Final Report Summary - COORDSPACE (Chemistry of Coordination Space: Extraction, Storage, Activation and Catalysis)
The aims of the project were originally defined in 2008 via four Workpackages:
Workpackage 1: Synthesis of ligand precursors and metal-organic framework (MOF) synthesis;
Workpackage 2: Gas and volatile organic compound (voc) adsorption, purification and activation;
Workpackage 3: Catalytic H2 production;
Workpackage 4: Metal cation and anion extraction and transport.
The research has progressed very much as planned, and particular progress and focus has been placed on the synthesis of porous hybrid materials and their ability to store and selectively bind gaseous substrates, especially H2, CO2, SO2, CH4, acetylene, ethylene and related volatile organic substrates (eg aromatic substrates) and of precious metal values. Photocatalytic H2 production has been successfully achieved using low molecular weight complex mimics that model the structure and function of hydrogenase enzymes. Inherent across our metal complex and materials research is the ability to chemically modify, dope and tune structure and properties, and at the heart of this project has been the design and discovery of new functional materials for specific applications. Particular highlights of the research include:
• the synthesis of a very wide range of new poly-dentate organic ligands/tectons and their incorporation into new families of MOF materials showing permanent porosity and novel substrate storage, selectivity and binding (J. Am. Chem. Soc., 2009, 131, 2159-2171; Chemistry Eur. J., 2009, 15, 4829-4835; Inorg. Chem., 2009, 48, 11067-11078; Chemistry Eur. J., 2010, 46, 13671-13679; Chem. Comm., 2011, 47, 8304-8306);
• the synthesis in 2009 of a porous polyhedral metal organic framework (NOTT-112) showing very high H2 storage capacity (above 10wt% and 50 g/L) and the formation of a range of analogous materials that have given insights into the structural and topological features that underpin their properties (ChemComm, 2009, 1025-1027; J. Am. Chem. Soc., 2010, 132, 4092-4094; Chem. Comm., 2011, 47, 4487-4489; Chemistry Eur. J., 2011, 17, 11162-11170; Chem.Comm. 2011, 47, 9995-9997; Acc. Chem. Res., 2014, in press. DOI: 10.1021/ar400049h).
• the invention of a new methodologies for H2 storage modulated by cation exchange in which porous anionic frameworks are doped by different metal cations to enhance binding and the isosteric heat of adsorption of substrates (Nature Chemistry, 2009, 1, 487-493);
• the development of the “pore with gate” mechanism in hybrid materials in which gas can enter and leave the porous host only when the chemical valve (a metal or organic cation) is opened (Faraday Discussions, 2011, 151, 19-36; Inorg. Chem., 2011, 50, 9374-9384);
• the design, synthesis and characterisation of the first defect MOF material: this material shows high capacity and selectivity for CO2 storage and these properties have been modelled theoretically and rationalised based upon the observed defect structure (Nature Materials, 2012, 11, 710-716);
• The successful selective capture of CO2 using decorated MOFs (Chem. Sci, 2012, 3, 2993-2999; Chem. Sci., 2013, 4, 1731-1736; Angew. Chem. Int. Ed., 2013, 125, 13656-13660; Chemistry Eur. J., 2014, 20, in press)
• the design, synthesis and characterisation of an isostructural series of new water and thermally-stable MOF materials, denoted as NOTT-300, based upon M(III) centres (M = Al, Sc, Ga, In, Bi, Cr), and the modulation of the properties of these porous hosts by developing mixed metal hybrids that show enhanced catalytic, photo and storage properties;
• the direct visualisation of CO2 and SO2 capture and binding in NOTT-300(M) (M = Al, Ga, In) by diffraction and scattering techniques supported by DFT calculations within this robust porous host: supramolecular hydrogen bonding interactions stabilise host-guest interactions and explain the high selectivity that these materials show for CO2 and SO2 (Nature Chemistry, 2012, 4, 887-894);
• binding and storage of NOx substrates within MOF hosts and the characterisation of their binding and dynamics;
• selective hydrocarbon binding (methane vs ethylene vs acetylene) in NOTT-300(Al) and the full structural and dynamic analysis and characterisation of the supramolecular chemistry (hydrogen-binding, π-π stacking and van der Waals interactions) underpinning the selective binding of acetylene (Nature Chemistry, 2014, submitted);
• the chemical transformation of flexible MOF structures catalysed by SO2 and other external stimuli (J. Am. Chem. Soc., 2013, 135, 4954-4957);
• the discovery of a new class of porous organic material, SOF (Supramolecular Organic Framework) showing permanent porosity and excellent reversible gas uptake and discrimination: these materials may be derived from a single or from two different organic components that assemble via hydrogen-binding and π-π stacking to form robust three dimensional structures (J. Am. Chem. Soc., 2010, 132, 14457-14469);
• the successful application of green and sustainable synthesis of MOFs in near-critical water thus circumventing the use of toxic organic solvents such as dimethylformamide (Green Chemistry, 2012, 14, 117-122);
• the expansion of this green synthetic route to the development of continuous flow systems using high temperature water and ethanol for the scale-up and sustainable manufacture of MOFs (Green Chemistry, 2014, submitted);
• analysis of tiling and packing of H-bonded polycarboxylate tectons and the formation of novel bilayer structures on surfaces, thus defining new methodologies for the binding and assembly of molecules and MOFs at surfaces (Science, 2008, 322, 1077-1081; Nature Chemistry, 2011, 3, 14-16; Nature Chemistry, 2012, 4, 112-117; J. Chem. Phys. C, 2013, 117, 18381-18385);
• the formation and direct visualisation of a Cd66 nanosphere complex inside carbon nanotubes, the formation of related high nuclearity clusters and MOFs, and determination of the positions of gas molecules within these metal organic spheres (J. Am. Chem. Soc., 2012, 134, 55-58);
• synthesis of NiFe model complexes and systems that mimic the structural and functional properties of hydrogenase biosites (Dalton Trans., 2009, 925-931); this has been linked to the study of redox non-innocent metal complexes derived from S-based ligands (Chemistry Eur. J., 2011, 17, 10246-10258; Inorg. Chem., 2012, 51, 1450-1461; Inorg. Chem., 2013, 52, 660-670);
• successful design and delivery of new photocatalysts for hydrogen production from protons using NiFe hydrogenase model complexes coupled to photosensitizers and sacrificial donors. These studies have involved the novel use and full characterisation of intermediates and transient species by ultrafast time-resolved spectroscopy (Inorg. Chem., 2014, submitted);
• formation of MOFs and molecular species that act as hydrogen bonding ionophores for selective extraction and transport of base and precious metal chlorometallates and cations, and the successful application of ionophores for metal cation and anion binding and extraction (Chem. Comm., 2009, 583-585; Chemistry Eur. J., 2009, 15, 4836-4850; Chemistry Eur J., 2009, 15, 8861-8873; Chemistry Eur. J., 2012, 18, 7715-7728);
• attachment of metal complexes and arrays onto and into carbon nanotubes (Chemistry Eur J., 2011, 17, 668-674; Chem. Comm, 2011, 47, 5696-5698; Dalton Trans., 2013, 42, 5056-5067; Chemistry Eur. J., 2013, 19, 11999-12008);
• high pressure chemistry of metal complexes (Angew. Chem. Int. Ed., 2013, 52, 5093-5095).
Workpackage 1: Synthesis of ligand precursors and metal-organic framework (MOF) synthesis;
Workpackage 2: Gas and volatile organic compound (voc) adsorption, purification and activation;
Workpackage 3: Catalytic H2 production;
Workpackage 4: Metal cation and anion extraction and transport.
The research has progressed very much as planned, and particular progress and focus has been placed on the synthesis of porous hybrid materials and their ability to store and selectively bind gaseous substrates, especially H2, CO2, SO2, CH4, acetylene, ethylene and related volatile organic substrates (eg aromatic substrates) and of precious metal values. Photocatalytic H2 production has been successfully achieved using low molecular weight complex mimics that model the structure and function of hydrogenase enzymes. Inherent across our metal complex and materials research is the ability to chemically modify, dope and tune structure and properties, and at the heart of this project has been the design and discovery of new functional materials for specific applications. Particular highlights of the research include:
• the synthesis of a very wide range of new poly-dentate organic ligands/tectons and their incorporation into new families of MOF materials showing permanent porosity and novel substrate storage, selectivity and binding (J. Am. Chem. Soc., 2009, 131, 2159-2171; Chemistry Eur. J., 2009, 15, 4829-4835; Inorg. Chem., 2009, 48, 11067-11078; Chemistry Eur. J., 2010, 46, 13671-13679; Chem. Comm., 2011, 47, 8304-8306);
• the synthesis in 2009 of a porous polyhedral metal organic framework (NOTT-112) showing very high H2 storage capacity (above 10wt% and 50 g/L) and the formation of a range of analogous materials that have given insights into the structural and topological features that underpin their properties (ChemComm, 2009, 1025-1027; J. Am. Chem. Soc., 2010, 132, 4092-4094; Chem. Comm., 2011, 47, 4487-4489; Chemistry Eur. J., 2011, 17, 11162-11170; Chem.Comm. 2011, 47, 9995-9997; Acc. Chem. Res., 2014, in press. DOI: 10.1021/ar400049h).
• the invention of a new methodologies for H2 storage modulated by cation exchange in which porous anionic frameworks are doped by different metal cations to enhance binding and the isosteric heat of adsorption of substrates (Nature Chemistry, 2009, 1, 487-493);
• the development of the “pore with gate” mechanism in hybrid materials in which gas can enter and leave the porous host only when the chemical valve (a metal or organic cation) is opened (Faraday Discussions, 2011, 151, 19-36; Inorg. Chem., 2011, 50, 9374-9384);
• the design, synthesis and characterisation of the first defect MOF material: this material shows high capacity and selectivity for CO2 storage and these properties have been modelled theoretically and rationalised based upon the observed defect structure (Nature Materials, 2012, 11, 710-716);
• The successful selective capture of CO2 using decorated MOFs (Chem. Sci, 2012, 3, 2993-2999; Chem. Sci., 2013, 4, 1731-1736; Angew. Chem. Int. Ed., 2013, 125, 13656-13660; Chemistry Eur. J., 2014, 20, in press)
• the design, synthesis and characterisation of an isostructural series of new water and thermally-stable MOF materials, denoted as NOTT-300, based upon M(III) centres (M = Al, Sc, Ga, In, Bi, Cr), and the modulation of the properties of these porous hosts by developing mixed metal hybrids that show enhanced catalytic, photo and storage properties;
• the direct visualisation of CO2 and SO2 capture and binding in NOTT-300(M) (M = Al, Ga, In) by diffraction and scattering techniques supported by DFT calculations within this robust porous host: supramolecular hydrogen bonding interactions stabilise host-guest interactions and explain the high selectivity that these materials show for CO2 and SO2 (Nature Chemistry, 2012, 4, 887-894);
• binding and storage of NOx substrates within MOF hosts and the characterisation of their binding and dynamics;
• selective hydrocarbon binding (methane vs ethylene vs acetylene) in NOTT-300(Al) and the full structural and dynamic analysis and characterisation of the supramolecular chemistry (hydrogen-binding, π-π stacking and van der Waals interactions) underpinning the selective binding of acetylene (Nature Chemistry, 2014, submitted);
• the chemical transformation of flexible MOF structures catalysed by SO2 and other external stimuli (J. Am. Chem. Soc., 2013, 135, 4954-4957);
• the discovery of a new class of porous organic material, SOF (Supramolecular Organic Framework) showing permanent porosity and excellent reversible gas uptake and discrimination: these materials may be derived from a single or from two different organic components that assemble via hydrogen-binding and π-π stacking to form robust three dimensional structures (J. Am. Chem. Soc., 2010, 132, 14457-14469);
• the successful application of green and sustainable synthesis of MOFs in near-critical water thus circumventing the use of toxic organic solvents such as dimethylformamide (Green Chemistry, 2012, 14, 117-122);
• the expansion of this green synthetic route to the development of continuous flow systems using high temperature water and ethanol for the scale-up and sustainable manufacture of MOFs (Green Chemistry, 2014, submitted);
• analysis of tiling and packing of H-bonded polycarboxylate tectons and the formation of novel bilayer structures on surfaces, thus defining new methodologies for the binding and assembly of molecules and MOFs at surfaces (Science, 2008, 322, 1077-1081; Nature Chemistry, 2011, 3, 14-16; Nature Chemistry, 2012, 4, 112-117; J. Chem. Phys. C, 2013, 117, 18381-18385);
• the formation and direct visualisation of a Cd66 nanosphere complex inside carbon nanotubes, the formation of related high nuclearity clusters and MOFs, and determination of the positions of gas molecules within these metal organic spheres (J. Am. Chem. Soc., 2012, 134, 55-58);
• synthesis of NiFe model complexes and systems that mimic the structural and functional properties of hydrogenase biosites (Dalton Trans., 2009, 925-931); this has been linked to the study of redox non-innocent metal complexes derived from S-based ligands (Chemistry Eur. J., 2011, 17, 10246-10258; Inorg. Chem., 2012, 51, 1450-1461; Inorg. Chem., 2013, 52, 660-670);
• successful design and delivery of new photocatalysts for hydrogen production from protons using NiFe hydrogenase model complexes coupled to photosensitizers and sacrificial donors. These studies have involved the novel use and full characterisation of intermediates and transient species by ultrafast time-resolved spectroscopy (Inorg. Chem., 2014, submitted);
• formation of MOFs and molecular species that act as hydrogen bonding ionophores for selective extraction and transport of base and precious metal chlorometallates and cations, and the successful application of ionophores for metal cation and anion binding and extraction (Chem. Comm., 2009, 583-585; Chemistry Eur. J., 2009, 15, 4836-4850; Chemistry Eur J., 2009, 15, 8861-8873; Chemistry Eur. J., 2012, 18, 7715-7728);
• attachment of metal complexes and arrays onto and into carbon nanotubes (Chemistry Eur J., 2011, 17, 668-674; Chem. Comm, 2011, 47, 5696-5698; Dalton Trans., 2013, 42, 5056-5067; Chemistry Eur. J., 2013, 19, 11999-12008);
• high pressure chemistry of metal complexes (Angew. Chem. Int. Ed., 2013, 52, 5093-5095).