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 POPCRYSTAL
Project Precisely Oriented Porous Crystalline Films and Patterns
Researcher (PI) Paolo FALCARO
Host Institution (HI) TECHNISCHE UNIVERSITAET GRAZ
Call Details Consolidator Grant (CoG), PE5, ERC-2017-COG
Summary Metal-Organic Frameworks (MOFs) are nanoporous crystalline solids with narrow pore distributions and high accessible surface areas. MOFs are typically prepared in a polycrystalline form via the self-assembly of inorganic (nodes) and organic (links) building units. This bottom-up approach allows for properties such as, pore size, topology and chemical functionality to be precisely tailored. Such synthetic control has identified MOFs as promising platform material for device fabrication in the areas of microelectronics, photonics, sensing. However, current methods for fabricating MOF films and patterns cannot generate precisely oriented crystals on commercially relevant scales (i.e. cm). Thus, limiting access to applications that require anisotropic functional properties (e.g. optics, electronics, separation).
POPCRYSTAL will enable the fabrication of films and patterns composed of precisely oriented MOF crystals by exploiting crystalline ceramics to guide the aligned growth of MOF crystals. Remarkably, the scale of these heteroepitaxially grown MOFs is solely determined by the ceramic precursor which can be easily synthesized on areas covering mm2 to cm2.
POPCRYSTAL will advance a proof of concept study by addressing the following important research aims: the basic understanding of the formation mechanism and rules governing the heteroepitaxial relationship (WP1), the extension to different ceramic-MOF systems (WP2), the control over crystalline porous film and pattern features (WP3) and the fabrication of a proof-of-concept that will highlight the importance of aligned pores for separation (WP4).
In summary, by exploiting the heteroepitaxial growth mechanism between ceramics and MOFs POPOCRYSTAL will fabricate unprecedented crystalline MOF films and patterns with precisely oriented nanopores and nanochannels. Thus POPCRYSTAL intercrosses and connects nanoscale chemistry, controlled self-assembly on a macroscale and nanoporous-based device fabrication.
Summary
Metal-Organic Frameworks (MOFs) are nanoporous crystalline solids with narrow pore distributions and high accessible surface areas. MOFs are typically prepared in a polycrystalline form via the self-assembly of inorganic (nodes) and organic (links) building units. This bottom-up approach allows for properties such as, pore size, topology and chemical functionality to be precisely tailored. Such synthetic control has identified MOFs as promising platform material for device fabrication in the areas of microelectronics, photonics, sensing. However, current methods for fabricating MOF films and patterns cannot generate precisely oriented crystals on commercially relevant scales (i.e. cm). Thus, limiting access to applications that require anisotropic functional properties (e.g. optics, electronics, separation).
POPCRYSTAL will enable the fabrication of films and patterns composed of precisely oriented MOF crystals by exploiting crystalline ceramics to guide the aligned growth of MOF crystals. Remarkably, the scale of these heteroepitaxially grown MOFs is solely determined by the ceramic precursor which can be easily synthesized on areas covering mm2 to cm2.
POPCRYSTAL will advance a proof of concept study by addressing the following important research aims: the basic understanding of the formation mechanism and rules governing the heteroepitaxial relationship (WP1), the extension to different ceramic-MOF systems (WP2), the control over crystalline porous film and pattern features (WP3) and the fabrication of a proof-of-concept that will highlight the importance of aligned pores for separation (WP4).
In summary, by exploiting the heteroepitaxial growth mechanism between ceramics and MOFs POPOCRYSTAL will fabricate unprecedented crystalline MOF films and patterns with precisely oriented nanopores and nanochannels. Thus POPCRYSTAL intercrosses and connects nanoscale chemistry, controlled self-assembly on a macroscale and nanoporous-based device fabrication.
Max ERC Funding
1 996 315 €
Duration
Start date: 2018-05-01, End date: 2023-04-30
Project acronym VINCAT
Project A Unified Approach to Redox-Neutral C-C Couplings: Exploiting Vinyl Cation Rearrangements
Researcher (PI) Nuno Xavier Dias Maulide
Host Institution (HI) UNIVERSITAT WIEN
Call Details Consolidator Grant (CoG), PE5, ERC-2015-CoG
Summary The preparation of complex molecular architectures employing multi-component reactions where the number of bond-forming events is maximised is a central goal of the discipline of Organic Synthesis. The contemporary, pressing need for sustainable chemical reactions has raised the demand for novel reaction families that explore the concept of redox-neutrality and proceed with the generation of minimal waste. In this proposal, I present a unified and conceptually novel approach to atom-economical C-C bond formation in challenging contexts without the need for transition metal promoters or reagents. To this end, I propose the innovative harvesting of the potential of vinyl cation intermediates as platforms for the deployment of nucleophilic entities capable of orchestrating rearrangement reactions. The combination of such high-energy intermediates, generated under mild conditions, with the power of carefully designed rearrangements leads to an array of useful new transformations. Furthermore, the very high atom-economy and simplicity of these reactions renders them not only sustainable and environmentally friendly but also highly appealing for large-scale applications. Additional approaches to enantioselective synthesis further enhance the methods proposed.
The paradigm proposed herein for the exploitation of vinyl cations will also open up new vistas in the centuries-old aldol reaction and in amination chemistry. This showcases the vast potential of these simple principles of chemical reactivity. The myriad of new reactions and new product families made possible by VINCAT will decisively enrich the toolbox of the synthetic practitioner.
Summary
The preparation of complex molecular architectures employing multi-component reactions where the number of bond-forming events is maximised is a central goal of the discipline of Organic Synthesis. The contemporary, pressing need for sustainable chemical reactions has raised the demand for novel reaction families that explore the concept of redox-neutrality and proceed with the generation of minimal waste. In this proposal, I present a unified and conceptually novel approach to atom-economical C-C bond formation in challenging contexts without the need for transition metal promoters or reagents. To this end, I propose the innovative harvesting of the potential of vinyl cation intermediates as platforms for the deployment of nucleophilic entities capable of orchestrating rearrangement reactions. The combination of such high-energy intermediates, generated under mild conditions, with the power of carefully designed rearrangements leads to an array of useful new transformations. Furthermore, the very high atom-economy and simplicity of these reactions renders them not only sustainable and environmentally friendly but also highly appealing for large-scale applications. Additional approaches to enantioselective synthesis further enhance the methods proposed.
The paradigm proposed herein for the exploitation of vinyl cations will also open up new vistas in the centuries-old aldol reaction and in amination chemistry. This showcases the vast potential of these simple principles of chemical reactivity. The myriad of new reactions and new product families made possible by VINCAT will decisively enrich the toolbox of the synthetic practitioner.
Max ERC Funding
1 940 025 €
Duration
Start date: 2017-01-01, End date: 2021-12-31
