Antek G Wong-Foy

University of Michigan, Ann Arbor, Michigan, United States

Are you Antek G Wong-Foy?

Claim your profile

Publications (41)306.14 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: The application of a core-shell architecture allows the formation of a polymer-coated metal-organic framework (MOF) maintaining high surface area (2289-2857 m2g-1). The growth of a MOF shell from a MOF core was used to spatially localize initiators by post-synthetic modification. The confinement of initiators ensures that polymerization is restricted to the outer shell of the MOF.
    Chemical Communications 06/2015; DOI:10.1039/C5CC03027G · 6.72 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The development of high-capacity methane adsorbents would accelerate the adoption of natural gas as a vehicular fuel, thereby lowering CO2 emissions from the combustion of gasoline. In this regard metal-organic frameworks (MOFs) have emerged as promising methane storage materials due to their high capacities and tunable properties. Within this class, HKUST-1 [Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate]n is an important benchmark, as it exhibits methane densities that are amongst the highest reported. Furthermore, uptake in HKUST-1 can potentially be tuned by altering the methane-MOF interaction through metal substitution on coordinatively unsaturated sites (CUS). Predicting the impact of metal substitution remains a challenge, however, because general interatomic potentials commonly used in calculating uptake do not properly describe interactions involving CUS. Here, a new interatomic potential that explicitly accounts for these interactions is derived from quantum-mechanical calculations. The potential reproduces both the measured methane isotherm for HKUST-1 and the site preference for adsorption at CUS. Exten-sion to 17 metal-substituted variants confirms that CUS composition can dramatically alter uptake, with Ni- and Ca-based com-pounds predicted to slightly exceed the performance of Cu-HKUST-1. Trends in methane uptake correlate well with elementary MOF properties such as surface area, adsorption energy, and the electronegativity of the metal site.
    The Journal of Physical Chemistry C 05/2015; 119(24):150527120235004. DOI:10.1021/acs.jpcc.5b02768 · 4.84 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Thermodynamics drive crystalline organic molecules to be crystallized at temperatures below their melting point. Even though molecules can form supercooled liquids by rapid cooling, crystalline organic materials readily undergo a phase transformation to an energetically favorable crystalline phase upon subsequent heat treatment. Opposite to this general observation, here, we report molecular design of thermally stable supercooled liquid of diketopyrrolopyrrole (DPP) derivatives and their intriguing shear-triggered crystallization with dramatic optical property changes. Molten DPP8, one of the DPP derivatives, remains as stable supercooled liquid without crystallization through subsequent thermal cycles. More interestingly, under shear conditions, this supercooled liquid DPP8 transforms to its crystal phase accompanied by a 25-fold increase in photoluminescence (PL) quantum efficiency and a color change. By systematic investigation on supercooled liquid formation of crystalline DPP derivatives and their correlation with chemical structures, we reveal that the origin of this thermally stable supercooled liquid is a subtle force balance between aromatic interactions among the core units and van der Waals interactions among the aliphatic side chains acting in opposite directions. Moreover, by applying shear force to a supercooled liquid DPP8 film at different temperatures, we demonstrated direct writing of fluorescent patterns and propagating fluorescence amplification, respectively. Shear-triggered crystallization of DPP8 is further achieved even by living cell attachment and spreading, demonstrating the high sensitivity of the shear-triggered crystallization which is about 6 orders of magnitude more sensitive than typical mechanochromism observed in organic materials.
    05/2015; 1(2):150513072837007. DOI:10.1021/acscentsci.5b00091
  • Jialiu Ma, Antek G Wong-Foy, Adam J Matzger
    [Show abstract] [Hide abstract]
    ABSTRACT: A 2D zirconium-based microporous coordination polymer derived from the tritopic linker 1,3,5-(4-carboxylphenyl)benzene, UMCM-309a, has been synthesized. This noninterpenetrated material possesses a Zr6(μ3-O)4(μ3-OH)4(RCO2)6(OH)6(H2O)6 cluster with six hexagonal-planar-coordinated linkers. UMCM-309a is stable in an aqueous HCl solution for over 4 months. The use of different monocarboxylates as modulators leads to similar 2D structures with different layer spacings; moreover, removal of the modulator yields the parent UMCM-309a.
    Inorganic Chemistry 04/2015; 54(10). DOI:10.1021/acs.inorgchem.5b00413 · 4.79 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Design and synthesis of porous solids employing both reversible coordination chemistry and reversible covalent bond formation is described. The combination of two different linkage modes in a single material presents a link between two distinct classes of porous materials as exemplified by metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). This strategy, in addition to being a compelling material-discovery method, also offers a platform for developing a fundamental understanding of the factors influencing the competing modes of assembly. We also demonstrate that even temporary formation of reversible connections between components may be leveraged to make new phases thus offering design routes to polymorphic frameworks. Moreover, this approach has the striking potential of providing a rich landscape of structurally complex materials from commercially available or readily accessible feedstocks. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Angewandte Chemie International Edition in English 02/2015; 127(13). DOI:10.1002/anie.201411735 · 13.45 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Moisture can cause irreversible structural collapse in metal organic frameworks (MOFs) resulting in decreased internal surface areas and pore volumes. The details of such structural collapse with regard to pore size evolution during degradation are currently unknown due to a lack of suitable in situ probes of porosity. Here we acquire MOF porosity data under dynamic conditions by incorporating a flow-through system in tandem with positronium annihilation lifetime spectroscopy (PALS). From the decrease in porosity, we have observed an induction period for water degradation of some Zn4O-based MOFs that signals much greater stability than commonly believed to be possible. The sigmoidal trend in the degradation curve of unfunctionalized MOFs caused by water vapor has been established from the temporal component of pore size evolution as characterized by in situ PALS. IRMOF-3 is found to degrade at a lower relative humidity than MOF-5, a likely consequence of the amine groups in the structure, although, in contrast to MOF-5, residual porosity remains. The presence of an induction period and sigmoidal temporal behavior of the moisture-induced degradation mechanism of MOFs was also verified using powder X-ray diffraction analysis and ex situ gas adsorption measurements. Our work provides insight into porosity evolution under application-relevant conditions as well as identifying chemical and structural characteristics influencing stability.
    Journal of the American Chemical Society 02/2015; DOI:10.1021/ja512382f · 11.44 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: A strategy that allows the tuning of pore size in microporous coordination polymers (MCPs) through modification of their organic linkers is presented. When large substituents are introduced onto the linker, these pendent groups partially occupy the pores thus reducing pore size while serving as additional adsorption sites for gasses. The approach takes advantage of the fact that, for methane storage materials, small pores (0.4-0.8 nm in diameter) are more desirable than large pores since small pores promote optimal volumetric capacity. This method was demonstrated with IRMOF-8, a MCP constructed from Zn4O metal clusters and 2,6-naphthalenedicarboxylate (NDC) linkers. The NDC was functionalized through the addition of substituents including tbutylethynyl or phenylethynyl groups. High pressure methane uptake demonstrates that the IRMOF-8 derivatives have significantly better performance than the unfunctionalized material in terms of both excess volumetric uptake and deliverable capacity. Moreover, IRMOF-8 derivatives also give rise to stronger interactions with methane molecules as shown by higher heat of adsorption values.
    Langmuir 01/2015; 31(7). DOI:10.1021/la504607c · 4.38 Impact Factor
  • Ananya Dutta, Antek G. Wong-Foy, Adam J. Matzger
    [Show abstract] [Hide abstract]
    ABSTRACT: Incorporation of three distinct linkers with identical functionality in a coordination copolymer is accomplished in materials designated UMCM-10, -11, and -12. Uniaxial lattice expansion, achieved in these highly porous and non-interpenetrated materials, is utilized in size-selective guest incorporation.
    Chemical Science 07/2014; 5(10). DOI:10.1039/C3SC53549E · 8.60 Impact Factor
  • Ping Guo, Antek G Wong-Foy, Adam Jay Matzger
    [Show abstract] [Hide abstract]
    ABSTRACT: Air drying is a widespread and critical industrial process. Removal of water from air is commonly accomplished by passage through a desiccant such as alumina; modest water capacity and energy intensive regeneration are limitations of currently used sorbents. Microporous coordination polymers (MCPs) are demonstrated here to be efficient desiccants for the dehumidification of air and comparison of their capacity, regenerability and efficiency with commercial activated alumina is conducted. Complete regeneration using dry air with mild heating is achieved. The attainment of high capacity for the adsorption of water coupled to facile regeneration indicates that gas dehumidification may be an important application for MCPs.
    Langmuir 02/2014; 30(8). DOI:10.1021/la4043556 · 4.38 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Because of their high surface areas, crystallinity, and tunable properties, metal−organic frameworks (MOFs) have attracted intense interest as next-generation materials for gas capture and storage. While much effort has been devoted to the discovery of new MOFs, a vast catalog of existing MOFs resides within the Cambridge Structural Database (CSD), many of whose gas uptake properties have not been assessed. Here we employ data mining and automated structure analysis to identify, "cleanup," and rapidly predict the hydrogen storage properties of these compounds. Approximately 20 000 candidate compounds were generated from the CSD using an algorithm that removes solvent/guest molecules. These compounds were then characterized with respect to their surface area and porosity. Employing the empirical relationship between excess H 2 uptake and surface area, we predict the theoretical total hydrogen storage capacity for the subset of ∼4000 compounds exhibiting nontrivial internal porosity. Our screening identifies several overlooked compounds having high theoretical capacities; these compounds are suggested as targets of opportunity for additional experimental characterization. More importantly, screening reveals that the relationship between gravimetric and volumetric H 2 density is concave downward, with maximal volumetric performance occurring for surface areas of 3100−4800 m 2 /g. We conclude that H 2 storage in MOFs will not benefit from further improvements in surface area alone. Rather, discovery efforts should aim to achieve moderate mass densities and surface areas simultaneously, while ensuring framework stability upon solvent removal.
    Chemistry of Materials 07/2013; 25(16):3373. DOI:10.1021/cm401978e · 8.54 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: This paper describes the heterogenization of single-site transition-metal catalysts in metal-organic frameworks (MOFs) via cation exchange. A variety of cationic complexes of Pd, Fe, Ir, Rh, and Ru have been incorporated into ZJU-28, and the new materials have been characterized by optical microscopy, inductively coupled plasma optical emission spectroscopy, and powder X-ray diffraction. MOF-supported [Rh(dppe)(COD)]BF4 catalyzes the hydrogenation of 1-octene to n-octane. The activity of this supported catalyst compares favorably to its homogeneous counterpart, and it can be recycled at least four times. Overall, this work provides a new and general approach for supporting transition-metal catalysts in MOFs.
    Journal of the American Chemical Society 07/2013; 135(29). DOI:10.1021/ja402577s · 11.44 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Microporous coordination polymers (MCPs) have emerged as strong contenders for adsorption-based fuel storage and delivery in large part because of their high specific surface areas. The strategy of increasing surface area by increasing organic linker length has shown only sporadic success; as demonstrated by many members of the iconic Zn4O-based IRMOF series, for example, accessible porosity is often limited by interpenetration or pore collapse upon guest removal. In this work, we focus on Zn4O(ndc)3 (IRMOF-8, ndc = 2,6-naphthalene dicarboxylate), which exhibits typical surface areas of only 1000-2000 m(2)/g even though a surface area of more than 4000 m(2)/g is expected from geometric analysis of the originally reported crystal structure. We recently showed that a high surface area could be produced with zinc and ndc by room-temperature synthesis followed by activation with flowing supercritical CO2. In this work, we investigate in detail the porosity of both the low- and high-surface-area materials. Positron annihilation lifetime spectroscopy (PALS) is used to show that the low-surface-area material suffers from near-complete interpenetration, explaining why traditional synthetic routes have failed to yield materials with the expected porosity. Furthermore, the high-pressure hydrogen and methane sorption properties of noninterpenetrated Zn4O(ndc)3 are examined, and PALS is used to show that pore filling is not operative during room-temperature CH4 sorption even at pressures approaching 100 bar. These results provide insight into how gas adsorbs in high-surface-area materials at high pressure and reinforce previous contentions that increasing surface area alone is not sufficient for the simultaneous optimization of deliverable gravimetric and volumetric gas uptake in MCPs.
    Langmuir 06/2013; 29(25). DOI:10.1021/la401323t · 4.38 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Positronium (Ps) is shown to exist in a delocalized state in self-assembled metalorganic crystals that have large 1.3-1.5 nm cell sizes. Belonging to a class of materials with record high accessible specific surface areas, these highly porous crystals are the first to allow direct probing with simple annihilation lifetime techniques of the transport properties of long-lived triplet Ps in what is hypothesized to be a Bloch state. Delocalized Ps has unprecedented (high) Ps mobility driven primarily by weak phonon scattering with unusual and profound consequences on how Ps probes the lattice.
    Physical Review Letters 05/2013; 110(19):197403. DOI:10.1103/PhysRevLett.110.197403 · 7.73 Impact Factor
  • Baojian Liu, Antek G Wong-Foy, Adam J Matzger
    [Show abstract] [Hide abstract]
    ABSTRACT: Flowing supercritical CO(2) was used to activate a cross section of microporous coordination polymers (MCPs) directly from DMF, thus avoiding exchange with a volatile solvent. Most MCPs displayed exceptional surface areas directly after treatment although those with coordinatively unsaturated metals benefit from heating. The method presents an advance in efficiency of activation and quality of material obtained.
    Chemical Communications 01/2013; 49(14). DOI:10.1039/c2cc37793d · 6.72 Impact Factor
  • Jeremy I Feldblyum, Antek G Wong-Foy, Adam J Matzger
    [Show abstract] [Hide abstract]
    ABSTRACT: The synthesis and successful activation of IRMOF-8 (Zn(4)O(ndc)(3), ndc = naphthalene-2,6-dicarboxylate) is presented. Room temperature synthesis effectively suppresses interpenetration. Although conventional activation under reduced pressure leads to structural collapse, activation by flowing supercritical CO(2) yields a guest-free material with a BET surface area of 4461 m(2) g(-1).
    Chemical Communications 08/2012; 48(79):9828-30. DOI:10.1039/c2cc34689c · 6.72 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Although a multitude of microporous coordination polymers (MCPs) with ultrahigh surface area have been reported in the last decade, none of these can come close to matching the cost/performance ratio of conventional sorbents such as zeolites and carbons for most applications. There is a need to drastically reduce the cost of MCPs and this goal cannot be achieved through complex linker synthesis strategies so often used to boost MCP performance. Here two new MCPs: UMCM-8 (Zn4O(benzene-1,4-dicarboxylate)1.5(naphthalene-2,6-dicarboxylate)1.5), and UMCM-9 (Zn4O(naphthalene-2,6-dicarboxylate)1.5(biphenyl-4,4′-dicarboxylate)1.5) are described and the concept of using mixtures of readily available linear linkers that enforce different spacings between network nodes is introduced as a means to reduce interpenetration. These new MCPs demonstrate Brunauer–Emmett–Teller (BET) surface areas over 4000 m2 g−1 and high pore volumes over 1.80 cm3 g−1.
    Chemical Science 05/2012; 3(8):2429-2432. DOI:10.1039/C2SC20407J · 8.60 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: High reversibility during crystallization leads to relatively defect-free crystals through repair of nonperiodic inclusions, including those derived from impurities. Microporous coordination polymers (MCPs) can achieve a high level of crystallinity through a related mechanism whereby coordination defects are repaired, leading to single crystals. In this work, we discovered and exploited the fact that this process is far from perfect for MCPs and that a minority ligand that is coordinatively identical to but distinct in shape from the majority linker can be inserted into the framework, resulting in defects. The reaction of Zn(II) with 1,4-benzenedicarboxylic acid (H(2)BDC) in the presence of small amounts of 1,3,5-tris(4-carboxyphenyl)benzene (H(3)BTB) leads to a new crystalline material, MOF-5(O(h)), that is nearly identical to MOF-5 but has an octahedral morphology and a number of defect sites that are uniquely functionalized with dangling carboxylates. The reaction with Pd(OAc)(2) impregnates the metal ions, creating a heterogeneous catalyst with ultrahigh surface area. The Pd(II)-catalyzed phenylation of naphthalene within Pd-impregnated MOF-5(O(h)) demonstrates the potential utility of an MCP framework for modulating the reactivity and selectivity of such transformations. Furthermore, this novel synthetic approach can be applied to different MCPs and will provide scaffolds functionalized with catalytically active metal species.
    Journal of the American Chemical Society 11/2011; 133(50):20138-41. DOI:10.1021/ja2094316 · 11.44 Impact Factor
  • Austin C Kizzie, Antek G Wong-Foy, Adam J Matzger
    [Show abstract] [Hide abstract]
    ABSTRACT: The CO(2)-capture performance of microporous coordination polymers of the M/DOBDC series (where M = Zn, Ni, Co, and Mg; DOBDC = 2,5-dioxidobenzene-1,4-dicarboxylate) was evaluated under flow-through conditions with dry surrogate flue gas (5/1 N(2)/CO(2)). The CO(2) capacities were found to track with static CO(2) sorption capacities at room temperature, with Mg/DOBDC demonstrating an exceptional capacity for CO(2) (23.6 wt %). The effect of humidity on the performance of Mg/DOBDC was investigated by collecting N(2)/CO(2)/H(2)O breakthrough curves at relative humidities (RHs) in the feed of 9, 36, and 70%. After exposure at 70% RH and subsequent thermal regeneration, only about 16% of the initial CO(2) capacity of Mg/DOBDC was recovered. However, in the case of Ni/DOBDC and Co/DOBDC, approximately 60 and 85%, respectively, of the initial capacities were recovered after the same treatment. These data indicate that although Mg/DOBDC has the highest capacity for CO(2), under the conditions used in this study, Co/DOBDC may be a more desirable material for deployment in CO(2) capture systems because of the added costs associated with flue gas dehumidification.
    Langmuir 05/2011; 27(10):6368-73. DOI:10.1021/la200547k · 4.38 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Random copolymerization is a core strategy of the polymer industry, enabling broad tuning of materials properties through mixing monomers with similar reactivities. In coordination polymers, analogous results have recently been achieved using combinations of isomorphic linkers copolymerized by appropriate metals; in general, the properties of the resultant coordination copolymers can be described as a linear combination of the properties of the constituent building blocks. Here we demonstrate that this need not be the case: coordination copolymerization is a powerful strategy for directing phase formation. For example, reaction of 1,4-benzenedicarboxylic acid with Zn2+ typically affords phase-impure material in N,N-dimethylformamide whereas using an amino functionalized linker leads to pure high surface area material with the structure of MOF-5. However, mixed-linker copolymers derived from a combination of both linkers display surface areas comparable to that of MOF-5 synthesized in N,N-diethylformamide, indicating that even a minor linker component can direct phase selection. In a second illustration, the pore blockage of the bulky group in 9,10-bis(triisopropylsilyloxy)phenanthrene-2,7-dicarboxylate (TPDC) not only suppresses the framework interpenetration of biphenyl-based IRMOF architectures but also blocks adsorption sites, yielding a low surface area material. However, the random coordination copolymerization of Zn2+ with a mixture of TPDC and 3,3′,5,5′-tetramethyl-4,4′-biphenyldicarboxylate (Me4BPDC) controls the level of framework interpenetration and the degree of pore blockage, resulting in higher surface area (up to 3000 m2/g) copolymers than the noninterpenetrated Zn4O(TPDC)3 and interpenetrated Zn4O(Me4BPDC)3 frameworks.
    Crystal Growth & Design 04/2011; 11(6):2059–2063. DOI:10.1021/cg200271e · 4.56 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: N-Heteroarene substitution into biphenyl-based linkers enhances the uptake of electron-rich organosulfur molecules in a series of isostructural microporous coordination polymers.
    Chemical Communications 02/2011; 47(5):1452-4. DOI:10.1039/c0cc03482g · 6.72 Impact Factor