ayant des degrés et / ou un nombre d'insaturations différents.
metal-organic framework for separating hydrocarbons
mixture Hydrocarbon separation Product MmOkXlLp
02582-01 CNRS
Utilisation d'un solide hybride cristallin poreux comme catalyseur de réduction d'oxydes d'azote et dispositifs
metal-organic framework as denox catalyst for reducing
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The
CNRS
and
FIST SA
in few words…
France Innovation Scientifique et Transfert (FIST SA), established in 1992, is a French public limited company, now a subsidiary of the CNRS at 70% and 30% Bpifrance Financement. Its mission is to transfer innovative technologies, mainly originating from the CNRS, to the industry.
Its action extends from the receipt of projects to the granting of exploitation rights through consulting in Intellectual Property strategies, participation in the filing of patent applications, search of industrial partners, negotiating and drafting of exploitation contracts, and management of patent portfolios.
FIST SA has managed to develop a strong expertise in the following areas: Technology evaluation
Technology transfer Patent mapping Technology scouting
Intellectual Property consulting and management
FIST SA proposes services and products in: Technology evaluation and transfer Patent mapping - Customized studies Patent mapping - Multi-clients studies
Key figures of the activity on behalf of the CNRS
Management of approximately 2 200 patent families
Negotiation of 100 exploitation contracts per year since 2010 Management of 1 300 exploitation contracts
The Centre National de la Recherche Scientifique (National Center for Scientific Research) is a public organization under the responsibility of the French Ministry of Education and Research.
Key figures
3.4Md€ Budget for 2013
32,920 employees (at the end of 2013) 1,144 research units
11 offices abroad
43,000 publications per year in average 19 Nobel Price laureates
12 Fields Medal laureates
>700 spin-offs created since 2000
