Rhodium-Based Metal-Organic Polyhedra Assemblies for Selective CO2 Photoreduction.

Heterogenization of molecular catalysts via their immobilization within extended structures often results in a lowering of their catalytic properties due to a change in their coordination sphere. Metal-organic polyhedra (MOP) are an emerging class of well-defined hybrid compounds with a high number of accessible metal sites organized around an inner cavity, making them appealing candidates for catalytic applications. Here, we demonstrate a design strategy that enhances the catalytic properties of dirhodium paddlewheels heterogenized within MOP (Rh-MOP) and their three-dimensional assembled supramolecular structures, which proved to be very efficient catalysts for the selective photochemical reduction of carbon dioxide to formic acid. Surprisingly, the catalytic activity per Rh atom is higher in the supramolecular structures than in its molecular sub-unit Rh-MOP or in the Rh-metal-organic framework (Rh-MOF) and yields turnover frequencies of up to 60 h-1 and production rates of approx. 76 mmole formic acid per gram of the catalyst per hour, unprecedented in heterogeneous photocatalysis. The enhanced catalytic activity is investigated by X-ray photoelectron spectroscopy and electrochemical characterization, showing that self-assembly into supramolecular polymers increases the electron density on the active site, making the overall reaction thermodynamically more favorable. The catalyst can be recycled without loss of activity and with no change of its molecular structure as shown by pair distribution function analysis. These results demonstrate the high potential of MOP as catalysts for the photoreduction of CO2 and open a new perspective for the electronic design of discrete molecular architectures with accessible metal sites for the production of solar fuels.

Adsorber heat exchanger using Al-fumarate beads for heat-pump applications - a transport study.

Metal-Organic Frameworks (MOFs), thanks to their type V water adsorption isotherms ("S-Shape") and large water capacities, are considered as potential breakthrough adsorbents for heat-pump applications. In particular, Al(OH)-fumarate could enable efficient regeneration at a lower temperature than silica-gel which would allow us to address the conversion of waste heat at low temperature such as found in data centers. Despite its greater adsorption capacity features, heat and mass transport limitations could jeopardize the potential performance of Al(OH)-fumarate. Heat and mass transport depend on the size of the bodies (mm range), their packing and on the pore structures, i.e. macro-mesopore volumes and sizes. This paper describes the cost-efficient and scalable synthesis and shaping processes of Al(OH)-fumarate beads of various sizes appropriate for use in water Adsorption Heat-Pumps (AHPs). The objective was to study transport limitations (i.e. mass and heat) in practical e beads which meet mechanical stability requirements. Dynamic data at the grain scale was obtained by the Large Temperature Jump method while dynamic data at the adsorber scale was obtained on a heat exchanger filled with more than 1 kg of Al(OH)-fumarate beads. Whereas the binder content had little impact on mass and heat transfer in this study, we found that Knudsen diffusion in mesopores of the grain may be the main limiting factor at the grain scale. At the adsorber scale, heat-transfer within the bed packing as well as to the heat exchanger is likely responsible for the slow adsorption and desorption kinetics which have been observed for very low desorption temperature. Finally, the dynamic aspects of the observed water adsorption isotherm shift with temperature are discussed in light of reported reversible structure modification upon temperature triggered water adsorption-desorption.

Molecular Porous Photosystems Tailored for Long-Term Photocatalytic CO2 Reduction.

The molecular-level structuration of two full photosystems into conjugated porous organic polymers is reported. The strategy of heterogenization gives rise to photosystems which are still fully active after 4 days of continuous illumination. Those materials catalyze the carbon dioxide photoreduction driven by visible light to produce up to three grams of formate per gram of catalyst. The covalent tethering of the two active sites into a single framework is shown to play a key role in the visible light activation of the catalyst. The unprecedented long-term efficiency arises from an optimal photoinduced electron transfer from the light harvesting moiety to the catalytic site as anticipated by quantum mechanical calculations and evidenced by in situ ultrafast time-resolved spectroscopy.

Hydrogenation Size-Selective Pt/Hollow Beta Catalysts.

The aim of the present work is to synthesize a zeolite-based catalyst with a hollow morphology and highly dispersed metal nanoparticles (NPs) encapsulated inside the zeolite micropores. For this purpose, we have studied a treatment using tetraalkylammonium (TAA) bromides for the selective removal of a large Pt particle from the outer surface of a hollow Beta zeolite. TEM analysis reveals that we succeeded in the synthesis of a hollow beta zeolite single crystal with encapsulated particles, with a high dispersion of 50-60 %. The molecular-sieve-type mechanism of the obtained catalysts was evaluated in the model reaction of toluene and mesitylene catalytic hydrogenation. Thanks to the high dispersion. a 10-fold activity enhancement has been obtained with respect to hollow beta zeolites with encapsulated NPs recently described in the literature.

Sensitive Photoacoustic IR Spectroscopy for the Characterization of Amino/Azido Mixed-Linker Metal-Organic Frameworks.

Photoacoustic Fourier-transform infrared spectroscopy makes it possible to determine the organic composition of mixed-linker metal-organic frameworks. The sound produced upon IR irradiation enables the discrimination of azido and amino linkers in three different MOF platforms with a sensitivity that is two orders of magnitude higher than that achieved using classic IR analysis.

Molecular Level Characterization of the Structure and Interactions in Peptide-Functionalized Metal-Organic Frameworks.

We use density functional theory, newly parameterized molecular dynamics simulations, and last generation 15 N dynamic nuclear polarization surface enhanced solid-state NMR spectroscopy (DNP SENS) to understand graft-host interactions and effects imposed by the metal-organic framework (MOF) host on peptide conformations in a peptide-functionalized MOF. Focusing on two grafts typified by MIL-68-proline (-Pro) and MIL-68-glycine-proline (-Gly-Pro), we identified the most likely peptide conformations adopted in the functionalized hybrid frameworks. We found that hydrogen bond interactions between the graft and the surface hydroxyl groups of the MOF are essential in determining the peptides conformation(s). DNP SENS methodology shows unprecedented signal enhancements when applied to these peptide-functionalized MOFs. The calculated chemical shifts of selected MIL-68-NH-Pro and MIL-68-NH-Gly-Pro conformations are in a good agreement with the experimentally obtained 15 N NMR signals. The study shows that the conformations of peptides when grafted in a MOF host are unlikely to be freely distributed, and conformational selection is directed by strong host-guest interactions.

Breakthrough in Xenon Capture and Purification Using Adsorbent-Supported Silver Nanoparticles.

Rare gas capture and purification is a major challenge for energy, environment, and health applications. Of utmost importance for the nuclear industry, novel separation processes for Xe are urgently needed for spent nuclear fuel reprocessing and nuclear activity monitoring. The recovered, non-radioactive Xe is also of high economic value for lighting, surgical anesthetic, etc. Here, using adsorption and breakthrough experiments and statistical mechanics molecular simulation, we show the outstanding performance of zeolite-supported silver nanoparticles to capture/separate Xe at low concentrations (0.087-100 ppm). We also establish the efficiency of temperature swing adsorption based on such adsorbents for Xe separation from Kr/Xe mixtures and air streams corresponding to off-gases generated by nuclear reprocessing. This study paves the way for the development of novel, cost-efficient technologies relying on the large selectivity/capacity of adsorbent-supported silver nanoparticles which surpass all materials ever tested.

A Pt/Al2O3-supported metal-organic framework film as the size-selective core-shell hydrogenation catalyst.

The substituted imidazolate-based MOF (SIM-1) easily forms a homogeneous layer at the surface of millimetric platinum-loaded alumina beads. This new core-shell SIM-1@Pt/Al2O3 catalyst shows the fine molecular sieving effect for the Pt-catalyzed hydrogenation of carbon-carbon double bonds.

Enantiopure Peptide-Functionalized Metal-Organic Frameworks.

We present herein the first example of metal-organic frameworks postfunctionalized with peptides. Our microwave-assisted postsynthetic modification method yields enantiopure peptides anchored inside MOF cavities. Al-MIL-101-NH2, In-MIL-68-NH2, and Zr-UiO-66-NH2 were chosen as starting platforms. A single amino acid and various oligopeptides are grafted with yields up to 60% after a 30 min microwave-assisted coupling-deprotection sequence. This allows efficient preparation of a library of functional hybrid solids for molecular recognition applications such as sensing, separation, or asymmetric catalysis, as demonstrated here for the chiral aldol reaction.

Superstructure of a substituted zeolitic imidazolate metal-organic framework determined by combining proton solid-state NMR spectroscopy and DFT calculations.

We report the supercell crystal structure of a ZIF-8 analog substituted imidazolate metal-organic framework (SIM-1) obtained by combining solid-state nuclear magnetic resonance and powder X-ray diffraction experiments with density functional theory calculations.

Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.

The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2 -storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ∼10 % molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2 . There is no precedent for a MOF catalyzing the latter reaction so far.

Antimicrobial activity of cobalt imidazolate metal-organic frameworks.

Two cobalt imidazolate metal-organic frameworks were evaluated as a bactericidal material against the growth of the Gram-negative bacteria Pseudomonas putida and Escherichia coli. Under the most unfavourable conditions, within the exponential growth phase and in the culture media for both microorganisms, the growth inhibition reached over 50% for concentrations of biocidal material in the 5-10mgL(-1) range. The release of metal gives excellent durability with the antibacterial effect persisting after 3months. Both cobalt-based materials can be prepared with simple, cheap and easily accessible commercial ligands, leading to a more affordable possible future application as antimicrobial materials.

Water adsorption in MOFs: fundamentals and applications.

This review article presents the fundamental and practical aspects of water adsorption in Metal-Organic Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aqueous media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.

Assessing chemical heterogeneity at the nanoscale in mixed-ligand metal-organic frameworks with the PTIR technique.

Recently, the use of mixtures of organic-building-block linkers has given chemists an additional degree of freedom for engineering metal-organic frameworks (MOFs) with specific properties; however, the poor characterization of the chemical complexity of such MixMOF structures by conventional techniques hinders the verification of rational design. Herein, we describe the application of a technique known as photothermal induced resonance to individual MixMOF microcrystals to elucidate their chemical composition with nanoscale resolution. Results show that MixMOFs isoreticular to In-MIL-68, obtained either directly from solution or by postsynthetic linker exchange, are homogeneous down to approximately 100 nm. Additionally, we report a novel in situ process that enables the engineering of anisotropic domains in MOF crystals with submicron linker-concentration gradients.

Size-selective hydrogenation at the subnanometer scale over platinum nanoparticles encapsulated in silicalite-1 single crystal hollow shells.

Highly controlled "ship-in-a-bottle" platinum nanoparticles in silicalite-1 hollow single crystals have been prepared. This catalyst is highly active for toluene hydrogenation but shows no activity for the hydrogenation of 1,3,5-trimethylbenzene.

Ultimate size control of encapsulated gold nanoparticles.

We report an original and scalable synthesis pathway to produce encapsulated gold nanoparticles. Precise control of the gold particles is achieved in the range of 1-10 nm through the impregnation of silicalite-1 with a controlled concentration of gold solution, followed by dissolution-recrystallization of the zeolite.

An alternative pathway for the synthesis of isocyanato- and urea-functionalised metal-organic frameworks.

We have developed a generic two-step post-functionalisation technique for transforming amino-functionalised MOFs into their isocyanate analogues. The first part of the synthetic pathway consists in the conversion of the amino moieties into azido groups. Next, the thermal activation of these azido groups leads to nitrene species that can react with carbon monoxide to yield the desired products. As a proof of concept, this method was applied to the highly stable Al-MIL-53-NH2 and to the acid-sensitive In-MIL-68-NH2. The resulting nitrene species were highly reactive, with side reactions dominating initially. This issue was overcome through the use of a mixed-linker strategy applied during the MOF synthesis that decreased the nitrene radical density within the pore, thereby permitting In-MIL-68-NH2 to be converted into its isocyanate analogue with 100% selectivity. To illustrate the potential of this method for grafting a wide library of potentially active organic groups inside MOFs, amines were condensed onto isocyanato MOFs to form urea analogues.

MOF-supported selective ethylene dimerization single-site catalysts through one-pot postsynthetic modification.

The one-pot postfunctionalization allows anchoring a molecular nickel complex into a mesoporous metal-organic framework (Ni@(Fe)MIL-101). It is generating a very active and reusable catalyst for the liquid-phase ethylene dimerization to selectively form 1-butene. Higher selectivity for 1-butene is found using the Ni@(Fe)MIL-101 catalyst than reported for molecular nickel diimino complexes.