Co-reporter:Muhanned R. Khdhayyer, Elisa Esposito, Alessio Fuoco, Marcello Monteleone, Lidietta Giorno, Johannes C. Jansen, Martin P. Attfield, Peter M. Budd
Separation and Purification Technology 2017 Volume 173() pp:304-313
Publication Date(Web):1 February 2017
DOI:10.1016/j.seppur.2016.09.036
•Metal Organic Frameworks UiO-66 improve the performance of PIM-1 gas separation membranes.•The separation performance of the MMMs exceeds the 2008 Robeson upper bound for various gas pairs.•The effect of UiO-66 on PIM-1 can be described by the Maxwell model.•Methanol treatment greatly enhances the permeability.•Mixed gas permeation experiments confirm an excellent separation performance.This work presents a study of the gas transport properties for a novel class of mixed matrix membranes (MMMs) based on the polymer of intrinsic microporosity PIM-1 loaded with UiO-66 [Zr6O4(OH)4(O2CC6H4CO2)6] based metal-organic frameworks (MOFs). Three isoreticular MOFs were dispersed in the polymer matrix, standard UiO-66, UiO-66-NH2 (functionalized with an amino group) and UiO-66-(COOH)2 (functionalized with two carboxylic groups), in order to investigate the effect of the functionalization of the linker on the gas transport. The pure gas permeabilities of He, H2, O2, N2, CH4, CO2 were studied, for the as prepared membranes and after methanol treatment, focusing attention on the potential use of these membranes for CO2/CH4 separation. The pure gas transport of the MMMs was described on the basis of the Maxwell model. The predictions of the model are discussed and compared with the experimental permeability and selectivity of the MMMs and neat PIM-1. Mixed gas permeation tests were performed on a representative sample to investigate the actual separation performance with industrially relevant gas mixtures. These confirmed the good perspectives of these MMMs in applications like CO2 removal from biogas or from flue gas.
Co-reporter:Lei Gao, Monica Alberto, Patricia Gorgojo, Gyorgy Szekely, Peter M. Budd
Journal of Membrane Science 2017 Volume 529(Volume 529) pp:
Publication Date(Web):1 May 2017
DOI:10.1016/j.memsci.2017.02.008
•First report on thin film composite membranes of PIM-1 on PVDF support.•Phosphoric acid used to control PVDF surface pore size and porosity.•High fluxes achieved in butanol pervaporation.•High pervaporation separation index of 112 is achieved.•Permeability of PIM-1 layer depends on thickness in the range 1–3 µm.Membranes that enable the recovery of organic compounds from dilute aqueous solution are desired for applications such as biobutanol production. The polymer of intrinsic microporosity PIM-1 shows promise for organophilic separations and here it is incorporated into thin film composite (TFC) membranes in order to increase the flux of permeate. Asymmetric polyvinylidene fluoride (PVDF) supports were prepared with pore sizes at the surface in the size range 25–55 nm and fractional surface porosities in the range 0.38–0.69, as determined by atomic force microscopy (AFM). The addition of phosphoric acid to the PVDF dope solution helped to control the pore size and porosity. Supports were coated with PIM-1 to form TFC membranes with active layer thicknesses in the range 1.0–2.9 µm. Membranes were tested for the pervaporation of a 1-butanol/water mixture (5 wt%). At 65 °C, values of total flux up to 9 kg m−2 h−1 were obtained, with separation factors up to 18.5 and values of pervaporation separation index (PSI) up to 112 kg m−2 h−1.Download high-res image (207KB)Download full-size image
Co-reporter:Tamoghna Mitra, Rupesh S. Bhavsar, Dave J. Adams, Peter M. Budd and Andrew I. Cooper
Chemical Communications 2016 vol. 52(Issue 32) pp:5581-5584
Publication Date(Web):21 Mar 2016
DOI:10.1039/C6CC00261G
High-free-volume glassy polymers, such as polymers of intrinsic microporosity (PIMs) and poly(trimethylsilylpropyne), have attracted attention as membrane materials due to their high permeability. However, loss of free volume over time, or aging, limits their applicability. Introduction of a secondary filler phase can reduce this aging but either cost or instability rules out scale up for many fillers. Here, we report a cheap, acid-tolerant, nanoparticulate hypercrosslinked polymer ‘sponge’ as an alternative filler. On adding the filler, permeability is enhanced and aging is strongly retarded. This is accompanied by a CO2/N2 selectivity that increases over time, surpassing the Robeson upper bound.
Co-reporter:Rebecca E. Dey, Xia Zhong, Peter J. Youle, Qi Guang Wang, Ian Wimpenny, Sandra Downes, Judith A. Hoyland, David C. Watts, Julie E. Gough, and Peter M. Budd
Macromolecules 2016 Volume 49(Issue 7) pp:2656-2662
Publication Date(Web):March 23, 2016
DOI:10.1021/acs.macromol.5b02594
Poly(vinylphosphonic acid-co-acrylic acid) (PVPA-co-AA) has recently been identified as a possible candidate for use in bone tissue engineering. It is hypothesized that the strong binding of PVPA-co-AA to calcium in natural bone inhibits osteoclast activity. The free radical polymerization of acrylic acid (AA) with vinylphosphonic acid (VPA) has been investigated with varying experimental conditions. A range of copolymers were successfully produced and their compositions were determined quantitatively using 31P NMR spectroscopy. Monomer conversions were calculated using 1H NMR spectroscopy and a general decrease was found with increasing VPA content. Titration studies demonstrated an increase in the degree of dissociation as a function of VPA in the copolymer. However, a VPA content ca. 30 mol % was found to be the optimum for calcium chelation, suggesting that this composition is the most promising for biomaterials applications. Assessment of cell metabolic activity showed that PVPA-co-AA has no detrimental effect on cells, regardless of copolymer composition.
Co-reporter:Aleksandra Gonciaruk, Khalid Althumayri, Wayne J. Harrison, Peter M. Budd, Flor R. Siperstein
Microporous and Mesoporous Materials 2015 Volume 209() pp:126-134
Publication Date(Web):June 2015
DOI:10.1016/j.micromeso.2014.07.007
•A polymer of intrinsic microporosity membrane containing graphene was studied.•The adsorption capacity was not affected by the presence of graphene.•SEM images show structural differences between the pure polymer and the composite.•Simulations show monomers–graphene interactions due to their structural similarity.•Quantitative agreement requires scaling down the gas–solid interaction strength.This work presents a combined molecular simulation and experimental study to understand the effect of graphene on the packing and gas adsorption performance of a new class of polymers, known as polymers of intrinsic microporosity (PIMs). PIMs can be processed to membranes or other useful forms and their chemistry can be tailored for specific applications. Their rigid and contorted macromolecular structures give rise to a large amount of microvoids attractive for small molecule adsorption. We show that the presence of graphene in the composite affects the structure of the membrane as evidenced by the change in colour and SEM micrographs, but it does not reduce significantly the adsorption capacity of the material.Figure optionsDownload full-size imageDownload high-quality image (149 K)Download as PowerPoint slide
Co-reporter:Jonathan M. Hughes;Karen Tiede;John Lewis
Journal of Applied Polymer Science 2015 Volume 132( Issue 1) pp:
Publication Date(Web):
DOI:10.1002/app.41229
ABSTRACT
PolyHIPEs of ethylene glycol dimethacrylate (EGDMA) and styrene/divinylbenzene were prepared by polymerization of water-in-oil high internal phase emulsions (HIPEs) within high pressure liquid chromatography (HPLC) columns. The columns were incorporated into a HPLC system affixed to an inductively-coupled plasma mass spectrometer, and their potential for the separation of engineered nanoparticles was investigated. Triplicate injections of 5 and 10 nm gold particles injected onto a poly(styrene-co-divinylbenzene) polyHIPE column produced an average difference in retention time of 135 s. On a poly(EGDMA) column, triplicate injections of dysprosium containing polystyrene particles of 52 and 155 nm produced a difference in retention time of 8 s. In both cases the smaller particles eluted from the column first. Comparison, using scanning electron microscopy, of the polyHIPE columns after the separations, against freestanding monoliths produced from the same HIPEs, revealed no apparent change in the internal porous structure of the polyHIPEs. © 2015 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 132, 41229.
Co-reporter:Jonathan M. Hughes;Andrew Grieve;Pranab Dutta;Karen Tiede;John Lewis
Journal of Applied Polymer Science 2015 Volume 132( Issue 24) pp:
Publication Date(Web):
DOI:10.1002/app.42061
ABSTRACT
For the safe commercialization of nanoparticle technology, there is a need for reference materials that can be used in studies related to the environmental fate of nanoparticles. This work produced metal-containing polystyrene nanoparticles with target parameters such as high monodispersity, tailorable size range (33–193 nm), and variable surface charge. In addition, the combination of organic and inorganic components made them detectable by all of the main analytical techniques routinely used in nanoparticle characterization, e.g., TEM, DCS, DLS, and ICP-MS (the latter when interfaced to chromatographic instrumentation). The lanthanides Gd, Dy, and Nd were investigated as the inorganic component because of their high response when analyzed by ICP-MS, and because of their low environmental abundance. Particles were prepared by emulsion polymerization using one of two stabilizers: the nonionic surfactant Pluronic F68 or the anionic surfactant sodium dodecyl sulfate © 2015 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42061.
Co-reporter:Bekir Satilmis, Mohammed N. Alnajrani, and Peter M. Budd
Macromolecules 2015 Volume 48(Issue 16) pp:5663-5669
Publication Date(Web):August 6, 2015
DOI:10.1021/acs.macromol.5b01196
The polymer of intrinsic microporosity PIM-1 was modified by reaction with ethanolamine and with diethanolamine, and the modified polymers characterized by infrared spectroscopy, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis and nitrogen adsorption. Various possible reaction products were considered, and the results indicated that hydroxyalkylaminoalkylamide structures were obtained. Gas adsorption measurements showed that ethanolamine modification increased the ideal CO2/N2 selectivity. Studies of dye adsorption from aqueous solution demonstrated that the reaction products showed strong selectivity for the anionic dye Orange II, compared to the cationic dye Safranin O. Mass uptakes of the anionic dye by ethanolamine-modified PIM-1 samples were up to 2 orders of magnitude higher than for the parent polymer.
Co-reporter:Bekir Satilmis and Peter M. Budd
RSC Advances 2014 vol. 4(Issue 94) pp:52189-52198
Publication Date(Web):09 Oct 2014
DOI:10.1039/C4RA09907A
Chemical modification can be used to tailor the properties of PIM-1, the prototypical polymer of intrinsic microporosity, which shows promise for applications such as membrane and adsorption processes for gas and liquid separations. Base-catalysed hydrolysis of PIM-1 has previously been assumed to yield only carboxylated products. In this work, hydrolysis was carried out at 120 °C with 20% NaOH and at 100 °C with 10% NaOH in a water–ethanol mixture, and a combination of IR, UV, 1H NMR and elemental analysis was used to demonstrate that the hydrolysis products contain a mixture of amide, carboxylic acid, ammonium carboxylate and sodium carboxylate structures. The amide-PIM-1 structure has not previously been reported. Even the most fully hydrolysed samples had a substantial proportion of amide, with most samples being >50% amide. On hydrolysis there was a decrease in the water contact angle (from 85° for PIM-1 to about 60° for the most fully hydrolysed samples) and a decrease in the BET surface area. The adsorption of dyes from aqueous solution was shown to depend on the composition of the polymer. Uptake of the cationic dye Safranin O increased dramatically with increasing percentage carboxylation, the most highly carboxylated sample showing 31 times the uptake of the parent polymer, whereas uptake of the anionic dye Orange II decreased with increasing percentage carboxylation.
Co-reporter:Christopher R. Mason, Louise Maynard-Atem, Kane W. J. Heard, Bekir Satilmis, Peter M. Budd, Karel Friess, Marek Lanc̆, Paola Bernardo, Gabriele Clarizia, and Johannes C. Jansen
Macromolecules 2014 Volume 47(Issue 3) pp:1021-1029
Publication Date(Web):January 24, 2014
DOI:10.1021/ma401869p
Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine–PIM-1 showed higher CO2 uptake and higher CO2/N2 sorption selectivity than the parent polymer, with very evident dual-mode sorption behavior. In gas permeation with six light gases, the individual contributions of solubility and diffusion to the overall permeability was determined via time-lag analysis. The high CO2 affinity drastically restricts diffusion at low pressures and lowers CO2 permeability compared to the parent PIM-1. Furthermore, the size-sieving properties of the polymer are increased, which can be attributed to a higher stiffness of the system arising from hydrogen bonding of the amine groups. Thus, for the H2/CO2 gas pair, whereas PIM-1 favors CO2, amine–PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.
Co-reporter:Hosna Shamsipur, Bann A. Dawood, Peter M. Budd, Paola Bernardo, Gabriele Clarizia, and Johannes C. Jansen
Macromolecules 2014 Volume 47(Issue 16) pp:5595-5606
Publication Date(Web):August 4, 2014
DOI:10.1021/ma5011183
Membrane gas separations require materials with high permeability and good selectivity. For glassy polymers, the gas transport properties depend strongly on the amount and distribution of free volume, which may be enhanced either by engineering the macromolecular backbone to frustrate packing in the solid state or by thermal conversion of a soluble precursor to a more rigid structure of appropriate topology. The first approach gives polymers of intrinsic microporosity (PIMs), while the second approach is used in thermally rearranged (TR) polymers. Recent research has sought to combine these approaches, and here a new range of thermally rearrangeable PIM-polyimides are reported, derived from dianhydrides incorporating a spiro center. Hydroxyl-functionalized polyimides were prepared using two different diamines: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (bisAPAF) and 4,6-diaminoresorcinol (DAR). Thermal treatment at 450 °C under N2 for 1 h yielded polybenzoxazole (PBO) polymers, which showed increased permeability, compared to the precursor, in membrane gas permeation experiments. A polymer based on DAR (PIM-PBO-3) exhibited a CO2/N2 selectivity of 30 as prepared, higher than the values of 21–23 obtained for polymers derived from bisAPAF with the same dianhydride (PIM-PBO-1).
Co-reporter:Christopher R. Mason, Maria Giovanna Buonomenna, Giovanni Golemme, Peter M. Budd, Francesco Galiano, Alberto Figoli, Karel Friess, Vladimir Hynek
Polymer 2013 Volume 54(Issue 9) pp:2222-2230
Publication Date(Web):19 April 2013
DOI:10.1016/j.polymer.2013.02.032
The preparation and characterization of novel PIM-1/silicalite-1 (MFI) mixed matrix membranes (MMMs) are reported. Silicalite-1 crystals of size 350 nm were synthesized and functionalized with 2-phenylethyl groups to favour a higher hydrophobicity in the PIM-1 matrix. MMMs with different functionalized crystal loadings (from 8.4 to 35.5 v%) were prepared, characterized and tested in the separation of ethanol from aqueous mixtures with different concentration (5 and 9 wt%) via pervaporation. Pure gas transport properties were also measured for the MMM with the highest filler loading. The enhancement in both ethanol/water separation factor (5.7 vs. 4.3) and CO2/N2 selectivity (30 vs. 24) compared to neat PIM-1 indicates a positive effect of the silicalite-1 on the molecular separations investigated.
Co-reporter:Alexra F. Bushell; Peter M. Budd;Dr. Martin P. Attfield;Dr. James T. A. Jones;Dr. Tom Hasell; Andrew I. Cooper;Dr. Paola Bernardo;Fabio Bazzarelli;Dr. Gabriele Clarizia;Dr. Johannes C. Jansen
Angewandte Chemie International Edition 2013 Volume 52( Issue 4) pp:1253-1256
Publication Date(Web):
DOI:10.1002/anie.201206339
Co-reporter:Alexra F. Bushell; Peter M. Budd;Dr. Martin P. Attfield;Dr. James T. A. Jones;Dr. Tom Hasell; Andrew I. Cooper;Dr. Paola Bernardo;Fabio Bazzarelli;Dr. Gabriele Clarizia;Dr. Johannes C. Jansen
Angewandte Chemie 2013 Volume 125( Issue 4) pp:1291-1294
Publication Date(Web):
DOI:10.1002/ange.201206339
Co-reporter:Christopher R. Mason, Louise Maynard-Atem, Nasser M. Al-Harbi, Peter M. Budd, Paola Bernardo, Fabio Bazzarelli, Gabriele Clarizia, and Johannes C. Jansen
Macromolecules 2011 Volume 44(Issue 16) pp:6471-6479
Publication Date(Web):July 27, 2011
DOI:10.1021/ma200918h
A novel polymer of intrinsic microporosity, thioamide-PIM-1, has been prepared by postmodification of PIM-1, using phosphorus pentasulfide as a thionating agent in the presence of sodium sulfite. The chemistry was first tested on a low molecular weight model compound, 3,13-dicyanobenzo-1,2,4′,5′-bis(1,4-benzodioxane). For the polymer, up to 80% conversion of nitrile to thioamide was achieved. Modification leads to a reduction in the BET surface area of the polymer, from 770 m2 g–1 for the parent PIM-1 to 263 m2 g–1 on 80% conversion of nitrile to thioamide. After modification, the polymer is no longer soluble in chlorinated solvents such as CHCl3, but is soluble in polar aprotic solvents such as THF, DMF, DMSO, and DMAc. Self-supported membranes of thioamide-PIM-1 were cast from THF. Single gas permeability measurements showed increased selectivities but reduced permeabilities compared to the parent polymer. Ethanol treatment, which removes occluded THF as well as enhancing free volume, has a pronounced effect on membrane permeability. For the as-prepared membrane, an ideal CO2/N2 selectivity of 38.5 was achieved with a CO2 permeability of 150 barrer. Ethanol treatment increased the CO2 permeability to 1120 barrer, with a decrease in CO2/N2 ideal selectivity to 30.3.
Co-reporter:Peter M. Budd and Neil B. McKeown
Polymer Chemistry 2010 vol. 1(Issue 1) pp:63-68
Publication Date(Web):04 Jan 2010
DOI:10.1039/B9PY00319C
For gas separation membranes, materials are required that offer high permeability as well as good selectivity for a desired separation. For glassy polymers, the gas transport properties depend on the amount and distribution of free volume and on chain mobility. The most highly permeable polymers have rigid, twisted macromolecular backbones that give rise to microvoids. Examples include substituted polyacetylenes, perfluoropolymers, addition-type polynorbornene, polymers of intrinsic microporosity (PIMs) and some polyimides. High permeability membranes may also be produced by thermal rearrangement of precursor polymers.
Co-reporter:Thomas Emmler, Kathleen Heinrich, Detlev Fritsch, Peter M. Budd, Nhamo Chaukura, Dennis Ehlers, Klaus Rätzke and Franz Faupel
Macromolecules 2010 Volume 43(Issue 14) pp:6075-6084
Publication Date(Web):June 21, 2010
DOI:10.1021/ma1008786
High free volume, film-forming copolymers were prepared in which a proportion of the spiro-units of PIM-1 were replaced with units derived from 9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene-2,3,6,7-tetrol (CO1). A full investigation of free volume, utilizing N2 sorption, positron annihilation lifetime spectroscopy (PALS), Xe sorption and 129Xe NMR spectroscopy, was undertaken for copolymer PIM1-CO1-40 (spiro-units:CO1 = 60:40) and a comparison is made with PIM-1. All techniques indicate that the copolymer, like PIM-1, possesses free volume holes or pores on the nanometre length scale (i.e., microporosity as defined by IUPAC). For the batch of PIM-1 studied here, the sample as received showed anomalous N2 sorption, Xe sorption and 129Xe NMR behavior that could be interpreted in terms of reduced porosity in the size range 0.6−0.7 nm, as compared to the copolymer. The anomalous behavior was eliminated on conditioning or relaxation of the polymer, e.g., by Xe sorption at 100 °C and 3 bar. PALS for both PIM1-CO1-40 and PIM-1 indicates a maximum in the average free volume hole size, and in the width of the distribution of hole sizes, on increasing temperature. This maximum appears to be a feature of high free volume polymers and may be related to the onset of localized oscillations of backbone moieties.
Co-reporter:Neil B. McKeown and Peter M. Budd
Macromolecules 2010 Volume 43(Issue 12) pp:5163-5176
Publication Date(Web):May 20, 2010
DOI:10.1021/ma1006396
The past decade has seen the development of microporous materials (i.e., materials containing pores of dimensions <2 nm) derived wholly from organic components. Here we review this nascent area with a particular emphasis on amorphous polymers that possess intrinsic microporosity (IM), which is defined as microporosity that arises directly from the shape and rigidity of component macromolecules. Although IM can be readily identified within soluble non-network polymers and oligomers, for network polymers it is harder to differentiate IM from template effects that are responsible for the microporosity within hyper-cross-linked networks. The numerous examples of microporous polymers assembled from rigid monomers by the formation of rigid linking groups are surveyed and their IM assessed. The potential applications of these materials are highlighted.
Co-reporter:Bader S. Ghanem, Neil B. McKeown, Peter M. Budd, Nasser M. Al-Harbi, Detlev Fritsch, Kathleen Heinrich, Ludmila Starannikova, Andrei Tokarev and Yuri Yampolskii
Macromolecules 2009 Volume 42(Issue 20) pp:7881-7888
Publication Date(Web):August 27, 2009
DOI:10.1021/ma901430q
A range of polyimides with characteristics similar to a polymer of intrinsic microporosity (PIM) were prepared by reaction with various aromatic diamines of a bis(carboxylic anhydride) incorporating a spiro-center. The polymers exhibited high surface area, as determined by nitrogen adsorption, and high thermal stability. Membrane gas permeation experiments showed PIM-polyimides to be among the most permeable of all polyimides and to have selectivities close to the upper bound for several important gas pairs. A group contribution method was used to predict permeability coefficients and separation factors for further PIM-polyimide structures, revealing worthwhile targets for future synthetic efforts.
Co-reporter:Helen J. Mackintosh, Peter M. Budd and Neil B. McKeown
Journal of Materials Chemistry A 2008 vol. 18(Issue 5) pp:573-578
Publication Date(Web):10 Dec 2007
DOI:10.1039/B715660J
Cobalt phthalocyanine and iron porphyrin network polymers of intrinsic microporosity (network-PIMs) were prepared and their performance as heterogeneous catalysts compared with that of low molar mass analogues. Spiro-linked Co phthalocyanine network-PIMs prepared from preformed chlorinated phthalocyanines showed lower surface areas and lower catalytic activity than those prepared by a phthalocyanine-forming reaction from a rigid precursor incorporating a spiro-centre. However, all the phthalocyanine network-PIMs were much more effective catalysts than low molar mass Co phthalocyanine for the decomposition of hydrogen peroxide, the oxidation of cyclohexene and the oxidation of hydroquinone. An Fe porphyrin network-PIM showed a higher surface area than any of the phthalocyanine polymers and showed higher activity for the oxidation of hydroquinone, also outperforming a low molar mass FeCl porphyrin.
Co-reporter:Bader S. Ghanem, Kadhum J. Msayib, Neil B. McKeown, Kenneth D. M. Harris, Zhigang Pan, Peter M. Budd, Anna Butler, James Selbie, David Book and Allan Walton
Chemical Communications 2007 (Issue 1) pp:67-69
Publication Date(Web):15 Nov 2006
DOI:10.1039/B614214A
A novel triptycene-based polymer of intrinsic microporosity (Trip-PIM) displays enhanced surface area (1065 m2 g−1) and reversibly adsorbs 1.65% hydrogen by mass at 1 bar/77 K and 2.71% at 10 bar/77 K.
Co-reporter:Neil B. McKeown;David Book
Macromolecular Rapid Communications 2007 Volume 28(Issue 9) pp:995-1002
Publication Date(Web):24 APR 2007
DOI:10.1002/marc.200700054
Microporous organic polymers offer the possibility of storing hydrogen safely at low temperatures and moderate pressures via physisorption. A range of polymers of intrinsic microporosity (PIMs) have been studied. The best PIM to date is based on a triptycene monomer and takes up 2.7% H2 by mass at 10 bar/77 K. Hypercrosslinked polymers (HCPs) also show promising performance, particularly at pressures >10 bar. The form of the H2 isotherm is influenced by the micropore distribution, a higher concentration of ultramicropores (pore size <0.7 nm), as found in PIMs, being associated with enhanced low pressure adsorption. The performance of polymers relative to other microporous materials (carbons and metal-organic frameworks) is compared and promising methods to enhance the hydrogen uptake of microporous polymers are suggested.
Co-reporter:Peter M. Budd, Anna Butler, James Selbie, Khalid Mahmood, Neil B. McKeown, Bader Ghanem, Kadhum Msayib, David Book and Allan Walton
Physical Chemistry Chemical Physics 2007 vol. 9(Issue 15) pp:1802-1808
Publication Date(Web):16 Feb 2007
DOI:10.1039/B618053A
The challenge of storing hydrogen at high volumetric and gravimetric density for automotive applications has prompted investigations into the potential of cryo-adsorption on the internal surface area of microporous organic polymers. A range of Polymers of Intrinsic Microporosity (PIMs) has been studied, the best PIM to date (a network-PIM incorporating a triptycene subunit) taking up 2.7% H2 by mass at 10 bar/77 K. HyperCrosslinked Polymers (HCPs) also show promising performance as H2 storage materials, particularly at pressures >10 bar. The N2 and H2 adsorption behaviour at 77 K of six PIMs and a HCP are compared. Surface areas based on Langmuir plots of H2 adsorption at high pressure are shown to provide a useful guide to hydrogen capacity, but Langmuir plots based on low pressure data underestimate the potential H2 uptake. The micropore distribution influences the form of the H2 isotherm, a higher concentration of ultramicropores (pore size <0.7 nm) being associated with enhanced low pressure adsorption.
Co-reporter:Neil B. McKeown, Bader Gahnem, Kadhum J. Msayib, Peter M. Budd, Carin E. Tattershall, Khalid Mahmood, Siren Tan, David Book, Henrietta W. Langmi,Allan Walton
Angewandte Chemie International Edition 2006 45(11) pp:1804-1807
Publication Date(Web):
DOI:10.1002/anie.200504241
Co-reporter:Neil B. McKeown ;Bader Gahnem Dr.;Kadhum J. Msayib Dr. Dr.;Carin E. Tattershall Dr.;Khalid Mahmood Dr.;Siren Tan;David Book Dr.;Henrietta W. Langmi Dr.;Allan Walton Dr.
Angewandte Chemie 2006 Volume 118(Issue 11) pp:
Publication Date(Web):10 FEB 2006
DOI:10.1002/ange.200504241
Drei strukturell diverse Polymere mit intrinsischer Mikroporosität (PIMs) adsorbieren erhebliche Mengen Wasserstoff (1.4–1.7 Gew.-% bei 77 K). Sie bilden eine neue Klasse von organischen Wasserstoffspeichermaterialien, die an spezifische Anforderungen für die Wasserstoffphysisorption angepasst werden können.
Co-reporter:Detlev Fritsch;Neil B. McKeown
Macromolecular Symposia 2006 Volume 245-246(Issue 1) pp:403-405
Publication Date(Web):7 FEB 2007
DOI:10.1002/masy.200651356
We are developing new types of polymer – termed polymers of intrinsic microporosity (PIMs) – which in the solid state behave like molecular sieves. As pervaporation membranes, they show selectivity for organics over water. As gas separation membranes, they exhibit a remarkable combination of high permeability and good selectivity for gas pairs such as O2/N2.
Co-reporter:Peter M. Budd, Neil B. McKeown and Detlev Fritsch
Journal of Materials Chemistry A 2005 vol. 15(Issue 20) pp:1977-1986
Publication Date(Web):08 Feb 2005
DOI:10.1039/B417402J
The concept of free volume is useful for explaining aspects of the chain mobility and permeability of polymers, even though its precise definition is subject to debate. Polymers that trap a large amount of interconnected free volume in the glassy state behave in many respects like microporous materials and potentially find application in membrane separations and heterogeneous catalysis. The development is outlined of a new type of polymer, for which the molecular structure contains sites of contortion (e.g. spiro-centres) within a rigid backbone (e.g. ladder polymer). These polymers of intrinsic microporosity (PIMs) include both insoluble network polymers and soluble non-network polymers that may be processed into membranes or other useful forms. Experimental methods are discussed for elucidating the free volume or micropore distribution, and the behaviour of PIMs is compared with that of the ultrapermeable polymer poly(1-trimethylsilyl-1-propyne).
Co-reporter:Peter M. Budd, Kadhum J. Msayib, Carin E. Tattershall, Bader S. Ghanem, Kevin J. Reynolds, Neil B. McKeown, Detlev Fritsch
Journal of Membrane Science 2005 Volume 251(1–2) pp:263-269
Publication Date(Web):1 April 2005
DOI:10.1016/j.memsci.2005.01.009
When polymeric membranes are employed to remove selectively one component from a gaseous mixture, there is generally a trade-off between selectivity and permeability. Data are presented for two polymers of intrinsic microporosity, PIM-1 and PIM-7, which show a significant advance across the previous upper bound of performance for commercially important gas pairs, including O2/N2 and CO2/CH4. The exceptional properties of PIMs arise from their rigid but contorted molecular structures, which frustrate packing and so create free volume, coupled with chemical functionality giving strong intermolecular interactions.
Co-reporter:P. Bernardo, F. Bazzarelli, F. Tasselli, G. Clarizia, C.R. Mason, L. Maynard-Atem, P.M. Budd, M. Lanč, K. Pilnáček, O. Vopička, K. Friess, D. Fritsch, Yu.P. Yampolskii, V. Shantarovich, J.C. Jansen
Polymer (24 March 2017) Volume 113() pp:283-294
Publication Date(Web):24 March 2017
DOI:10.1016/j.polymer.2016.10.040
Co-reporter:Bekir Satilmis, Peter M. Budd
Journal of Colloid and Interface Science (15 April 2017) Volume 492() pp:
Publication Date(Web):15 April 2017
DOI:10.1016/j.jcis.2016.12.048
Nitrile groups in the polymer of intrinsic microporosity PIM-1 were modified by base-catalysed hydrolysis, by reaction with ethanolamine and diethanolamine, and by reduction to amine, and the products investigated for their ability to take up a range of dyes from aqueous or ethanolic solution. Hydrolysed products exhibited selectivity for cationic over anionic species, while other products showed the reverse selectivity. At low pH, amine-PIM-1 adsorbed more than its own weight of the anionic dyes Orange II and Acid Red I from aqueous solution. It was demonstrated that adsorbed Orange II can be removed with basic ethanol. Mixtures of oppositely charged dyes undergo precipitation, but selective adsorption of one dye leads to dissolution of the other from the precipitate. Thermal treatment of the chemically modified polymers at 300 °C for 48 h in an inert atmosphere led to structural changes that reduced the dye adsorption capacity. On the basis of a combination of thermogravimetric and elemental analysis with ATR-IR and NMR spectroscopy, feasible structures are suggested for the thermally-treated polymers.Figure optionsDownload full-size imageDownload high-quality image (61 K)Download as PowerPoint slide
Co-reporter:Peter M. Budd, Anna Butler, James Selbie, Khalid Mahmood, Neil B. McKeown, Bader Ghanem, Kadhum Msayib, David Book and Allan Walton
Physical Chemistry Chemical Physics 2007 - vol. 9(Issue 15) pp:NaN1808-1808
Publication Date(Web):2007/02/16
DOI:10.1039/B618053A
The challenge of storing hydrogen at high volumetric and gravimetric density for automotive applications has prompted investigations into the potential of cryo-adsorption on the internal surface area of microporous organic polymers. A range of Polymers of Intrinsic Microporosity (PIMs) has been studied, the best PIM to date (a network-PIM incorporating a triptycene subunit) taking up 2.7% H2 by mass at 10 bar/77 K. HyperCrosslinked Polymers (HCPs) also show promising performance as H2 storage materials, particularly at pressures >10 bar. The N2 and H2 adsorption behaviour at 77 K of six PIMs and a HCP are compared. Surface areas based on Langmuir plots of H2 adsorption at high pressure are shown to provide a useful guide to hydrogen capacity, but Langmuir plots based on low pressure data underestimate the potential H2 uptake. The micropore distribution influences the form of the H2 isotherm, a higher concentration of ultramicropores (pore size <0.7 nm) being associated with enhanced low pressure adsorption.
Co-reporter:Tamoghna Mitra, Rupesh S. Bhavsar, Dave J. Adams, Peter M. Budd and Andrew I. Cooper
Chemical Communications 2016 - vol. 52(Issue 32) pp:NaN5584-5584
Publication Date(Web):2016/03/21
DOI:10.1039/C6CC00261G
High-free-volume glassy polymers, such as polymers of intrinsic microporosity (PIMs) and poly(trimethylsilylpropyne), have attracted attention as membrane materials due to their high permeability. However, loss of free volume over time, or aging, limits their applicability. Introduction of a secondary filler phase can reduce this aging but either cost or instability rules out scale up for many fillers. Here, we report a cheap, acid-tolerant, nanoparticulate hypercrosslinked polymer ‘sponge’ as an alternative filler. On adding the filler, permeability is enhanced and aging is strongly retarded. This is accompanied by a CO2/N2 selectivity that increases over time, surpassing the Robeson upper bound.
Co-reporter:Helen J. Mackintosh, Peter M. Budd and Neil B. McKeown
Journal of Materials Chemistry A 2008 - vol. 18(Issue 5) pp:NaN578-578
Publication Date(Web):2007/12/10
DOI:10.1039/B715660J
Cobalt phthalocyanine and iron porphyrin network polymers of intrinsic microporosity (network-PIMs) were prepared and their performance as heterogeneous catalysts compared with that of low molar mass analogues. Spiro-linked Co phthalocyanine network-PIMs prepared from preformed chlorinated phthalocyanines showed lower surface areas and lower catalytic activity than those prepared by a phthalocyanine-forming reaction from a rigid precursor incorporating a spiro-centre. However, all the phthalocyanine network-PIMs were much more effective catalysts than low molar mass Co phthalocyanine for the decomposition of hydrogen peroxide, the oxidation of cyclohexene and the oxidation of hydroquinone. An Fe porphyrin network-PIM showed a higher surface area than any of the phthalocyanine polymers and showed higher activity for the oxidation of hydroquinone, also outperforming a low molar mass FeCl porphyrin.
Co-reporter:Bader S. Ghanem, Kadhum J. Msayib, Neil B. McKeown, Kenneth D. M. Harris, Zhigang Pan, Peter M. Budd, Anna Butler, James Selbie, David Book and Allan Walton
Chemical Communications 2007(Issue 1) pp:NaN69-69
Publication Date(Web):2006/11/15
DOI:10.1039/B614214A
A novel triptycene-based polymer of intrinsic microporosity (Trip-PIM) displays enhanced surface area (1065 m2 g−1) and reversibly adsorbs 1.65% hydrogen by mass at 1 bar/77 K and 2.71% at 10 bar/77 K.
(3,3'-
dimethyl[1,1'-binaphthalene]-4,4'-diyl)]](http://img.cochemist.com/ccimg/182400/182366-84-3.png)
(3,3'-
dimethyl[1,1'-binaphthalene]-4,4'-diyl)]](http://img.cochemist.com/ccimg/182400/182366-84-3_b.png)
![Diquinoxalino[2,3-a:2',3'-c]phenazine, 2,3,8,9,14,15-hexachloro-](/data/chemimg/3164000/389121-44-2.png)
![Diquinoxalino[2,3-a:2',3'-c]phenazine, 2,3,8,9,14,15-hexachloro-](/data/chemimg/3164000/389121-44-2_b.png)
![Poly[imino[(2S)-1-oxo-2-[3-oxo-3-(phenylmethoxy)propyl]-1,2-ethanediyl
]]](http://img.cochemist.com/ccimg/25100/25038-53-3.png)
![Poly[imino[(2S)-1-oxo-2-[3-oxo-3-(phenylmethoxy)propyl]-1,2-ethanediyl
]]](http://img.cochemist.com/ccimg/25100/25038-53-3_b.png)
![7,7'-Spirobi[7H-cyclopent[g]isobenzofuro[5,6-b][1,4]benzodioxin]-1,1',3,3'-tetrone, 8,8',9,9'-tetrahydro-9,9,9',9'-tetramethyl-](/data/chemimg/129700/939797-02-1.png)
![7,7'-Spirobi[7H-cyclopent[g]isobenzofuro[5,6-b][1,4]benzodioxin]-1,1',3,3'-tetrone, 8,8',9,9'-tetrahydro-9,9,9',9'-tetramethyl-](/data/chemimg/129700/939797-02-1_b.png)
