title: Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga2(OH)2(L)] (H4L = Biphenyl-3,3',5,5'-tetracarboxylic Acid), MFM-300(Ga2).
abstract: Metal-organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga2(OH)2(L)] (H4L = biphenyl-3,3',5,5'-tetracarboxylic acid), designated as MFM-300(Ga2), (MFM = Manchester Framework Material replacing NOTT designation), by solvothermal reaction of Ga(NO3)3 and H4L in a mixture of DMF, THF, and water containing HCl for 3 days. MFM-300(Ga2) crystallizes in the tetragonal space group I4122, a = b = 15.0174(7) Å and c = 11.9111(11) Å and is isostructural with the Al(III) analogue MFM-300(Al2) with pores decorated with -OH groups bridging Ga(III) centers. The isostructural Fe-doped material [Ga(1.87)Fe(0.13)(OH)2(L)], MFM-300(Ga(1.87)Fe(0.13)), can be prepared under similar conditions to MFM-300(Ga2) via reaction of a homogeneous mixture of Fe(NO3)3 and Ga(NO3)3 with biphenyl-3,3',5,5'-tetracarboxylic acid. An Fe(III)-based material [Fe3O(1.5)(OH)(HL)(L)(0.5)(H2O)(3.5)], MFM-310(Fe), was synthesized with Fe(NO3)3 and the same ligand via hydrothermal methods. [MFM-310(Fe)] crystallizes in the orthorhombic space group Pmn21 with a = 10.560(4) Å, b = 19.451(8) Å, and c = 11.773(5) Å and incorporates μ3-oxo-centered trinuclear iron cluster nodes connected by ligands to give a 3D nonporous framework that has a different structure to the MFM-300 series. Thus, Fe-doping can be used to monitor the effects of the heteroatom center within a parent Ga(III) framework without the requirement of synthesizing the isostructural Fe(III) analogue [Fe2(OH)2(L)], MFM-300(Fe2), which we have thus far been unable to prepare. Fe-doping of MFM-300(Ga2) affords positive effects on gas adsorption capacities, particularly for CO2 adsorption, whereby MFM-300(Ga(1.87)Fe(0.13)) shows a 49% enhancement of CO2 adsorption capacity in comparison to the homometallic parent material. We thus report herein the highest CO2 uptake (2.86 mmol g(-1) at 273 K at 1 bar) for a Ga-based MOF. The single-crystal X-ray structures of MFM-300(Ga2)-solv, MFM-300(Ga2), MFM-300(Ga2)·2.35CO2, MFM-300(Ga(1.87)Fe(0.13))-solv, MFM-300(Ga(1.87)Fe(0.13)), and MFM-300(Ga(1.87)Fe(0.13))·2.0CO2 have been determined. Most notably, in situ single-crystal diffraction studies of gas-loaded materials have revealed that Fe-doping has a significant impact on the molecular details for CO2 binding in the pore, with the bridging M-OH hydroxyl groups being preferred binding sites for CO2 within these framework materials. In situ synchrotron IR spectroscopic measurements on CO2 binding with respect to the -OH groups in the pore are consistent with the above structural analyses. In addition, we found that, compared to MFM-300(Ga2), Fe-doped MFM-300(Ga(1.87)Fe(0.13)) shows improved catalytic properties for the ring-opening reaction of styrene oxide, but similar activity for the room-temperature acetylation of benzaldehyde by methanol. The role of Fe-doping in these systems is discussed as a mechanism for enhancing porosity and the structural integrity of the parent material.
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.
authors.forename: Cristina P
authors.initials: CP
authors.lastname: Krap
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.
authors.forename: Ruth
authors.initials: R
authors.lastname: Newby
authors.affiliation: Instituto de Technologia Quimica (UPV-CSIC), Universidad Politecnica de Valencia , Avenida de los Naranjos s/n, Valencia, 46022, Spain.
authors.forename: Amarajothi
authors.initials: A
authors.lastname: Dhakshinamoorthy
authors.affiliation: Instituto de Technologia Quimica (UPV-CSIC), Universidad Politecnica de Valencia , Avenida de los Naranjos s/n, Valencia, 46022, Spain.
authors.forename: Hermenegildo
authors.initials: H
authors.lastname: García
authors.affiliation: School of Physics, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.|Department of Chemical and Process Engineering, University of Strathclyde , James Weir Building, 75 Montrose Street, Glasgow G1 1XJ, U.K.
authors.forename: Izabela
authors.initials: I
authors.lastname: Cebula
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.|School of Chemistry, Cardiff University , Main Building, Park Place, Cardiff, CF10 3AT, U.K.
authors.forename: Timothy L
authors.initials: TL
authors.lastname: Easun
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.
authors.forename: Mathew
authors.initials: M
authors.lastname: Savage
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.
authors.forename: Jennifer E
authors.initials: JE
authors.lastname: Eyley
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.
authors.forename: Shan
authors.initials: S
authors.lastname: Gao
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, U.K.
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.affiliation: Instituto de Technologia Quimica (UPV-CSIC), Universidad Politecnica de Valencia , Avenida de los Naranjos s/n, Valencia, 46022, Spain.
authors.forename: Peter H
authors.initials: PH
authors.lastname: Beton
authors.affiliation: Diamond Light Source , Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, U.K.
authors.forename: Mark R
authors.initials: MR
authors.lastname: Warren
authors.affiliation: Diamond Light Source , Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, U.K.
authors.forename: David R
authors.initials: DR
authors.lastname: Allan
authors.affiliation: Diamond Light Source , Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, U.K.
authors.forename: Mark D
authors.initials: MD
authors.lastname: Frogley
authors.affiliation: Diamond Light Source , Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, U.K.
authors.forename: Chiu C
authors.initials: CC
authors.lastname: Tang
authors.affiliation: Diamond Light Source , Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, U.K.
authors.forename: Gianfelice
authors.initials: G
authors.lastname: Cinque
authors.affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester, M13 9PL, U.K.
authors.forename: Sihai
authors.initials: S
authors.lastname: Yang
authors.affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester, M13 9PL, U.K.
authors.forename: Martin
authors.initials: M
authors.lastname: Schröder