Hexiang Deng

Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks

Many Mixed Linkers in MOFs Crystallization can separate different molecules because different molecules cannot generally be accommodated equally well in the same crystal lattice. However, in metal-organic framework (MOF) compounds, the organic linkers do not pack closely to other parts of the lattice, so it may be possible to mix several linkers that are derivatives of a parent compound with the same end groups. Deng et al. (p. 846) show that zinc-based MOFs can be made that mix 1,4-benzenedicarboxylate and up to eight of its derivatives in a random fashion. The effects of such mixing on porosity and absorption characteristics is nonlinear; in one case, a mixed-linker compound was four times better for selecting CO2 versus CO compared with the best MOF bearing only one of the component linkers. The adsorption characteristics for mixed linkers can exceed that expected from just combining the single-linker compounds. We show that metal-organic frameworks (MOFs) can incorporate a large number of different functionalities on linking groups in a way that mixes the linker, rather than forming separate domains. We made complex MOFs from 1,4-benzenedicarboxylate (denoted by “A” in this work) and its derivatives -NH2, -Br, -(Cl)2, -NO2, -(CH3)2, -C4H4, -(OC3H5)2, and -(OC7H7)2 (denoted by “B” to “I,” respectively) to synthesize 18 multivariate (MTV) MOF-5 type structures that contain up to eight distinct functionalities in one phase. The backbone (zinc oxide and phenylene units) of these structures is ordered, but the distribution of functional groups is disordered. The complex arrangements of several functional groups within the pores can lead to properties that are not simply linear sums of those of the pure components. For example, a member of this series, MTV-MOF-5-EHI, exhibits up to 400% better selectivity for carbon dioxide over carbon monoxide compared with its best same-link counterparts.

Large-Pore Apertures in a Series of Metal-Organic Frameworks

Maximizing Molecular Pore Diameters Amorphous materials, such as activated carbon, can have pore diameters of several nanometers, but the synthesis of ordered structures with very large pore diameters is often thwarted by the creation of interpenetrating networks or difficulties in removing guest molecules. Deng et al. (p. 1018) avoided these problems in the synthesis of metal-organic frameworks (MOFs) with very large diameters (some exceeding 3 nanometers) by using a combination of short and very long linking groups. The compounds formed channels almost 10 nanometers in diameter that could be visualized by electron microscopy and that were large enough to accommodate protein molecules. Metal-organic frameworks with hexagonal channel pores up to almost 100 angstroms in diameter have been synthesized. We report a strategy to expand the pore aperture of metal-organic frameworks (MOFs) into a previously unattained size regime (>32 angstroms). Specifically, the systematic expansion of a well-known MOF structure, MOF-74, from its original link of one phenylene ring (I) to two, three, four, five, six, seven, nine, and eleven (II to XI, respectively), afforded an isoreticular series of MOF-74 structures (termed IRMOF-74-I to XI) with pore apertures ranging from 14 to 98 angstroms. All members of this series have noninterpenetrating structures and exhibit robust architectures, as evidenced by their permanent porosity and high thermal stability (up to 300°C). The pore apertures of an oligoethylene glycol–functionalized IRMOF-74-VII and IRMOF-74-IX are large enough for natural proteins to enter the pores.

Mapping of Functional Groups in Metal-Organic Frameworks

Mapping Molecular Linkers In metal-organic framework compounds, inorganic centers (metal atoms or clusters) are linked by bidentate organic groups. Normally, the same group is used throughout the structure, but recently, synthesis with linkers bearing different functional groups has produced well-defined materials. Kong et al. (p. 882, published online 25 July) combined solid-state nuclear magnetic resonance and molecular simulations to map the distributions of linkers in these materials as random, well-mixed, or clustered. Solid-state nuclear magnetic resonance and simulations map the distribution of linking groups in metal-organic frameworks. We determined the heterogeneous mesoscale spatial apportionment of functional groups in a series of multivariate metal-organic frameworks (MTV-MOF-5) containing BDC (1,4-benzenedicarboxylate) linkers with different functional groups—B (BDC-NH2), E (BDC-NO2), F [(BDC-(CH3)2], H [BDC-(OC3H5)2], and I [BDC-(OC7H7)2]—using solid-state nuclear magnetic resonance measurements combined with molecular simulations. Our analysis reveals that these methods discern between random (EF), alternating (EI and EHI), and various cluster (BF) forms of functional group apportionments. This combined synthetic, characterization, and computational approach predicts the adsorptive properties of crystalline MTV-MOF systems. This methodology, developed in the context of ordered frameworks, is a first step in resolving the more general problem of spatial disorder in other ordered materials, including mesoporous materials, functionalized polymers, and defect distributions within crystalline solids.

Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177

Metal-organic framework-177 (MOF-177) is one of the most porous materials whose structure is composed of octahedral Zn4O(-COO)6 and triangular 1,3,5-benzenetribenzoate (BTB) units to make a three-dimensional extended network based on the qom topology. This topology violates a long-standing thesis where highly symmetric building units are expected to yield highly symmetric networks. In the case of octahedron and triangle combinations, MOFs based on pyrite (pyr) and rutile (rtl) nets were expected instead of qom. In this study, we have made 24 MOF-177 structures with different functional groups on the triangular BTB linker, having one or more functionalities. We find that the position of the functional groups on the BTB unit allows the selection for a specific net (qom, pyr, and rtl), and that mixing of functionalities (-H, -NH2, and -C4H4) is an important strategy for the incorporation of a specific functionality (-NO2) into MOF-177 where otherwise incorporation of such functionality would be difficult. Such mixing of functionalities to make multivariate MOF-177 structures leads to enhancement of hydrogen uptake by 25%.

Synthesis and Characterization of Metal–Organic Framework-74 Containing 2, 4, 6, 8, and 10 Different Metals

Metal-organic frameworks (MOFs) containing more than two kinds of metal ions mixed in one secondary building unit are rare because the synthesis often yields mixed MOF phases rather than a pure phase of a mixed-metal MOF (MM-MOF). In this study, we use a one-pot reaction to make microcrystalline MOF-74 [M2(DOT); DOT = dioxidoterephthalate] with 2 (Mg and Co), 4 (Mg, Co, Ni, and Zn), 6 (Mg, Sr, Mn, Co, Ni, and Zn), 8 (Mg, Ca, Sr, Mn, Fe, Co, Ni, and Zn), and 10 (Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Zn, and Cd) different kinds of divalent metals. The powder X-ray diffraction patterns of MM-MOF-74 were identical with those of single-metal MOF-74, and no amorphous phases were found by scanning electron microscopy. The successful preparation of guest-free MM-MOF-74 samples was confirmed by N2 adsorption measurements. Elemental analysis data also support the fact that all metal ions used in the MOF synthesis are incorporated within the same MOF-74 structure. Energy-dispersive X-ray spectroscopies indicate that metal ions are heterogeneously distributed within each of the crystalline particles. This approach is also employed to incorporate metal ions (i.e., Ca, Sr, Ba, and Cd) from which the parent MOF structure could not be made as a single-metal-containing MOF.

Photophysical pore control in an azobenzene-containing metal–organic framework

The synthesis and structure of an azobenzene functionalized isoreticular metal–organic framework (azo-IRMOF-74-III) [Mg2(C26H16O6N2)] are described and the ability to controllably release a guest from its pores in response to an external stimulus has been demonstrated. Azo-IRMOF-74-III is an isoreticular expansion of MOF-74 with an etb topology and a 1-D hexagonal pore structure. The structure of azo-IRMOF-74-III is analogous to that of MOF-74, as demonstrated by powder X-ray diffraction, with a surface area of 2410 m2 g−1 BET. Each organic unit within azo-IRMOF-74-III is decorated with a photoswitchable azobenzene unit, which can be toggled between its cis and trans conformation by excitation at 408 nm. When propidium iodide dye was loaded into the MOF, spectroscopic studies showed that no release of the luminescent dye was observed under ambient conditions. Upon irradiation of the MOF at 408 nm, however, the rapid wagging motion inherent to the repetitive isomerization of the azobenzene functionality triggered the release of the dye from the pores. This light-induced release of cargo can be modulated between an on and an off state by controlling the conformation of the azobenzene with the appropriate wavelength of light. This report highlights the ability to capture and release small molecules and demonstrates the utility of self-contained photo-active switches located inside highly porous MOFs.

Extra adsorption and adsorbate superlattice formation in metal-organic frameworks

Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate–adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate–adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption–desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of ‘extra adsorption domains’—that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

Designed amyloid fibers as materials for selective carbon dioxide capture

Significance New and improved materials capable of binding carbon dioxide are essential to addressing the global threat of accelerating climate change. The presently used industrial methods for carbon dioxide capture have severe drawbacks, including toxicity and energy inefficiency. Newer porous materials are so far less effective in water, invariably a component of combustion gases. Here, we present a material for carbon dioxide capture. This material, amyloid fibers in powdered form, selectively captures carbon dioxide in the presence of water and binds carbon dioxide strongly until it is released by heating, regenerating the robust amyloid fibers in an energy efficient process. New materials capable of binding carbon dioxide are essential for addressing climate change. Here, we demonstrate that amyloids, self-assembling protein fibers, are effective for selective carbon dioxide capture. Solid-state NMR proves that amyloid fibers containing alkylamine groups reversibly bind carbon dioxide via carbamate formation. Thermodynamic and kinetic capture-and-release tests show the carbamate formation rate is fast enough to capture carbon dioxide by dynamic separation, undiminished by the presence of water, in both a natural amyloid and designed amyloids having increased carbon dioxide capacity. Heating to 100 °C regenerates the material. These results demonstrate the potential of amyloid fibers for environmental carbon dioxide capture.

Deciphering the Spatial Arrangement of Metals and Correlation to Reactivity in Multivariate Metal–Organic Frameworks

Thirty-six porphyrin-based metal-organic frameworks (MOFs) with composition of (M3O)2(TCPP-M)3 and M3O trigonal SBUs of various metals, Mg3O, Mn3O, Co3O, Ni3O, and Fe3O including mixed-metal SBUs, MnxFe3-xO, NixFe3-xO, CoxNi3-xO, MnxCo3-xO, MnxMg3-xO, and MnxNi3-xO were synthesized and characterized. These multivariate MOFs (MTV-MOFs) were examined by X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectra, and for the first time, their metal spatial arrangement deciphered and were found to exist in the form of either domains or well-mixed. We find that MTV-MOFs with well-mixed metals in their SBUs, rather than the SBUs having one kind of metal but different from one SBU to another, perform better than the sum of their parts in the test reaction involving the photo-oxidation of 1,5-dihydroxynaphthalene.

Principles of Designing Extra-Large Pore Openings and Cages in Zeolitic Imidazolate Frameworks

We report three design principles for obtaining extra-large pore openings and cages in the metal-organic analogues of inorganic zeolites, zeolitic imidazolate frameworks (ZIFs). Accordingly, we prepared a series of 15 ZIFs, members of which have the largest pore opening (22.5 Å) and the largest cage size (45.8 Å) known for all porous tetrahedral structures. The key parameter allowing us to access these exceptional ZIFs is what we define as the steric index (δ), which is related to the size and shape of the imidazolate linkers employed in the synthesis. The three principles are based on using multiple linkers with specific range and ratios of δ to control the size of rings and cages from small to large, and therefore are universally applicable to all existing ZIFs. The ZIF with the largest cage size (ZIF-412) shows the best selectivity of porous materials tested toward removal of octane and p-xylene from humid air.