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A luminescent Zr(IV)-based metal-organic framework (MOF), with the underlying fcu topology, encompassing a π-conjugated organic ligand with a thiadiazole functionality, exhibits an unprecedented low detection limit of 66 nM for amines in aqueous solution. Markedly, this ultralow detection is driven by hydrogen-bonding interactions between the linker and the hosted amines. This observation is supported by density functional theory (DFT) calculations, which clearly corroborate the suppression of the twisting motion of thiadiazole core in the presence of amine, reducing significantly the nonradiative recombination pathways and subsequently enhancing the emission intensity. Credibly, nicotine regarded as a harmful chemical and bearing an amine pending group is also detected with high sensitivity, positioning this MOF as a potential sensor for practical environmental applications. This finding serves also as a benchmark to understand the sensing mechanism in MOFs.

Membrane-based gas separations are energy efficient processes; however, major challenges remain to develop high-performance membranes enabling the replacement of conventional separation processes. Herein, a new fluorinated MOF-based mixed-matrix membrane is reported, which is formed by incorporating the MOF crystals into selected polymers via a facile mixed-matrix approach. By finely controlling the molecular transport in the channels through the MOF apertures tuned by metal pillars and at the MOF-polymer interfaces, the resulting fluorinated MOF-based membranes exhibit excellent molecular sieving properties. These materials significantly outperform state-of-the-art membranes for simultaneous removal of H 2 S and CO 2 from natural gas-a challenging and economically important application. The robust fluorinated MOFs (NbOFFIVE-1-Ni, AlFFIVE-1-Ni), pave a way to efficient membrane separation processes that require precise discrimination of closely sized molecules., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The electrochemical carbon dioxide reduction reaction (CO 2 RR) produces diverse chemical species. Cu clusters with a judiciously controlled surface coordination number (CN) provide active sites that simultaneously optimize selectivity, activity, and efficiency for CO 2 RR. Here we report a strategy involving metal-organic framework (MOF)-regulated Cu cluster formation that shifts CO 2 electroreduction toward multiple-carbon product generation. Specifically, we promoted undercoordinated sites during the formation of Cu clusters by controlling the structure of the Cu dimer, the precursor for Cu clusters. We distorted the symmetric paddle-wheel Cu dimer secondary building block of HKUST-1 to an asymmetric motif by separating adjacent benzene tricarboxylate moieties using thermal treatment. By varying materials processing conditions, we modulated the asymmetric local atomic structure, oxidation state and bonding strain of Cu dimers. Using electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) experiments, we observed the formation of Cu clusters with low CN from distorted Cu dimers in HKUST-1 during CO 2 electroreduction. These exhibited 45% C 2 H 4 faradaic efficiency (FE), a record for MOF-derived Cu cluster catalysts. A structure-activity relationship was established wherein the tuning of the Cu-Cu CN in Cu clusters determines the CO 2 RR selectivity.

Membrane-based separations offer great potential for more sustainable and economical natural gas upgrading. Systematic studies of CO 2 /CH 4 separation over a wide range of temperatures from 65 °C (338 K) to as low as -40 °C (233 K) reveals a favorable separation mechanism toward CO 2 by incorporating Y- fum - fcu -MOF as a filler in a 6FDA-DAM polyimide membrane. Notably, the decrease of the temperature from 308 K down to 233 K affords an extremely high CO 2 /CH 4 selectivity (≈130) for the hybrid Y- fum - fcu -MOF/6FDA-DAM membrane, about four-fold enhancement, with an associated CO 2 permeability above 1000 barrers. At subambient temperatures, the pronounced CO 2 /CH 4 diffusion selectivity dominates the high permeation selectivity, and the enhanced CO 2 solubility promotes high CO 2 permeability. The differences in adsorption enthalpy and activation enthalpy for diffusion between CO 2 and CH 4 produce the observed favorable CO 2 permeation versus CH 4 . Insights into opportunities for using mixed-matrix membrane-based natural gas separations at extreme conditions are provided.

Membrane-based separations can improve energy efficiency and reduce the environmental impacts associated with traditional approaches. Nevertheless, many challenges must be overcome to design membranes that can replace conventional gas separation processes. Here, we report on the incorporation of engineered submicrometre-sized metal-organic framework (MOF) crystals into polymers to form hybrid materials that successfully translate the excellent molecular sieving properties of face-centred cubic (fcu)-MOFs into the resultant membranes. We demonstrate, simultaneously, exceptionally enhanced separation performance in hybrid membranes for two challenging and economically important applications: the removal of CO 2 and H 2 S from natural gas and the separation of butane isomers. Notably, the membrane molecular sieving properties demonstrate that the deliberately regulated and contracted MOF pore-aperture size can discriminate between molecular pairs. The improved performance results from precise control of the linkers delimiting the triangular window, which is the sole entrance to the fcu-MOF pore. This rational-design hybrid approach provides a general toolbox for enhancing the transport properties of advanced membranes bearing molecular sieve fillers with sub-nanometre-sized pore-apertures.

Herein we report the fabrication of an advanced sensor for the detection of hydrogen sulfide (H 2 S) at room temperature, using thin films of rare-earth metal (RE)-based metal-organic framework (MOF) with underlying fcu topology. This unique MOF-based sensor is made via the in situ growth of fumarate-based fcu-MOF (fum-fcu-MOF) thin film on a capacitive interdigitated electrode. The sensor showed a remarkable detection sensitivity for H 2 S at concentrations down to 100 ppb, with the lower detection limit around 5 ppb. The fum-fcu-MOF sensor exhibits a highly desirable detection selectivity towards H 2 S vs. CH 4 , NO 2 , H 2 , and C 7 H 8 as well as an outstanding H 2 S sensing stability as compared to other reported MOFs., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye.

The progressive liquid-phase layer-by-layer (LbL) growth of anisotropic multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P)(0.5)] (M: Cu(2+), Zn(2+); L: dicarboxylate linker; P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers (SAMs) on gold substrates as templates. It was found that the deposition of smooth, highly crystalline, and oriented multilayer films of these PCPs depends on the conditions at the early growth cycles. In the case of a two-step process with an equimolar mixture of L and P, growth along the [001] direction is strongly preferred. However, employing a three-step scheme with full separation of all components allows deposition along the [100] direction on carboxyl-terminated SAMs. Interestingly, the growth of additional layers on top of previously grown oriented seeding layers proved to be insensitive to the particular growth scheme and full retention of the initial orientation, either along the [001] or [100] direction, was observed. This homo- and heteroepitaxial LbL growth allows full control over the orientation and the layer sequence, including introduction of functionalized linkers and pillars., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

One step at a time: The in situ monitoring of the step-by-step formation of metal-organic frameworks (MOFs) by using surface plasmon resonance (SPR), allows the nucleation process and the formation of the secondary building units to be investigated. Growth rates on functionalized organic surfaces with different crystallographic orientations can also be studied.