Site-Memory-Triggered Reversible Acronym Encryption in a Nitrogen-Rich Pore-Partitioned MOF for Ultrasensitive Monitoring of Roxarsone and Dichloran over Multiple Platform.

Stimuli-responsive emission color modulation in fluorescent metal-organic frameworks (MOFs) promises luminescence-ink-based security application, while task-specific functionality-engineered pores can aid fast-responsive, discriminative, and ultralow detection of harmful organo-aromatics in the aqueous phase. Considering practical applicability, a self-calibrated fluoro-switch between encrypted and decrypted states is best suited for antiforgery measures, whereas image-based monitoring of organo-toxins by repetitive and handy methods over multiple platforms endorses in-field sensory potential. Herein, we constructed a mixed-ligand based chemically stable and bilayered-pillar MOF from -NH2-hooked pyridyl linker and tricarboxylate ligand that embraces negatively charged [Cd3(µ2-OH)(COO)6] node and shows pore-space-partitioning by nitrogen-rich flanked organic struts. Owing to the presence of a self-calibrating triazolylamine moiety-grafted auxiliary linker, this anionic MOF delineates reversible and multicyclic fluoro-swapping between protonated-encrypted and deprotonated-decrypted domains in the alternative presence of acid and base. Such pH-triggered, site-specific luminescence variation is utilized to construct highly regenerative anticounterfeiting labels for vivid acronym encryption. The intense fluorescence signature of the material is further harnessed in extremely selective and quick responsive sensing of harmful feed additive roxarsone (ROX) and dichloran (DCNA) pesticide in highly recyclable fashion with significant quenching and nanomolar limits of detection (ROX: 52 ppb; DCNA: 26.8 ppb). Notably, the ultrasensitive fluoro-detection of both these organo-toxins is successfully demonstrated via a handy paper-strip method as well as on the vegetable surface for real-time monitoring. Comprehensive density functional theory studies validate the electron transfer mechanism through redistribution of molecular orbital energy levels by each of the targeted analytes in this electron-rich framework besides evidencing MOF-analyte supramolecular interactions.

Prediction of the capture and utilization of atmospheric acidic gases by azo-based square-pillared fluorinated MOFs.

More than the permissible limit of acidic gases like CO2, SO2, and NO2 in the atmosphere are responsible for the formation of acid rain, the greenhouse effect and many other undesirable environmental hazards. So, the capture and utilization of these gases are essential for mankind. Herein, we proposed an azo-based square pillared MOF, [Ni(MF5)(1,2-bis(4-pyridy)diazene)2]n, with the CUS metal site, i.e. M = Al/Fe, for the selective capture and conversion of acidic gas molecules into commodity chemicals such as cyclic carbonate, sulphite and nitrite. With the aid of Density Functional Theory (DFT), [Ni(MF5)(1,2-bis(4-pyridy)diazene)2]n has been optimized, and the specific force field is derived via guest-host interaction. The Grand Canonical Monte Carlo (GCMC) simulation has been used to explore the guest-host interactions over a wide range of pressures, and their respective stability under pre-humidification is evaluated. The adsorption prediction reveals that MFFIVE-Ni-apy have a higher adsorptive capacity (37.1 mmol g-1), and especially ALFFIVE-Ni-apy possesses a higher affinity towards guest molecules (CO2, SO2) rather than FEFFIVE-Ni-apy. Additionally, the adsorption of gases in the presence of humidity reveals that ALFFIVE-Ni-apy has an optimal adsorption capacity for all investigated acidic gases even at 38.5 RH%. The absorbed acidic gases on MFFIVE-Ni-apy were used for the theoretical investigations on cycloaddition with the aid of DFT as an application perspective of the toxic gases instead of expelling into atmosphere. The Climbing Image Nudged Elastic Band (CI-NEB) approach was used to discover the transition state in this scenario, in which the cycloaddition of adsorbed CO2, SO2, and NO2 gases with epoxides leads to the formation of cyclic carbonates, sulphites, and nitrates, respectively.

Coordination Unsaturation and Basic Site-Immobilized Nanochannel in a Chemorobust MOF for 3-Fold-Increased High-Temperature Selectivity and Fixation of CO2 under Mild Conditions with Nanomolar Recognition of Roxarsone.

A multifaceted metal-organic framework (MOF) with task-specific site-engineered pores can promise high-temperature and moisture-tolerant capture and non-redox fixation of CO2 under mild conditions as well as ultrasensitive detection of carcinogenic contaminants in water. Herein, we report a pillar-bilayered MOF that holds a nanochannel with contrasting functionalities for both these sustainable applications with improved performance characteristics. The twofold entangled robust framework exhibits CO2 adsorption at elevated temperatures with considerable MOF-gas interaction. Interestingly, CO2 selectivity unveils nearly a 3-fold improvement upon the rise of temperature, affording a CO2/N2 value of 820 at 313 K, which outperforms many porous adsorbents. Additionally, breakthrough simulation establishes complete separation and attests the potential of this MOF in the separation of flue gas mixture. Importantly, minor CO2 loss during multiple capture-release cycles and under a relative humidity of 75% promise practical usability of the material. Density functional theory (DFT) not only portrays the atomistic level snapshots of temperature-triggered CO2 inclusion inside this microporous vessel alongside the role of diverse CO2-philic sites but also validates the basis of N2-phobicity of an azo-functionalized linker on such increased selectivity. The guest-free MOF further demonstrates non-redox and recyclable CO2 fixation with wide epoxide tolerance under solvent-free mild conditions and even works at atmospheric pressure and room temperature. The crucial roles of high-density acid-base sites in both adsorption and catalysis are supported by control experiments and by comparing the activity of an unfunctionalized MOF. The hydrolytic stability and strong luminescence signature benefit the framework in aqueous-phase selective and fast responsive detection of detrimental roxarsone (ROX) with high quenching (7.56 × 104 M-1) and very low sensitivity (68 nM). Apart from varying degrees of an energy-transfer mechanism, the fluorosensing of ROX is comprehensively supported by in-depth DFT studies that manifest alteration of MOF energy levels in the presence of organoarsenic compounds and depict MOF-analyte supramolecular interactions.

Investigation of Guest-Induced Flexibility in Pyrazine Derivative of ALFFIVE MOF via Molecular Simulation.

One of the important understandings of porous solids like metal-organic frameworks (MOFs) is their flexibility. Therefore, there are certain computational studies on flexible MOFs in the literature, primarily concentrating on MIL-53, UiO-66, and DUT-49. Here, investigation of another class of MOF, that is, [Ni(1,4-pyrazine)2(AlF5)]n, was shown to have guest-induced flexible characteristics; nevertheless, the mechanism for the emergence of flexibility is uncertain. We simulated the structural flexibility of [Ni(1,4-pyrazine)2(AlF5)]n, named ALFFIVE-Ni-pyr-TBP, upon adsorption of a guest molecule based on force fields using the molecular dynamics (MD) method and Monte Carlo (MC) simulations. As the first step towards understanding guest-induced flexibility, the MC simulations were performed by relaxing the framework and then further comparing it with the rigid framework. Subsequently, MD simulations were executed on the ALFFIVE-Ni-pyr-TBP framework with and without the guest molecules. In the case of moisture adsorption, the MOF system was identified to undergo a geometric transformation from trigonal bipyramidal to square bipyramidal geometry due to the strong interaction of oxygen of the water with the metal aluminum. However, some tilting in the pyrazine ligand was observed in the presence of all the guest molecules. Therefore, the detailed guest-induced flexibility described in this work could support the ALFFIVE series to be explored for future adsorption applications.

Highly Luminescent MOF and Its In Situ Fabricated Sustainable Corn Starch Gel Composite as a Fluoro-Switchable Reversible Sensor Triggered by Antibiotics and Oxo-Anions.

Frequent use of antibiotics and the growth of industry lead to the pollution of several natural resources which is one of the major consequences for fatality to human health. Exploration of smart sensing materials is highly anticipated for ultrasensitive detection of those hazardous organics. The robust porous hydrogen bonded network encompassing a free-NH2 moiety, Zn(II)-based metal-organic framework (MOF) (1), is used for the selective detection of antibiotics and toxic oxo-anions at the ppb level. The framework is able to detect the electronically dissimilar antibiotic sulfadiazine and nitrofurazone via fluorescence "turn-on" and "turn-off" processes, respectively. The antibiotic-triggered reversible fluoro-switching phenomena (fluorescence "on-off-on") are also observed by using the fluorimetric method. An extensive theoretical investigation was performed to establish the fluoro-switching response of 1, triggered by a class of antibiotics and also the sensing of oxo-anions. This investigation reveals that the interchange of the HOMO-LUMO energy levels of fluorophore and analytes is responsible for such a fluoro-switchable sensing activity. Sensor 1 showed the versatile detection ability which is reflected by the detection of a carcinogenic nitro-group-containing drug "roxarsone". In view of the sustainable environment along with quick-responsive merit of 1, an in situ MOF gel composite (1@CS; CS = corn starch) is prepared using 1 and CS due to its useful potential features such as biocompatibility, toxicologically innocuous, good flexibility, and low commercial price. The MOF composite exhibited visual detection of the above analytes as well as antibiotic-triggered reversible fluoro-switchable colorimetric "on-off-on" response. Therefore, 1@CS represents a promising smart sensing material for monitoring of the antibiotics and oxo-anions, particularly appropriate for the real-field analysis of carcinogenic drug molecule "roxarsone" in food specimens.

Tunable Capacitive Behavior in Metallopolymer-based Electrochromic Thin Film Supercapacitors.

Volumetric capacitance is a more critical performance parameter for rechargeable power supply in lightweight and microelectronic devices as compared to gravimetric capacitance in larger devices. To this end, we report three electrochromic metallopolymer-based electrode materials containing Fe2+ as the coordinating metal ion with high volumetric capacitance and energy densities in a symmetric two-electrode supercapacitor setup. These metallopolymers exhibited volumetric capacitance up to 866.2 F cm-3 at a constant current density of 0.25 A g-1. The volumetric capacitance (poly-Fe-L2: 544.6 F cm-3 > poly-Fe-L1: 313.8 F cm-3 > poly-Fe-L3: 230.8 F cm-3 at 1 A g-1) and energy densities (poly-Fe-L2: 75.5 mWh cm-3 > poly-Fe-L1: 43.6 mWh cm-3 > poly-Fe-L3: 31.2 mWh cm-3) followed the order of the electrical conductivity of the metallopolymers and are among the best values reported for metal-organic systems. The variation in the ligand structure was key toward achieving different electrical conductivities in these metallopolymers with excellent operational stability under continuous cycling. High volumetric capacitances and energy densities combined with tunable electro-optical properties and electrochromic behavior of these metallopolymers are expected to contribute to high performance and compact microenergy storage systems. We envision that the integration of smart functionalities with thin film supercapacitors would warrant the surge of miniaturized on-chip microsupercapacitors integrated in-plane with other microelectronic devices for wearable applications.

Nanoencapsulation of Ru(p-cymene) Complex Bearing Ginger-based Natural Product into Liposomal Nanoformulation to Improve Its Cellular Uptake and Antiproliferative Activity.

The organometallic compounds are prospective candidates in the row of developing metallochemotherapeutics with the aim of overcoming the limitations of platinum drugs. In order to explore the anticancer properties of organometallic compounds with the natural medicines, two Ru(II)-p-cymene complexes containing the natural products, viz., 6-gingerol (6G) and benzylated-6-gingerdione (B-6GD) have been synthesized and characterized well. The phenolic group of the Ru(6G) complex facilitates its higher cell-free antioxidant activity than its analogue complex. Also, the same complex shows higher cytotoxicity toward A549 lung and HeLa-S3 cervical cancer cells than the Ru(B-6GD) complex but lower cytotoxicity toward A2058 metastatic melanoma cancer cells. Both complexes are shown to easily accumulate in melanoma cancer cells, and their degree of cytotoxicity in the same cells is found to be positively correlated with cell uptake. The cytotoxicity of complexes arises from their intracellular activity, mainly due to the induction of singlet oxygen production in cancer cells. The subcellular fractionation study shows that mitochondria and ER-Golgi membranes might be their predominant targets. Also, the mechanistic investigation revealed that Ru(B-6GD) induces caspase-dependent non-apoptotic cell death whereas Ru(6G) can induce caspase-independent non-apoptotic cell death. Furthermore, both complexes are found to moderately alter the adhesion properties of cancer cells, which is beneficial for antimetastatic treatment. Despite the potential pharmacological activity, Ru(6G) is encapsulated into polymer-supported liposomes to reduce its toxicity and further improve its anticancer potency. The π-conjugated yne-ene chain of polydiacetylene aids in the development of a stable nanoformulation, which achieved a slow release of the complex. Most importantly, the cancer cell uptake of the liposome-encapsulated Ru(6G) complex is 20 times enhanced and the total ROS formation in cancer cells is significantly increased compared to the non-encapsulated complex. However, the nanoformulation does not alter the antimetastatic potency of the encapsulated complex.

Chemically Robust and Bifunctional Co(II)-Framework for Trace Detection of Assorted Organo-toxins and Highly Cooperative Deacetalization-Knoevenagel Condensation with Pore-Fitting-Induced Size-Selectivity.

Acute detection of assorted classes of organo-toxins in a practical environment is an important sustainable agenda, whereas cooperative and recyclable catalysis can mitigate hazards by minimizing energy requirements and reducing waste generation. We constructed an acid-/base-stable Co(II)-framework with a unique network topology, wherein unidirectional porous channels are decorated by anionic [Co2(µ2-OH)(COO)4(H2O)3] secondary building units and neutral [CoN2(COO)2] nodes. An intense luminescent signature of the hydrolytically robust framework is harnessed for the selective, fast-responsive, and regenerable detection of two detrimental organo-aromatics, 4-aminophenol (4-AP) and 2,4,6-trinitrophenol (TNP). Alongside remarkable quenching, their nanomolar detection limits (4-AP: 99.5 nM; TNP: 67.2 nM) rank among the lowest reported values in water and corroborate their ultra-sensitivity. Density functional theory (DFT) calculations verify the electron-transfer route of sensing through portraying redistribution of energy levels of molecular orbitals in a three-dimensional network by each analyte and further envisages non-covalent host-guest interactions. Benefiting from the concurrent existence of an open-metal site and a triphenylamine-moiety-functionalized ligand, the activated framework acts as an outstandingly cooperative heterogeneous catalyst in deacetalization-Knoevenagel condensation under mild conditions. The acid-base dual catalysis is detailed for the first time from combined inputs of control experiments and DFT validations. To the best of tandem reaction, larger-sized substrate exhibits insignificant conversion, and certifies rarest pore-fitting induced size-selectivity.

Fluorinated metal organic frameworks, MFFIVE-Ni-L (M = Fe/Al, L = pyr), with coordinatively unsaturated metal site for CO2 separation from flue gas in the presence of humidity by computational methods.

The anthropogenic emission of greenhouse gases, mainly CO2, is considered to be one of the most challenging environmental threats related to global climatic change. Herein, for the first time, we accurately interpreted the interaction of guest molecules such as H2O, CO2 and N2, the main constituent of flue gas, to a coordinatively unsaturated (CUS) square pillared fluorinated metal organic framework (MOF) using a grand canonical Monte Carlo (GCMC) simulation with the help of a specific forcefield. This specific forcefield is derived from the interaction energy profile of the guest molecules to the framework attained from the periodic-density functional theory (DFT) calculations. The DFT-derived forcefield effectively safeguarded the ability of the coordinatively unsaturated square pillared fluorinated MOF for CO2 separation in the presence of moisture.

Rational Design of a ZnII MOF with Multiple Functional Sites for Highly Efficient Fixation of CO2 under Mild Conditions: Combined Experimental and Theoretical Investigation.

The development of efficient heterogeneous catalysts suitable for carbon capture and utilization (CCU) under mild conditions is a promising step towards mitigating the growing concentration of CO2 in the atmosphere. Herein, we report the construction of a hydrogen-bonded 3D framework, {[Zn(hfipbba)(MA)]⋅3 DMF}n (hfipbba=4,4'-(hexaflouroisopropylene)bis(benzoic acid)) (HbMOF1) utilizing ZnII center, a partially fluorinated, long-chain dicarboxylate ligand (hfipbba), and an amine-rich melamine (MA) co-ligand. Interestingly, the framework possesses two types of 1D channels decorated with CO2 -philic (-NH2 and -CF3 ) groups that promote the highly selective CO2 adsorption by the framework, which was supported by computational simulations. Further, the synergistic involvement of both Lewis acidic and basic sites exposed in the confined 1D channels along with high thermal and chemical stability rendered HbMOF1 a good heterogeneous catalyst for the highly efficient fixation of CO2 in a reaction with terminal/internal epoxides at mild conditions (RT and 1 bar CO2 ). Moreover, in-depth theoretical studies were carried out using periodic DFT to obtain the relative energies for each stage involved in the catalytic reaction and an insight mechanistic details of the reaction is presented. Overall, this work represents a rare demonstration of rational design of a porous ZnII MOF incorporating multiple functional sites suitable for highly efficient fixation of CO2 with terminal/internal epoxides at mild conditions supported by comprehensive theoretical studies.

Supramolecular Surface Charge Regulation in Ionic Covalent Organic Nanosheets: Reversible Exfoliation and Controlled Bacterial Growth.

Poor control on the exfoliation of covalent organic frameworks (COFs) remains a disadvantage for their application as two-dimensional nanosheets. An equally important problem is the reversible control at the available surface charges on COFs. Herein, a strategy for the reversible exfoliation, re-stacking, and surface-charge control of a propidium iodide based ionic covalent organic framework, PI-TFP, using cucurbit[7]uril (CB[7]) induced molecular recognition, is reported. The surface charge on PI-TFP facilitates its initial self-exfoliation. However, complexation with CB[7] resulted in re-stacking with concomitant decrease in zeta potential from +28±3.0 to +0.004±0.003 mV. Addition of 1-adamantylamine hydrochloride (AD) facilitates decomplexation of PI-TFP from CB[7], resulting in exfoliation and an increase in zeta potential to +24±3.0 mV. Such control on the exfoliation, re-stacking, and the associated regulation of the surface charge in PI-TFP was exploited for controlling bacterial growth. Thus, the activity of E. coli and S. aureus bacteria obtained with the self-exfoliated PI-TFP could be reversibly controlled by the CB[7]/AD pair.

Water-Tolerant DUT-Series Metal-Organic Frameworks: A Theoretical-Experimental Study for the Chemical Fixation of CO2 and Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ-Valerolactone.

A series of highly thermally and hydrolytically stable porous solids with intriguing properties of zirconium- and hafnium-based metal-organic frameworks (MOFs) [Dresden University of Technology (DUT) series] was synthesized. The DUT MOFs were found to be effective catalysts for both epoxide-CO2 cycloaddition reactions and the catalytic transfer hydrogenation (CTH) of ethyl levulinate (EL). In particular, 12-connected DUT-52(Zr) showed higher catalytic activity than eight- and six-connected catalysts in the synthesis of cyclic carbonates as well as in the production of γ-valerolactone (GVL). The secondary building unit connectivity, coexistence of a moderate number of acidic and basic sites, Brunauer-Emmett-Teller surface area, and combined effects of the pores of the MOFs seem to influence the catalytic activity. The reaction mechanism for the DUT-52(Zr)-mediated cycloaddition reaction of CO2 and the CTH reactions were investigated in detail by using periodic density functional theory calculations. To the best of our knowledge, this is the first detailed computational study for the formation of GVL from EL by using MOF as the catalyst. In addition, grand canonical Monte Carlo simulations predicted the strong interaction of CO2 molecules with the DUT-52(Zr) framework. Remarkably, the DUT-series catalysts possess extraordinary tolerance toward water. Further, DUT-52(Zr) is recyclable and is an efficient catalyst for cycloaddition and CTH reactions for at least five uses without obvious reductions in the activity or structural integrity.

Cycloaddition of CO2 with an Epoxide-Bearing Oxindole Scaffold by a Metal-Organic Framework-Based Heterogeneous Catalyst under Ambient Conditions.

The synthesis and characterization of a mixed ligand metal-organic framework (MOF) with good thermal and chemical stability, {[Co(BDC)(L)·2H2O]·xG}n (CoMOF-2), involving an aromatic dicarboxylate (H2BDC = 1,4-benzenedicarboxylic acid) and an acyl-decorated N-donor linker [L = (E)-N'-(pyridin-4-ylmethylene) isonicotinohydrazide] by various physicochemical techniques, including Single crystal X-Ray Diffraction (SXRD), are reported. The MOF showed a good affinity for CO2 capture, and Grand Canonical Monte Carlo simulation studies exposed strong interactions of CO2 with the functionalized N-donor ligand of the framework. CoMOF-2 and KI act as an efficient binary catalyst for the sustainable utilization of CO2 with spiro-epoxy oxindole to spirocyclic carbonate under ambient conditions. Notably, herein we report MOF-based catalysis for the cycloaddition of oxindole-based epoxides with CO2 for harvesting new spirocyclic carbonates. Interestingly, we could isolate and crystallize six of the spirocyclic carbonate products, and the structure of the newly synthesized molecules has been established by SXRD analysis. We present a plausible proposed catalytic mechanism through activation of the epoxide ring by the Lewis acidic/basic sites present on the framework surface that is validated by molecular modeling.

Ionic-Liquid-Functionalized UiO-66 Framework: An Experimental and Theoretical Study on the Cycloaddition of CO2 and Epoxides.

A facile approach for modifying the UiO-66-NH2 metal-organic framework by incorporating imidazolium-based ionic liquids (ILs) to form bifunctional heterogeneous catalysts for the cycloaddition of epoxides to CO2 is reported. Methylimidazolium- and methylbenzimidazolium-based IL units (ILA and ILB, respectively) were introduced into the pore walls of the UiO-66-NH2 framework through a condensation reaction to generate ILA@U6N and ILB@U6N catalysts, respectively. The resultant heterogeneous catalysts, especially ILA@U6N, exhibited excellent CO2 adsorption capability, which makes them effective for cycloaddition reactions producing cyclic carbonates under mild reaction conditions in the absence of any cocatalyst or solvent. The significantly enhanced activity of ILA@U6N is attributed to the synergism between the coordinately unsaturated Lewis acidic Zr4+ centers and Br- ions in the bifunctional heterogeneous catalysts. The size effect of the ILs on coupling between the epoxide and CO2 was also studied for ILA@U6N and ILB@U6N. A periodic DFT study was performed to provide evidence of possible intermediates, transition states, and pathways, as well as to gain deeper insight into the mechanism of the ILA@U6N-catalyzed cycloaddition reaction between epichlorohydrin and CO2 .

The effect of crystallite size on pressure amplification in switchable porous solids.

Negative gas adsorption (NGA) in ordered mesoporous solids is associated with giant contractive structural transitions traversing through metastable states. Here, by systematically downsizing the crystal dimensions of a mesoporous MOF (DUT-49) from several micrometers to less than 200 nm, counterintuitive NGA phenomena are demonstrated to critically depend on the primary crystallite size. Adsorbing probe molecules, such as n-butane or nitrogen, gives insights into size-dependent activation barriers and thermodynamics associated with guest-induced network contraction. Below a critical crystal size, the nitrogen adsorption-induced breathing is completely suppressed as detected using parallelized synchrotron X-ray diffraction-adsorption instrumentation. In contrast, even the smallest particles show NGA in the presence of n-butane, however, associated with a significantly reduced pressure amplification. Consequently, the magnitude of NGA in terms of amount of gas expulsed and pressure amplification can be tuned, potentially paving the way towards innovative concepts for pressure amplification in micro- and macro-system engineering.

Metal-Organic Frameworks for Cultural Heritage Preservation: The Case of Acetic Acid Removal.

The removal of low concentrations of acetic acid from indoor air at museums poses serious preservation problems that the current adsorbents cannot easily address owing to their poor affinity for acetic acid and/or their low adsorption selectivity versus water. In this context, a series of topical water-stable metal-organic frameworks (MOFs) with different pore sizes, topologies, hydrophobic characters, and functional groups was explored through a joint experimental-computational exploration. We demonstrate how a subtle combination of sufficient hydrophobicity and optimized host-guest interactions allows one to overcome the challenge of capturing traces of this very polar volatile organic compound in the presence of humidity. The optimal capture of acetic acid was accomplished with MOFs that do not show polar groups in the inorganic node or have lipophilic but polar (e.g., perfluoro) groups functionalized to the organic linkers, that is, the best candidates from the list of explored MOFs are MIL-140B and UiO-66-2CF3. These two MOFs present the appropriate pore size to favor a high degree of confinement, together with organic spacers that allow an enhancement of the van der Waals interactions with the acetic acid. We establish in this work that MOFs can be a viable solution to this highly challenging problem in cultural heritage protection, which is a new field of application for this type of hybrid materials.

Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration.

Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

Gas/vapour separation using ultra-microporous metal-organic frameworks: insights into the structure/separation relationship.

The separation of related molecules with similar physical/chemical properties is of prime industrial importance and practically entails a substantial energy penalty, typically necessitating the operation of energy-demanding low temperature fractional distillation techniques. Certainly research efforts, in academia and industry alike, are ongoing with the main aim to develop advanced functional porous materials to be adopted as adsorbents for the effective and energy-efficient separation of various important commodities. Of special interest is the subclass of metal-organic frameworks (MOFs) with pore aperture sizes below 5-7 Å, namely ultra-microporous MOFs, which in contrast to conventional zeolites and activated carbons show great prospects for addressing key challenges in separations pertaining to energy and environmental sustainability, specifically materials for carbon capture and separation of olefin/paraffin, acetylene/ethylene, linear/branched alkanes, xenon/krypton, etc. In this tutorial review we discuss the latest developments in ultra-microporous MOF adsorbents and their use as separating agents via thermodynamics and/or kinetics and molecular sieving. Appreciably, we provide insights into the distinct microscopic mechanisms governing the resultant separation performances, and suggest a plausible correlation between the inherent structural features/topology of MOFs and the associated gas/vapour separation performance.

Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites.

Selective dinitrogen binding to transition metal ions mainly covers two strategic domains: biological nitrogen fixation catalysed by metalloenzyme nitrogenases, and adsorptive purification of natural gas and air. Many transition metal-dinitrogen complexes have been envisaged for biomimetic nitrogen fixation to produce ammonia. Inspired by this concept, here we report mesoporous metal-organic framework materials containing accessible Cr(III) sites, able to thermodynamically capture N2 over CH4 and O2. This fundamental study integrating advanced experimental and computational tools confirmed that the separation mechanism for both N2/CH4 and N2/O2 gas mixtures is driven by the presence of these unsaturated Cr(III) sites that allows a much stronger binding of N2 over the two other gases. Besides the potential breakthrough in adsorption-based technologies, this proof of concept could open new horizons to address several challenges in chemistry, including the design of heterogeneous biomimetic catalysts through nitrogen fixation.

A pressure-amplifying framework material with negative gas adsorption transitions.

Adsorption-based phenomena are important in gas separations, such as the treatment of greenhouse-gas and toxic-gas pollutants, and in water-adsorption-based heat pumps for solar cooling systems. The ability to tune the pore size, shape and functionality of crystalline porous coordination polymers--or metal-organic frameworks (MOFs)--has made them attractive materials for such adsorption-based applications. The flexibility and guest-molecule-dependent response of MOFs give rise to unexpected and often desirable adsorption phenomena. Common to all isothermal gas adsorption phenomena, however, is increased gas uptake with increased pressure. Here we report adsorption transitions in the isotherms of a MOF (DUT-49) that exhibits a negative gas adsorption; that is, spontaneous desorption of gas (methane and n-butane) occurs during pressure increase in a defined temperature and pressure range. A combination of in situ powder X-ray diffraction, gas adsorption experiments and simulations shows that this adsorption behaviour is controlled by a sudden hysteretic structural deformation and pore contraction of the MOF, which releases guest molecules. These findings may enable technologies using frameworks capable of negative gas adsorption for pressure amplification in micro- and macroscopic system engineering. Negative gas adsorption extends the series of counterintuitive phenomena such as negative thermal expansion and negative refractive indices and may be interpreted as an adsorptive analogue of force-amplifying negative compressibility transitions proposed for metamaterials.