Effect of amino functional groups on the surface properties and Lewis's acid base parameters of UiO-66(NH2) by inverse gas chromatography.

Amino-functionalized metal organic frameworks (MOFs) have attracted much attention for various applications such as carbon dioxide capture, water remediation and catalysis. The focus of this study is to determine the surface and Lewis's acid-base properties of UiO-66(NH2) crystals by the inverse gas chromatography (IGC) technique at infinite dilution. The latter was applied to evaluate the dispersive component of the surface energy γsd(T) by using thermal model and several molecular models. The obtained results proved that γsd(T) decreases when the temperature increases. The best results were achieved by using the thermal model that takes into account the effect of the temperature on the surface areas of the organic molecules. We also observed a decrease of the Gibbs surface free energy of adsorption by increasing the temperature of the different organic solvents. The polar interactions of UiO-66(NH2) were obtained by using the methods of Saint-Flour Papirer, Donnet et al., Brendlé-Papirer and the different molecular models. The Lewis's acid base constants KA and KD were further calculated by determining the different variables of adsorption of the probes on the solid surface and the obtained values were 1.07 and 0.45 for KA and KD respectively, with an acid-base ratio (KA/KD) of 2.38. These values showed the high acidic surface of the solid substrate; whereas, the values of the entropic acid base parameters, ωA, ωD and ωA/ωD respectively equal to 1.0×10-3, 3.8×10-4 and 2.73, also highlighted the important acidity of UiO-66-(NH2) surface. These important findings suggest that the surface defects (missing linkers and/or clusters) in UiO-66(NH2) are the main determining factor of the acid-base properties of UiO-66 based structures.

Controlled Growth of Highly Defected Zirconium-Metal-Organic Frameworks via a Reaction-Diffusion System for Water Remediation.

The relentless growth of metal-organic framework (MOF) chemistry is paralleled by the persistent urge to control the MOFs physical and chemical properties. While this control is mostly achieved by solvothermal syntheses, room temperature procedures stand out as more convenient and sustainable pathways for the production of MOF materials. Herein, a novel approach to control the crystal size and defect numbers of a dihydroxy-functionalized zirconium-based metal-organic framework (UiO-66(OH)2) at room temperature is reported. Through a reaction-diffusion method in a 1D system, zirconium salt was diffused into an agar gel matrix containing the organic linker to form nanocrystals of UiO-66(OH)2 with tailored structural features that include crystal size distribution, surface area, and defect number. By variation of the synthesis parameters of the system, hierarchical MOF nanocrystals with an average size ranging from 30 nm up to 270 nm and surface areas between 201 and 500 m2 g-1 were obtained in a one-pot synthetic route. To stress the importance of crystal size, morphology, and structural defects on the adsorption properties of UiO-66(OH)2, the adsorption capacity of the MOF toward methylene blue dye was tested with the largest and most defected crystals achieving the best performance of 202 mg/g. The distinctive structural characteristics including the hierarchical micromesoporous frameworks, the nanosized particles, and the highly defective crystals obtained by our synthesis procedure are deemed challenging through the conventional synthesis methods. This work paves the way for engineering MOF crystals with tunable physical and chemical properties, using a green synthesis procedure, for their advantageous use in many desirable applications.

Electrospun Metal-Organic Framework-Fabric Nanocomposites as Efficient Bactericides.

In this work, we utilized electrospinning to develop advanced composite membranes of polyvinyl chloride (PVC) loaded with postmetalated metal-organic frameworks (MOFs), specifically UiO-66(COOH)2-Ag and ZIF-8-Ag. This innovative technique led to the creation of highly stable PVC/MOFs-Ag membrane composites, which were thoroughly characterized using various analytical techniques, including scanning electron microscopy, powder X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, porosity analysis, and water contact angle measurement. The results verified the successful integration of MOF crystals within the nanofibrous PVC membranes. The obtained composites exhibited larger fiber diameters for 5 and 10% MOF loadings and a smaller diameter for 20% loading. Additionally, they displayed greater average pore sizes than traditional PVC membranes across most MOF loading percentages. Furthermore, we examined the antibacterial properties of the fabricated membranes at different MOFs-Ag loadings. The findings revealed that the membranes demonstrated significant antibacterial activity up to 95% against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria as the MOFs-Ag loading increased, even when maintaining a constant silver concentration. This indicates a contact-based inhibition mechanism. The outcomes of this study have crucial implications for the development of novel, stable, and highly effective antibacterial materials, which could serve as superior alternatives for face masks and be integrated into materials requiring regular decontamination, as well as potential water filtration systems.

Selective Photocatalytic Dehydrogenation of Formic Acid by an In Situ-Restructured Copper-Postmetalated Metal-Organic Framework under Visible Light.

Formic acid is considered as one of the most promising liquid organic hydrogen carriers. Its catalytic dehydrogenation process generally suffers from low activity, low reaction selectivity, low stability of the catalysts, and/or the use of noble-metal-based catalysts. Herein we report a highly selective, efficient, and noble-metal-free photocatalyst for the dehydrogenation of formic acid. This catalyst, UiO-66(COOH)2-Cu, is built by postmetalation of a carboxylic-functionalized Zr-MOF with copper. The visible-light-driven photocatalytic dehydrogenation process through the release of hydrogen and carbon dioxide has been monitored in real-time via operando Fourier transform infrared spectroscopy, which revealed almost 100% selectivity with high stability (over 3 days) and a conversion yield exceeding 60% (around 5 mmol·gcat-1·h-1) under ambient conditions. These performance indicators make UiO-66(COOH)2-Cu among the top photocatalysts for formic acid dehydrogenation. Interestingly, the as-prepared UiO-66(COOH)2-Cu hetero-nanostructure was found to be moderately active under solar irradiation during an induction phase, whereupon it undergoes an in-situ restructuring process through intraframework cross-linking with the formation of the anhydride analogue structure UiO-66(COO)2-Cu and nanoclustering of highly active and stable copper sites, as evidenced by the operando studies coupled with steady-state isotopic transient kinetic experiments, transmission electron microscopy and X-ray photoelectron spectroscopy analyses, and Density Functional Theory calculations. Beyond revealing outstanding catalytic performance for UiO-66(COO)2-Cu, this work delivers an in-depth understanding of the photocatalytic reaction mechanism, which involves evolutive behavior of the postmetalated copper as well as the MOF framework over the reaction. These key findings pave the way toward the engineering of new and efficient catalysts for photocatalytic dehydrogenation of formic acid.

Surface thermodynamics and Lewis acid-base properties of metal-organic framework Crystals by Inverse gas chromatography at infinite dilution.

In this study, the surface thermodynamic properties and more particularly, the dispersive component γsd of the surface energy of crystals of a Zr-based MOF, UiO-66 (Zr6O4(OH)4(BDC)6; BDC = benzene 1,4-dicarboxylic acid), the specific interactions, and their acid-base constants were determined by using different molecular models and inverse gas chromatography methods. The determination of γsd of the UiO-66 surface was obtained by using several models such as Dorris-Gray and those based on the Fowkes relation by applying the various molecular models giving the surface areas of n-alkanes and polar organic molecules. Six models were used: Kiselev, spherical, geometric, Van der Waals, Redlich-Kwong, and cylindrical models. The obtained results were corrected by using our model taking into account the thermal effect on the surface areas of molecules. A linear equation was obtained between γsd and the temperature. The specific free energy, enthalpy and entropy of adsorption of polar molecules, as well as the acid and base constants of UiO-66 particles were determined with an excellent precision. It was also proved that the UiO-66 surface exhibited an amphoteric acid-base character with stronger acidity. The linear variations of the specific free energy of interaction as a function of the temperature allowed to obtain the specific surface enthalpy and entropy of adsorption, as well as the acid and base constants of UiO-66 by using ten different models and methods. The best results were obtained by using our model that gave the more precise values of the acid constant KA=0.57, the base constant KD=0.18 of the MOF particles and the ratio KA/KD = 3.14 clearly proving a strong acid character of the UiO-66 surface.

Metallated Isoindigo-Porphyrin Covalent Organic Framework Photocatalyst with a Narrow Band Gap for Efficient CO2 Conversion.

Photocatalytic CO2 reduction into formate (HCOO-) has been widely studied with semiconductor and molecule-based systems, but it is rarely investigated with covalent organic frameworks (COFs). Herein, we report a novel donor-acceptor COF named Co-PI-COF composed of isoindigo and metallated porphyrin subunits that exhibits high catalytic efficiency (∼50 µmol formate g-1 h-1) at low-power visible-light irradiation and in the absence of rare metal cocatalysts. Density functional theory calculations and experimental diffuse-reflectance measurements are used to explain the origin of catalytic efficiency and the particularly low band gap (0.56 eV) in this material. The mechanism of photocatalysis is also studied experimentally and is found to involve electron transfer from the sacrificial agent to the excited Co-PI-COF. The observed high-efficiency conversion could be ascribed to the enhanced CO2 adsorption on the coordinatively unsaturated cobalt centers, the narrow band gap, and the efficient transfer of the charge originating from the postsynthetic metallation. It is anticipated that this study will pave the way toward the design of new simple and efficient catalysts for photocatalytic CO2 reduction into useful products.

Tuning the structural properties of cadmium-aluminum layered double hydroxide for enhanced photocatalytic dye degradation.

The distinctive layered structure, chemical stability and tunability of layered double hydroxides (LDHs) have led to extensive investigations in various areas of photocatalysis, including photocatalytic water splitting, carbon dioxide photoreduction, and degradation of organic pollutants. Here, a series of visible light active cadmium-aluminum layered double hydroxides (CdAl LDHs) with various Cd2+ : Al3+ ratios is synthesized via the reaction-diffusion framework (RDF) leading thereby to a hierarchal spherical structure of the LDH. The aim of this study is to develop an optimal CdAl LDH photocatalyst that is activated by solar light irradiation and tested for methylene blue (MB) degradation. The structural and physicochemical properties of the synthesized materials are determined by several imaging and spectroscopic techniques. The photocatalytic study reveals a strong dependence of the photocatalytic activity of the CdAl LDH on the cationic ratio with an optimal performance at a ratio Cd2+ : Al3+ equal to 3 : 1. A mechanism is proposed whereby the activity is ascribed to the formation of intermediate reactive oxidative species (ROS) during the photodegradation reactions and scrutinised by invoking different ROS quenchers and corroborated by density functional theory (DFT) calculations.

Two-Dimensional Metal-Organic Framework Nanosheets as a Dual Ratiometric and Turn-off Luminescent Probe.

Current research on metal-organic framework (MOF) luminescent sensing probes focuses on the design of three-dimensional bulk-sized MOFs that in return limits their up-close interactions with targeted guest molecules. In this work, we report a two-dimensional (2D) copper-based metal-organic framework, namely, AUBM-6, synthesized via solvothermal method from isonicotinic acid linker and copper(II) ion. The resulting 2D-layered MOF crystals were highly fluorescent in their exfoliated form and, therefore, explored for detecting several solvents, where a ratiometric selectivity was shown toward acetone. Metal ion sensing was also performed, by which fluorescent detection was observed to have the highest turn-off quenching efficiency toward Pd2+.

Liesegang Banding for Controlled Size and Growth of Zeolitic-Imidazolate Frameworks.

Here, the formation of periodic precipitation (Liesegang bands) from hybrid (organic-inorganic) components is reported, namely ZIF-8, ZIF-67, and their mixed metal derivatives. The spacing and width laws that characterize the Liesegang system are determined and the resulting pattern is exploited to crystal engineer various sizes and doping of the ZIF material. Several key parameters that govern the crystallization process of ZIF-8 are investigated in each band and the growth of the particles in each band is found to follow an Ostwald ripening mechanism.

Metal-Organic Framework Photocatalyst Incorporating Bis(4'-(4-carboxyphenyl)-terpyridine)ruthenium(II) for Visible-Light-Driven Carbon Dioxide Reduction.

In this study, we report the successful incorporation of the photoactive bis(4'-(4-carboxyphenyl)-terpyridine)ruthenium(II) (Ru(cptpy)2) strut into a robust metal-organic framework (MOF), AUBM-4. The single crystal X-ray analysis revealed the formation of a new one-dimensional structure of Ru(cptpy)2 complexes linked together by Zr atoms that are eight coordinated with O atoms. The chemically stable MOF structure was employed as an efficient photocatalyst for carbon dioxide conversion to formate under visible light irradiation. To the best of our knowledge, the obtained conversion rate is among the highest reported in the literature for similar systems. Our strategy of using the Ru(cptpy)2 complex as a linker to construct the MOF catalyst appears to be very promising in artificial photosynthesis.

Enhancing porphyrin photostability when locked in metal-organic frameworks.

Porphyrins have been widely used in many optical devices given their unique photochemical properties. Their poor photostability has, however, limited their wide applications in bioimaging and biosensing schemes. Herein, we report the remarkable photostability enhancement of the porphyrin, carboxyphenyl porphyrin (TCPP-H2) when locked in a zirconium based metal-organic framework (MOF-525). Steady-state ensemble fluorescence spectroscopy experiments showed minimal changes (2%) in the recorded signal when MOF-525 was continuously illuminated as compared to a 16% decrease for free porphyrins. Single particle fluorescence imaging revealed bright microparticles with exceptional photostability and no-blinking within the experiment window. This study highlights the use of metal-organic frameworks for preparing photostable microstructures by leveraging on their unique self-assembly properties.

Crystal Growth of ZIF-8, ZIF-67, and Their Mixed-Metal Derivatives.

A facile method to produce zeolitic imidazolate frameworks (ZIF-8, ZIF-67, and solid-solution ZIFs (mixed Co and Zn)) is reported. ZIF crystals are produced via a reaction-diffusion framework (RDF) by diffusing an outer solution at a relatively high concentration of the 2-methyl imidazole linker (HmIm) into an agar gel matrix containing the metal ions (zinc(II) and/or cobalt(II)) at room temperature. Accordingly, a propagating supersaturation wave, initiated at the interface between the outer solution and the gel matrix, leads to a precipitation front with a gradient of crystal sizes ranging between 100 nm and 55 µm along the reaction tube. While the precipitation fronts of ZIF-8 and ZIF-67 travel the same distance for the same initial conditions, ZIF-8 crystals therein are consistently smaller than the ZIF-67 crystals due to the disparity of their rate of nucleation and growth. The effects of the temperature, the concentration of the reagents, and the thickness of the gel matrix on the growth of the ZIF crystals are investigated. We also show that by using RDF we can envisage the formation mechanism of the ZIF crystals, which consists of the aggregation of ZIF nanospheres to form the ZIF-8 dodecahedrons. Moreover, using RDF, the formation of a solid-solution ZIF via the incorporation of Co(II) and Zn(II) cations within the same framework is achieved in a controlled manner. Finally, we demonstrate that doping ZIF-8 by Co(II) enhances the photodegradation of methylene blue dye under visible light irradiation in the absence of hydrogen peroxide.

A highly stable indium based metal organic framework for efficient arsenic removal from water.

A new porous indium metal organic framework namely (AUBM-1) was successfully synthesized via a solvothermal reaction of pyromellitic acid and indium chloride. Single crystal X-ray analysis revealed the formation of a 3D framework with a pts topology. The resulting MOF structure showed high chemical stability at different pH values. Thus, the activated indium MOF was applied for As removal from water for the first time and showed a high arsenate uptake capacity of 103.1 mg g-1 at neutral pH, which is higher than the commercial adsorbents (usually less than 100 mg g-1 at neutral pH). Finally, the kinetics and thermodynamic studies revealed that the As adsorption was an endothermic process and followed a pseudo-second-order kinetic model.

Postmetalated Zirconium Metal Organic Frameworks as a Highly Potent Bactericide.

Metal-organic frameworks (MOFs) have emerged as an important class of hybrid organic-inorganic materials. One of the reasons they have gained remarkable attention is attributed to the possibility of altering them by postsynthetic modification, thereby providing access to new and novel advanced materials. MOFs have been applied in catalysis, gas storage, gas separation, chemical sensing, and drug delivery. However, their bactericidal use has rarely been explored. Herein, we developed a two-step process for the synthesis of zirconium-based MOFs metalated with silver cations as a potent antibacterial agent. The obtained products were thoroughly characterized by powder X-ray diffraction, scanning electron microscopy, UV-visible, IR, thermogravimetric, and Brunauer-Emmett-Teller analyses. Their potency was evaluated against E. coli with a reported minimal inhibitory concentration and minimal bactericidal concentration of as low as 6.5 µg/mL of silver content. Besides the novelty of the system, the advantage of this strategy is that the MOFs could be potentially regenerated and remetalated after each antibacterial test, unlike previously reported frameworks, which involved the destruction of the framework.

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5.

The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat-1 h-1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2 to valuable chemicals and fuels.

Encapsulation of curcumin in cyclodextrin-metal organic frameworks: Dissociation of loaded CD-MOFs enhances stability of curcumin.

Curcumin has been successfully encapsulated in cyclodextrin-metal organic frameworks (CD-MOFs) without altering their crystallinity. The interaction between curcumin and CD-MOFs is strong through hydrogen bond type interaction between the OH group of cyclodextrin of CD-MOFs and the phenolic hydroxyl group of the curcumin. Interestingly, dissolving the curcumin loaded CD-MOFs crystals in water results in formation of a unique complex between curcumin, γCD and potassium cations. In fact, the initial interaction between curcumin and CD-MOF is crucial for the formation of the latter. This new complex formed in alkaline media at pH 11.5 has maximum absorbance at 520nm and emittance at 600nm. Most importantly, the stability of curcumin in this complex was enhanced by at least 3 orders of magnitude compared to free curcumin and curcumin:γ-CD at pH 11.5. These results suggest a promising benign system of CD-MOFs, which can be used to store and stabilize curcumin for food applications.

Cadmium-Aluminum Layered Double Hydroxide Microspheres for Photocatalytic CO2 Reduction.

We report the synthesis of cadmium-aluminum layered double hydroxide (CdAl LDH) using the reaction-diffusion framework. As the hydroxide anions diffuse into an agar gel matrix containing the mixture of aluminum and cadmium salts at a given ratio, they react to give the LDH. The LDH self-assembles inside the pores of the gel matrix into a unique spherical-porous shaped microstructure. The internal and external morphologies of the particles are studied by electron microscopy and tomography revealing interconnected channels and a high surface area. This material is shown to exhibit a promising performance in the photoreduction of carbon dioxide using solar light. Moreover, the palladium-decorated version shows a significant improvement in its reduction potential at room temperature.

New hydrogen-evolution heteronanostructured photocatalysts: Pt-Nb3 O7 (OH) and Cu-Nb3 O7 (OH).

Nanorods of triniobium hydroxide heptaoxide, Nb3 O7 (OH), were synthesized by means of a hydrothermal method. Subsequently, Pt and CuO nanoparticles were introduced on the surface of Nb3 O7 (OH) nanorods by a microwave-assisted solvothermal nucleation and growth technique. The resulting Pt- and CuO-decorated Nb3 O7 (OH) nanorods demonstrated uniform particle dispersion and were fully characterized by X-ray diffraction, electron microscopy, and spectroscopic analysis. Furthermore, the solar-powered photocatalytic hydrogen production properties of these heteronanostructures were studied. The solar-driven H2 formation rate over Pt-Nb3 O7 (OH) was determined to be 710.4 ± 1.7 µmol g(-1) h(-1) with a quantum efficiency of ϕ=5.40% at λ=380 nm. Interestingly, the as-prepared CuO-Nb3 O7 (OH) heteronanostructure was found to be inactive under solar irradiation during an induction phase, whereupon it undergoes an in situ photoreduction process to form the photocatalytically active Cu-Nb3 O7 (OH). This restructuring process was monitored by an in situ measurement of the time-evolution of the optical absorption spectra. The solar-powered H2 production for the restructured compound was determined to be 290.3 ± 5.1 µmol g(-1) h(-1) .

Large-pore apertures in a series of metal-organic frameworks.

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.