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Ammonia is a widely used toxic industrial chemical that can cause severe respiratory ailments. Therefore, understanding and developing materials for its efficient capture and controlled release is necessary. One such class of materials is 3D porous metal-organic frameworks (MOFs) with exceptional surface areas and robust structures, ideal for gas storage/transport applications. Herein, interactions between ammonia and UiO-67-X (X: H, NH 2 , CH 3 ) zirconium MOFs were studied under cryogenic, ultrahigh vacuum (UHV) conditions using temperature-programmed desorption mass spectrometry (TPD-MS) and in-situ temperature-programmed infrared (TP-IR) spectroscopy. Ammonia was observed to interact with μ 3 -OH groups present on the secondary building unit of UiO-67-X MOFs via hydrogen bonding. TP-IR studies revealed that under cryogenic UHV conditions, UiO-67-X MOFs are stable towards ammonia sorption. Interestingly, an increase in the intensity of the C-H stretching mode of the MOF linkers was detected upon ammonia exposure, attributed to NH-π interactions with linkers. These same binding interactions were observed in grand canonical Monte Carlo simulations. Based on TPD-MS, binding strength of ammonia to three MOFs was determined to be approximately 60 kJ mol -1 , suggesting physisorption of ammonia to UiO-67-X. In addition, missing linker defect sites, consisting of H 2 O coordinated to Zr 4+ sites, were detected through the formation of nNH 3 ⋅H 2 O clusters, characterized through in-situ IR spectroscopy. Structures consistent with these assignments were identified through density functional theory calculations. Tracking these bands through adsorption on thermally activated MOFs gave insight into the dehydroxylation process of UiO-67 MOFs. This highlights an advantage of using NH 3 for the structural analysis of MOFs and developing an understanding of interactions between ammonia and UiO-67-X zirconium MOFs, while also providing directions for the development of stable materials for efficient toxic gas sorption., (© 2021 Wiley-VCH GmbH.)

While metal-organic frameworks (MOFs) have been identified as promising materials for sensitizing near-infrared emitting lanthanide ions (Ln 3+ ) for biological imaging, long-wavelength excitation of such materials requires large, highly delocalized organic linkers or guest-chromophores. Incorporation of such species generally coincides with fewer Ln 3+ emitters per unit volume. Herein, the excitation bands of ytterbium-based MOFs are extended to 800 nm via the postsynthetic coupling of acetylene units to form a high density of conjugated π-systems throughout MOF pores. The resulting long wavelength excitation/absorption bands are a synergistic property of the composite material as they are not observed in the individual organic components after disassociation of the MOFs, thus circumventing the need for large organic chromophores. We demonstrate that the long wavelength excitation and emission properties of these modified MOFs are maintained in the biological conditions of cell culture (aqueous environment, salts, heating), pointing toward their promising use for biological imaging applications.

Incorporating diverse components into metal–organic frameworks (MOFs) can expand their scope of properties and applications. Stratified MOFs (sMOFs) consist of compositionally unique concentric domains (strata), offering unprecedented complexity through partitioning of structural and functional components. However, the labile nature of metal‐ligand coordination handicaps achieving compositionally distinct domains due to ligand exchange reactions occurring concurrently with secondary strata growth. To achieve complex sMOF compositions, characterizing and controlling the competing processes of new strata growth and ligand exchange are vital. This work systematically examines controlling ligand exchange in UiO‐67 sMOFs by tuning ligand sterics. We present quantitative methods for assessing and visualizing the outcomes of strata growth and ligand exchange that rely on high‐angle annular dark‐field images and elemental mapping via scanning transmission electron microscopy‐energy dispersive X‐ray spectroscopy. In addition, we leverage ligand sterics to create 'blocking layers' that minimize ligand exchange between strata which are particularly susceptible to ligand exchange and inter‐strata ligand mixing. Finally, we evaluate strata compositional integrity in various solvents and find that sMOFs can maintain their compositions for >12 months in some cases. Collectively, these studies and methods enhance understanding and control over ligand placement in multi‐domain MOFs, factors that underscore careful tunning of properties and function. [ABSTRACT FROM AUTHOR]

The effective utilization of light is crucial in the use of the solar energy for CO2 conversion into valuable fuels and chemicals, in which improving the photocatalytic materials' capacity to absorb light is a key. Herein, a 2D copper–porphyrin metal−organic framework (MOF)‐photosensitized titania, TiO2/Zn–CuTCPP, is reported, which can absorb wide range of light and photoreduce CO2 with high efficiency under full spectrum irradiation. Fluorescence spectral analysis elucidates the relationship between the photocatalytic activity and the electron–hole separation efficiency. In addition, mechanistic information obtained from electron paramagnetic resonance and in situ infrared analyses demonstrates that the presence of Cu–N4 site in the MOF structure is conducive to the generation of hydrogen free radicals (•H), which plays a key role in the formation of intermediates, thus facilitating the hydrogenation in the reaction process. Consequently, TiO2/Zn–CuTCPP significantly enhances the photocatalytic conversion of CO2 into CH4 with a yield 14 times higher than that of P25. [ABSTRACT FROM AUTHOR]

Formamides are important feedstocks for the manufacture of many fine chemicals. State‐of‐the‐art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom‐economy. Here, we report the first example of direct synthesis of N‐formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass‐derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal‐organic framework supported ruthenium catalyst, Ru/MFM‐300(Cr). Highly selective production of N‐formamides has been observed for a wide range of carbonyl compounds. Synchrotron X‐ray powder diffraction reveals the presence of strong host‐guest binding interactions via hydrogen bonding and parallel‐displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals. [ABSTRACT FROM AUTHOR]

Deuterium labelling of organic compounds is an important process in chemistry. We report the first example of photocatalytic dehalogenative deuteration of both arylhalides and alkylhalides (40 substrates) over a metal–organic framework, MFM‐300(Cr), using CD3CN as the deuterium source at room temperature. MFM‐300(Cr) catalyses high deuterium incorporation and shows excellent tolerance to various functional groups. Synchrotron X‐ray powder diffraction reveals the activation of halogenated substrates via confined binding within MFM‐300(Cr). In situ electron paramagnetic resonance spectroscopy confirms the formation of carbon‐based radicals as intermediates and reveals the reaction pathway. This protocol removes the use of precious‐metal catalysts from state‐of‐the‐art processes based upon direct hydrogen isotope exchange and shows high photocatalytic stability, thus enabling multiple catalytic cycles. [ABSTRACT FROM AUTHOR]

With increasing demands for high‐performance water sorption materials, metal‐organic frameworks (MOFs) have gained considerable attention due to their high maximum uptake capacities. In many cases, however, high overall capacity is not necessarily accomplishing high working capacity under operating conditions, due to insufficient hydrophilicity and/or water stability. Herein, we present a post‐synthetic modification (PSM) of MOF‐808, with di‐sulfonic acids enhancing simultaneously its hydrophilicity and water stability without sacrificing its uptake capacity of ≈30 mmol g−1. Di‐sulfonic acid PSM enabled a shift of the relative humidity (RH) associated with a sharp step in water vapor sorption from 35–40 % RH in MOF‐808 to below 25 % RH. While MOF‐808 lost uptake capacity and crystallinity over multiple sorption/desorption cycles, the di‐sulfonic acid PSM MOF‐808 retained >80 % of the original capacity. PSM MOF‐808 exhibited good hydrothermal stability up to 60 °C and high swing capacity. [ABSTRACT FROM AUTHOR]

Novel two-dimensional kagome metal–organic frameworks with mononuclear Zr4+/Hf4+ nodes chelated by benzene-1,4-dihydroxamate linkers were synthesized. The MOFs, namely SUM-1, are chemically robust and kinetically favorable, as confirmed by theoretical and experimental studies. SUM-1(Zr) can be readily made into large (∼100 μm) single crystals and nanoplates (∼50 nm), constituting a versatile MOF platform. [ABSTRACT FROM AUTHOR]

The kinetics of hydrolysis of dimethyl nitrophenyl phosphate (DMNP), a simulant of the nerve agent Soman, was studied and revealed transition metal salts as catalysts. The relative rates of DMNP hydrolysis by zirconium and hafnium chlorides are in accordance with their Lewis acidity. In situ conversion of zirconium chloride to zirconium oxy-hydroxide was identified as the key step. We propose a precursor-MOF activity relationship. [ABSTRACT FROM AUTHOR]

Abstract: Developing hybrid carbon materials with unique micro/nanostructured and multicomponent features is of great importance in catalysis, energy storage, and energy conversion. Herein, we demonstrate the formation of a novel kind of hybrid carbon material, that is, bimetallic nanoparticles supported by ultrathin (≈5.5 nm) and porous carbon nanosheets, by the pyrolysis of preformed bimetallic metal–organic framework nanosheets. This hybrid carbon nanostructure combines the advantages of highly exposed nanoparticles that are readily accessible to the reactant, multiple active sites such as metal–metal and metal–nitrogen sites and ultrathin carbon layers, and highly efficient electron transport. Owing to these unique features, the bimetallic carbon nanosheets exhibit excellent electrocatalytic performance for the oxygen reduction reaction. [ABSTRACT FROM AUTHOR]

Abstract: The catalytic performance of metal–organic frameworks (MOFs) for the synthesis of cyclic carbonate from carbon dioxide and epoxides has been explored under solvent and solvent‐free conditions, respectively. It was found that MOF catalysts have significantly improved catalytic activities in solvent‐free CO2 cycloaddition reactions than those in solvent. The mechanism was discussed with regard to the competition of solvent with substrate to adhere MOF catalysts during the reaction process. [ABSTRACT FROM AUTHOR]

The Td point group symmetry of rare earth (RE3+) metal clusters RE4(μ3-OH)4(COO)6 2+ makes them attractive building blocks for creating metal-organic frameworks (MOFs) with controllable topologies. Herein, we describe the design and synthesis of a series of isoreticular MOFs featuring pcu topology [MOF-1114(RE) and MOF-1115(RE)] with variable rare earth metal ions (RE3+ = Y3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+) and linear amino-functionalized dicarboxylate linkers of different lengths. In total, we report 22 MOFs that vary in both composition and structure yet share the same RE4(μ3-OH)4 cluster motif. We demonstrate that these pcu MOFs are cationic and that anion exchange can be used to affect the MOF properties. We also investigate the luminescence properties of a representative member of this MOF series [MOF-1114(Yb)] that exhibits near-infrared emission. We show that the excitation energy for Yb3+ sensitization can be carefully adjusted to lower energy via covalent postsynthetic modification at the amino group sites within the MOF. [ABSTRACT FROM AUTHOR]

Forming emulsions of carbon dioxide (CO2) and water can largely expand the utility of CO2. Herein we propose for the first time the utilization of a metal-organic framework (MOF) for emulsifying CO2 and water. Owing to the hybrid composition, MOF particles can easily assemble at the CO2/water interface to create a rigid protective barrier around the dispersed droplet. The MOF-stabilized CO2 and water emulsion has exceptional stability compared to those emulsions stabilized by surfactants or other solids. Moreover, the CO2 and water emulsion stabilized by MOF is 'tunable' due to the designable features of MOFs and adjustable character of CO2. Such a novel kind of emulsion composed of CO2, water, and MOF provides a facile route for constructing MOF superstructures with many advantages. The macroporous networks and hollow capsules of different kinds of MOFs have been successfully derived from CO2 and water emulsions. [ABSTRACT FROM AUTHOR]

Adenosine triphosphate (ATP) and other nucleotides can be irreversibly bound to the metal-organic framework (MOF) MIL-101(Cr). Analysis of X-ray diffraction data suggests that the location of the adsorbed ATP molecule is in proximity of the Cr 3 clusters. Solid-state NMR and DFT calculations indicate that ATP is bound to MIL-101(Cr) through linkages of the terminal phosphate group with Cr(III) of the framework. In the presence of Cu(II) ions, the MOF-supported nucleotides can function as stable and reusable enantioselective heterogeneous catalysts for reactions like Diels-Alder and Michael addition. Compared to the corresponding homogeneous nucleotide-based artificial metalloenzymes (ArMs), the MOF-supported nucleotide-based ArMs exhibit significantly enhanced activity and selectivity in certain cases, demonstrating their potential as a new class of enantioselective heterogeneous catalysts. [Display omitted] • Irreversible adsorption of nucleotides to metal-organic frameworks (MOFs). • MOF-supported nucleotide-based ArMs as a new class of enantioselective catalysts. • Enhanced catalytic properties exhibited by MOF-supported nucleotide-based ArMs. [ABSTRACT FROM AUTHOR]