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 Supramol
Project Towards Artificial Enzymes: Bio-inspired Oxidations in Photoactive Metal-Organic Frameworks
Researcher (PI) Wolfgang Schmitt
Host Institution (HI) THE PROVOST, FELLOWS, FOUNDATION SCHOLARS & THE OTHER MEMBERS OF BOARD OF THE COLLEGE OF THE HOLY & UNDIVIDED TRINITY OF QUEEN ELIZABETH NEAR DUBLIN
Call Details Consolidator Grant (CoG), PE5, ERC-2014-CoG
Summary Metal-organic frameworks (MOFs) are key compounds related to energy storage and conversion, as their unprecedented surface areas make them promising materials for gas storage and catalysis purposes. We believe that their modular construction principles allow the replication of key features of natural enzymes thus demonstrating how cavity size, shape, charge and functional group availability influence the performances in catalytic reactions. This proposal addresses the question of how such novel, bio-inspired metallo-supramolecular systems can be prepared and exploited for sustainable energy applications. A scientific breakthrough that demonstrates the efficient conversion of light into chemical energy would be one of the greatest scientific achievements with unprecedented impact to future generations. We focus on the following key aspects:
a) MOFs containing novel, catalytically active complexes with labile coordination sites will be synthesised using rigid organic ligands that allow us to control the topologies, cavity sizes and surface areas. We will incorporate photosensitizers to develop robust porous MOFs in which light-absorption initiates electron-transfer events that lead to the activation of a catalytic centre. In addition, photoactive molecules will serve as addressable ligands whereby reversible, photo-induced structural transformations impose changes to porosity and chemical attributes at the active sites.
b) Catalytic studies will focus on important oxidations of alkenes and alcohols. These reactions are relevant to H2-based energy concepts as the anodic liberation of protons and electrons can be coupled to their cathodic recombination to produce H2. The studies will provide proof-of-concept for the development of photocatalytic systems for the highly endergonic H2O oxidation reaction that will be explored using most stable MOFs. Further, gas storage and magnetic properties that may also be influenced by light-irradiation will be analysed.
Summary
Metal-organic frameworks (MOFs) are key compounds related to energy storage and conversion, as their unprecedented surface areas make them promising materials for gas storage and catalysis purposes. We believe that their modular construction principles allow the replication of key features of natural enzymes thus demonstrating how cavity size, shape, charge and functional group availability influence the performances in catalytic reactions. This proposal addresses the question of how such novel, bio-inspired metallo-supramolecular systems can be prepared and exploited for sustainable energy applications. A scientific breakthrough that demonstrates the efficient conversion of light into chemical energy would be one of the greatest scientific achievements with unprecedented impact to future generations. We focus on the following key aspects:
a) MOFs containing novel, catalytically active complexes with labile coordination sites will be synthesised using rigid organic ligands that allow us to control the topologies, cavity sizes and surface areas. We will incorporate photosensitizers to develop robust porous MOFs in which light-absorption initiates electron-transfer events that lead to the activation of a catalytic centre. In addition, photoactive molecules will serve as addressable ligands whereby reversible, photo-induced structural transformations impose changes to porosity and chemical attributes at the active sites.
b) Catalytic studies will focus on important oxidations of alkenes and alcohols. These reactions are relevant to H2-based energy concepts as the anodic liberation of protons and electrons can be coupled to their cathodic recombination to produce H2. The studies will provide proof-of-concept for the development of photocatalytic systems for the highly endergonic H2O oxidation reaction that will be explored using most stable MOFs. Further, gas storage and magnetic properties that may also be influenced by light-irradiation will be analysed.
Max ERC Funding
1 979 366 €
Duration
Start date: 2015-09-01, End date: 2020-08-31
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
