Project acronym 2D-CHEM
Project Two-Dimensional Chemistry towards New Graphene Derivatives
Researcher (PI) Michal Otyepka
Host Institution (HI) UNIVERZITA PALACKEHO V OLOMOUCI
Call Details Consolidator Grant (CoG), PE5, ERC-2015-CoG
Summary The suite of graphene’s unique properties and applications can be enormously enhanced by its functionalization. As non-covalently functionalized graphenes do not target all graphene’s properties and may suffer from limited stability, covalent functionalization represents a promising way for controlling graphene’s properties. To date, only a few well-defined graphene derivatives have been introduced. Among them, fluorographene (FG) stands out as a prominent member because of its easy synthesis and high stability. Being a perfluorinated hydrocarbon, FG was believed to be as unreactive as the two-dimensional counterpart perfluoropolyethylene (Teflon®). However, our recent experiments showed that FG is not chemically inert and can be used as a viable precursor for synthesizing graphene derivatives. This surprising behavior indicates that common textbook grade knowledge cannot blindly be applied to the chemistry of 2D materials. Further, there might be specific rules behind the chemistry of 2D materials, forming a new chemical discipline we tentatively call 2D chemistry. The main aim of the project is to explore, identify and apply the rules of 2D chemistry starting from FG. Using the knowledge gained of 2D chemistry, we will attempt to control the chemistry of various 2D materials aimed at preparing stable graphene derivatives with designed properties, e.g., 1-3 eV band gap, fluorescent properties, sustainable magnetic ordering and dispersability in polar media. The new graphene derivatives will be applied in sensing, imaging, magnetic delivery and catalysis and new emerging applications arising from the synergistic phenomena are expected. We envisage that new applications will be opened up that benefit from the 2D scaffold and tailored properties of the synthesized derivatives. The derivatives will be used for the synthesis of 3D hybrid materials by covalent linking of the 2D sheets joined with other organic and inorganic molecules, nanomaterials or biomacromolecules.
Summary
The suite of graphene’s unique properties and applications can be enormously enhanced by its functionalization. As non-covalently functionalized graphenes do not target all graphene’s properties and may suffer from limited stability, covalent functionalization represents a promising way for controlling graphene’s properties. To date, only a few well-defined graphene derivatives have been introduced. Among them, fluorographene (FG) stands out as a prominent member because of its easy synthesis and high stability. Being a perfluorinated hydrocarbon, FG was believed to be as unreactive as the two-dimensional counterpart perfluoropolyethylene (Teflon®). However, our recent experiments showed that FG is not chemically inert and can be used as a viable precursor for synthesizing graphene derivatives. This surprising behavior indicates that common textbook grade knowledge cannot blindly be applied to the chemistry of 2D materials. Further, there might be specific rules behind the chemistry of 2D materials, forming a new chemical discipline we tentatively call 2D chemistry. The main aim of the project is to explore, identify and apply the rules of 2D chemistry starting from FG. Using the knowledge gained of 2D chemistry, we will attempt to control the chemistry of various 2D materials aimed at preparing stable graphene derivatives with designed properties, e.g., 1-3 eV band gap, fluorescent properties, sustainable magnetic ordering and dispersability in polar media. The new graphene derivatives will be applied in sensing, imaging, magnetic delivery and catalysis and new emerging applications arising from the synergistic phenomena are expected. We envisage that new applications will be opened up that benefit from the 2D scaffold and tailored properties of the synthesized derivatives. The derivatives will be used for the synthesis of 3D hybrid materials by covalent linking of the 2D sheets joined with other organic and inorganic molecules, nanomaterials or biomacromolecules.
Max ERC Funding
1 831 103 €
Duration
Start date: 2016-06-01, End date: 2021-05-31
Project acronym CATA-LUX
Project Light-Driven Asymmetric Organocatalysis
Researcher (PI) Paolo Melchiorre
Host Institution (HI) FUNDACIO PRIVADA INSTITUT CATALA D'INVESTIGACIO QUIMICA
Call Details Consolidator Grant (CoG), PE5, ERC-2015-CoG
Summary Visible light photocatalysis and metal-free organocatalytic processes are powerful strategies of modern chemical research with extraordinary potential for the sustainable preparation of organic molecules. However, these environmentally respectful approaches have to date remained largely unrelated. The proposed research seeks to merge these fields of molecule activation to redefine their synthetic potential.
Light-driven processes considerably enrich the modern synthetic repertoire, offering a potent way to build complex organic frameworks. In contrast, it is extremely challenging to develop asymmetric catalytic photoreactions that can create chiral molecules with a well-defined three-dimensional arrangement. By developing innovative methodologies to effectively address this issue, I will provide a novel reactivity framework for conceiving light-driven enantioselective organocatalytic processes.
I will translate the effective tools governing the success of ground state asymmetric organocatalysis into the realm of photochemical reactivity, exploiting the potential of key organocatalytic intermediates to directly participate in the photoexcitation of substrates. At the same time, the chiral organocatalyst will ensure effective stereochemical control. This single catalyst system, where stereoinduction and photoactivation merge in a sole organocatalyst, will serve for developing novel enantioselective photoreactions. In a complementary dual catalytic approach, the synergistic activities of an organocatalyst and a metal-free photosensitiser will combine to realise asymmetric variants of venerable photochemical processes, which have never before succumbed to a stereocontrolled approach.
This proposal challenges the current perception that photochemistry is too unselective to parallel the impressive levels of efficiency reached by the asymmetric catalysis of thermal reactions, expanding the way chemists think about making chiral molecules
Summary
Visible light photocatalysis and metal-free organocatalytic processes are powerful strategies of modern chemical research with extraordinary potential for the sustainable preparation of organic molecules. However, these environmentally respectful approaches have to date remained largely unrelated. The proposed research seeks to merge these fields of molecule activation to redefine their synthetic potential.
Light-driven processes considerably enrich the modern synthetic repertoire, offering a potent way to build complex organic frameworks. In contrast, it is extremely challenging to develop asymmetric catalytic photoreactions that can create chiral molecules with a well-defined three-dimensional arrangement. By developing innovative methodologies to effectively address this issue, I will provide a novel reactivity framework for conceiving light-driven enantioselective organocatalytic processes.
I will translate the effective tools governing the success of ground state asymmetric organocatalysis into the realm of photochemical reactivity, exploiting the potential of key organocatalytic intermediates to directly participate in the photoexcitation of substrates. At the same time, the chiral organocatalyst will ensure effective stereochemical control. This single catalyst system, where stereoinduction and photoactivation merge in a sole organocatalyst, will serve for developing novel enantioselective photoreactions. In a complementary dual catalytic approach, the synergistic activities of an organocatalyst and a metal-free photosensitiser will combine to realise asymmetric variants of venerable photochemical processes, which have never before succumbed to a stereocontrolled approach.
This proposal challenges the current perception that photochemistry is too unselective to parallel the impressive levels of efficiency reached by the asymmetric catalysis of thermal reactions, expanding the way chemists think about making chiral molecules
Max ERC Funding
2 000 000 €
Duration
Start date: 2016-11-01, End date: 2021-10-31
Project acronym InanoMOF
Project Multifunctional micro- and nanostructures assembled from nanoscale metal-organic frameworks and inorganic nanoparticles
Researcher (PI) Daniel Maspoch Comamala
Host Institution (HI) FUNDACIO INSTITUT CATALA DE NANOCIENCIA I NANOTECNOLOGIA
Call Details Consolidator Grant (CoG), PE5, ERC-2013-CoG
Summary In InanoMOF, we aim to develop frontier Supramolecular and Nanochemistry methodologies for the synthesis of a novel class of structures via controlled assembly of nanoscale metal-organic frameworks (nanoMOFs) and inorganic nanoparticles (INPs). These methods will embody the premise that “controlled object-by-object nano-assembly is a ground-breaking approach to explore for producing systems of higher complexity with advanced functions”. The resulting hybrid nanoMOF@INPs will marry the unique properties of INPs (magnetism of iron oxide NPs and optics of Au NPs) to the functional porosity of MOFs.
The first part of InanoMOF encompasses the design, synthesis-assembly and characterisation of nanoMOF@INPs - advanced MOF-based sorbents that incorporate the functionality of the INPs used: magnetically controlled movement, in vivo detectability, enhanced biocompatibility and porosity, pollutant removal, or controlled sorption/delivery. The second part of InanoMOF entails studying the physicochemical properties of the synthesised nanoMOF@INPs and ascertaining their utility as drug-delivery/theranostic systems and as magnetic sorbents for pollutant removal. Specifically, we will study their stability in working media and determine their capacities for drug or pollutant sorption/delivery capacities. As proof-of-concept, we will study their toxicity in vitro and in vivo; enhancement of their in vitro therapeutic efficacy; and their capacity to remove pollutants (in real water and gasoline/diesel fuel samples) via magnetic assistance.
In InanoMOF we will endeavour to establish the synthetic bases for controlling the spatial ordering of nanoMOF crystals, whether alone or combined with other nanomaterials (e.g. INPs, graphene, etc.). We are confident that our work will ultimately enable researchers to create MOF-based composites having cooperative and synergistic properties and functions for myriad applications (e.g. heterogeneous catalysis, sensing and separation).
Summary
In InanoMOF, we aim to develop frontier Supramolecular and Nanochemistry methodologies for the synthesis of a novel class of structures via controlled assembly of nanoscale metal-organic frameworks (nanoMOFs) and inorganic nanoparticles (INPs). These methods will embody the premise that “controlled object-by-object nano-assembly is a ground-breaking approach to explore for producing systems of higher complexity with advanced functions”. The resulting hybrid nanoMOF@INPs will marry the unique properties of INPs (magnetism of iron oxide NPs and optics of Au NPs) to the functional porosity of MOFs.
The first part of InanoMOF encompasses the design, synthesis-assembly and characterisation of nanoMOF@INPs - advanced MOF-based sorbents that incorporate the functionality of the INPs used: magnetically controlled movement, in vivo detectability, enhanced biocompatibility and porosity, pollutant removal, or controlled sorption/delivery. The second part of InanoMOF entails studying the physicochemical properties of the synthesised nanoMOF@INPs and ascertaining their utility as drug-delivery/theranostic systems and as magnetic sorbents for pollutant removal. Specifically, we will study their stability in working media and determine their capacities for drug or pollutant sorption/delivery capacities. As proof-of-concept, we will study their toxicity in vitro and in vivo; enhancement of their in vitro therapeutic efficacy; and their capacity to remove pollutants (in real water and gasoline/diesel fuel samples) via magnetic assistance.
In InanoMOF we will endeavour to establish the synthetic bases for controlling the spatial ordering of nanoMOF crystals, whether alone or combined with other nanomaterials (e.g. INPs, graphene, etc.). We are confident that our work will ultimately enable researchers to create MOF-based composites having cooperative and synergistic properties and functions for myriad applications (e.g. heterogeneous catalysis, sensing and separation).
Max ERC Funding
1 942 665 €
Duration
Start date: 2014-04-01, End date: 2019-03-31
