Bimetallic Copper-Cerium-Based Metal-Organic Frameworks for Selective Carbon Dioxide Capture.

Metal-organic frameworks (MOFs) are highly regarded as valuable adsorbent materials in materials science, particularly in the field of CO2 capture. While numerous single-metal-based MOFs have demonstrated exceptional CO2 adsorption capabilities, recent advancements have explored the potential of bimetallic MOFs for enhanced performance. In this study, a CuCe-BTC MOF was synthesized through a straightforward hydrothermal method, and its improved properties, such as high surface area, smaller pore size, and larger pore volume, were compared with those of the bare Ce-BTC. The impact of the Cu/Ce ratio (1:4, 1:2, 1:1, and 3:2) was systematically investigated to understand how adding a second metal influences the CO2 adsorption performance of the Ce-BTC MOF. Various characterization techniques, including scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and N2 BET surface area analysis, were employed to assess the physical and chemical properties of the bare Ce-BTC and CuCe-BTC samples. Notably, CuCe-BTC-1:2 exhibited superior surface area (133 m2 g-1), small pore size (3.3 nm), and large pore volume (0.14 cm3 g-1) compared to the monometallic Ce-BTC. Furthermore, CuCe-BTC-1:2 demonstrated a superior CO2 adsorption capacity (0.74 mmol g-1), long-term stability, and good CO2/N2 selectivity. This research provides valuable insights into the design of metal-BTC frameworks and elucidates how introducing a second metal enhances the properties of the monometallic Ce-BTC-MOF, leading to improved CO2 capture performance.

Coordination Environment and Distance Optimization of Dual Single Atoms on Fluorine-Doped Carbon Nanotubes for Chlorine Evolution Reaction.

The chlorine evolution reaction (CER) is a crucial anode reaction in the chlor-alkali industrial process. Precious metal-based dimensionally stable anodes (DSAs) are commonly used as catalysts for CER but are constrained by their high cost and low selectivity. Herein, a Pt dual singe-atom catalyst (DSAC) dispersed on fluorine-doped carbon nanotubes (F-CNTs) is designed for an efficient and robust CER process. The prepared Pt DSAC demonstrates excellent CER activity with a low overpotential of 21 mV to achieve a current density of 10 mA cm-2 and a remarkable mass activity of 3802.6 A gpt-1 at an overpotential around 30 mV, outperforming those of commercial DSA and Pt single-atom catalysts. The excellent CER performance of Pt DSAC is attributed to the high atomic utilization and improved intrinsic activity. Notably, introducing fluorine atoms on CNTs increases the oxidation and chlorination resistance of Pt DSAC, and reduces the demetalization ratio of Pt atoms, resulting in excellent long-term CER stability. Theoretical calculations reveal that several Pt DSAC configurations with optimized first-shell ligands and interatomic distance display lower energy barriers for Cl intermediates generation and weaker ionic Pt-Cl bond interaction, which are favorable for the CER process.

Metal-Organic Framework-Derived Mesoporous B-Doped CoO/Co@N-Doped Carbon Hybrid 3D Heterostructured Interfaces with Modulated Cobalt Oxidation States for Alkaline Water Splitting.

Heteroatom-doped transition metal-oxides of high oxygen evolution reaction (OER) activities interfaced with metals of low hydrogen adsorption energy barrier for efficient hydrogen evolution reaction (HER) when uniformly embedded in a conductive nitrogen-doped carbon (NC) matrix, can mitigate the low-conductivity and high-agglomeration of metal-nanoparticles in carbon matrix and enhances their bifunctional activities. Thus, a 3D mesoporous heterostructure of boron (B)-doped cobalt-oxide/cobalt-metal nanohybrids embedded in NC and grown on a Ni foam substrate (B-CoO/Co@NC/NF) is developed as a binder-free bifunctional electrocatalyst for alkaline water-splitting via a post-synthetic modification of the metal-organic framework and subsequent annealing in different Ar/H2 gas ratios. B-CoO/Co@NC/NF prepared using 10% H2 gas (B-CoO/Co@NC/NF [10% H2 ]) shows the lowest HER overpotential (196 mV) and B-CoO/Co@NC/NF (Ar), developed in Ar, shows an OER overpotential of 307 mV at 10 mA cm-2 with excellent long-term durability for 100 h. The best anode and cathode electrocatalyst-based electrolyzer (B-CoO/Co@NC/NF (Ar)(+)//B-CoO/Co@NC/NF (10% H2 )(-)) generates a current density of 10 mA cm-2 with only 1.62 V with long-term stability. Further, density functional theory investigations demonstrate the effect of B-doping on electronic structure and reaction mechanism of the electrocatalysts for optimal interaction with reaction intermediates for efficient alkaline water-splitting which corroborates the experimental results.

Robust Zeolitic Tetrazole Framework for Electrocatalytic Dopamine Detection with High Selectivity.

A novel zeolitic tetrazolate framework (ZTF-8) has been synthesized by solvent-free heat-assisted (70 °C) mechanochemical grinding of zinc acetate and 5-methyl tetrazole in the presence of NaOH powder. The structure of ZTF-8 adopts the zeolitic sodalite (SOD) topology with uncoordinated N-heteroatom sites and resembles the structure of the well-known zeolitic imidazole framework ZIF-8. ZTF-8 is exceptionally stable in 0.1 M aqueous acid and base solutions for 60 days at 25 °C. The unique structure with uncoordinated N-heteroatom active sites and exceptional stability of ZTF-8 facilitated the electrocatalytic oxidation of dopamine to dopamine quinone at neutral pH. Without any postsynthetic modification, ZTF-8 is directly used for the facile electrochemical detection of dopamine over a wide range of concentrations (5-550 µM) with a high sensitivity (2410.8 µA mM-1 cm-2). It also demonstrated promising selectivity over other interferents of similar oxidation potential, such as ascorbic acid and uric acid. The DFT study revealed that the ZTF-8 framework has a higher binding energy (-145.07 kJ/mol) and stronger interaction with dopamine than its isostructural ZIF-8 structure (-130.42 kJ/mol).

Three-in-One C2 H2 -Selectivity-Guided Adsorptive Separation across an Isoreticular Family of Cationic Square-Lattice MOFs.

Energy-efficient selective physisorption driven C2 H2 separation from industrial C2-C1 impurities such as C2 H4 , CO2 and CH4 is of great importance in the purification of downstream commodity chemicals. We address this challenge employing a series of isoreticular cationic metal-organic frameworks, namely iMOF-nC (n=5, 6, 7). All three square lattice topology MOFs registered higher C2 H2 uptakes versus the competing C2-C1 gases (C2 H4 , CO2 and CH4 ). Dynamic column breakthrough experiments on the best-performing iMOF-6C revealed the first three-in-one C2 H2 adsorption selectivity guided separation of C2 H2 from 1:1 C2 H2 /CO2 , C2 H2 /C2 H4 and C2 H2 /CH4 mixtures. Density functional theory calculations critically examined the C2 H2 selective interactions in iMOF-6C. Thanks to the abundance of square lattice topology MOFs, this study introduces a crystal engineering blueprint for designing C2 H2 -selective layered metal-organic physisorbents, previously unreported in cationic frameworks.

Metal-Organic Framework-Enhanced Solid-Phase Microextraction Mass Spectrometry for the Direct and Rapid Detection of Perfluorooctanoic Acid in Environmental Water Samples.

We report the development of metal-organic framework (MOF)-based probes for the direct and rapid detection and quantification of perfluorooctanoic acid (PFOA) by mass spectrometry. Four water-resistant MOFs-ZIF-8, UiO-66, MIL88-A, and Tb2(BDC)3-were coated on poly(dopamine) precoated stainless steel needles and used to rapidly preconcentrate PFOA from water for direct analysis by nanoelectrospray ionization mass spectrometry. The analytical performance of each MOF for detecting PFOA was correlated with both the calculated binding energy of the MOF for PFOA and the relative change in the surface area of the MOF upon exposure to PFOA. MOF-functionalized probes can be used for the rapid (<5 min) and sensitive quantification of PFOA molecules at low ng L-1 levels in environmental water samples (i.e., tap water, rainwater, and seawater) with no sample preparation. The limit of detection of PFOA in ultrapure water was 11.0 ng L-1. Comparable accuracy to an accredited analytical method was achieved, despite the MOF-functionalized probe approach being ∼40 times quicker and requiring ∼10 times less sample. These features indicate that MOF-coated probes are promising for the direct and rapid monitoring of polyfluorinated substances and other pollutants in the field.

The Effect of Sterically Active Ligand Substituents on Gas Adsorption within a Family of 3D Zn-Based Coordination Polymers.

An investigation of the adsorption properties of two structurally related, 3D coordination polymers of composition Zn(2-Mehba) and Zn(2,6-Me2hba) (2-Mehba = the dianion of 2-methyl-4-hydroxybenzoic acid and 2,6-Me2hba = the dianion of 2,6-dimethyl-4-hydroxybenzoic acid) is presented. A common feature of these structures are parallel channels that are able to accommodate appropriately sized guest molecules. The structures differ with respect to the steric congestion within the channels arising from methyl groups appended to the bridging ligands of the network. The host network, Zn(2-Mehba), is able to take up appreciable quantities of H2 (77 K) and CO2 and CH4 (298 K) in a reversible manner. In regard to the adsorption of N2 by Zn(2-Mehba), there appears to be an unusual temperature dependence for the uptake of the gas such that when the temperature is increased from 77 to 298 K the uptake of N2 increases. The relatively narrow channels of Zn(2,6-Me2hba) are too small to allow the uptake of N2 and CH4, but H2 molecules can be adsorbed. A pronounced step at elevated pressures in CO2 and N2O isotherms for Zn(2,6-Me2hba) is noted. Calculations indicate that rotation of phenolate rings leads to a change in the available intraframework space during CO2 dosing.

Enhancing Multicomponent Metal-Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations.

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal-organic frameworks (MOFs) that contain the three-dimensional cubane-1,4-dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB-30), comprising cdc, 4,4'-biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π-π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.

A Robust Ethane-Trapping Metal-Organic Framework with a High Capacity for Ethylene Purification.

The separation of ethane from ethylene is of prime importance in the purification of chemical feedstocks for industrial manufacturing. However, differentiating these compounds is notoriously difficult due to their similar physicochemical properties. High-performance porous adsorbents provide a solution. Conventional adsorbents trap ethylene in preference to ethane, but this incurs multiple steps in separation processes. Alternatively, high-purity ethylene can be obtained in a single step if the adsorbent preferentially adsorbs ethane over ethylene. We herein report a metal-organic framework, MUF-15 (MUF, Massey University Framework), constructed from inexpensive precursors that sequesters ethane from ethane/ethylene mixtures. The productivity of this material is exceptional: 1 kg of MOF produces 14 L of polymer-grade ethylene gas in a single adsorption step starting from an equimolar ethane/ethylene mixture. Computational simulations illustrate the underlying mechanism of guest adsorption. The separation performance was assessed by measuring multicomponent breakthrough curves, which illustrate that the separation performance is maintained over a wide range of feed compositions and operating pressures. MUF-15 is robust, maintains its performance in the presence of acetylene, and is easily regenerated by purging with inert gas or by placing under reduced pressure.

CUB-5: A Contoured Aliphatic Pore Environment in a Cubic Framework with Potential for Benzene Separation Applications.

One prominent aspect of metal organic frameworks (MOFs) is the ability to tune the size, shape, and chemical characteristics of their pores. MOF-5, with its open cubic connectivity of Zn4O clusters joined by two-dimensional, terephthalate linkers, is the archetypal example: both functionalized and elongated linkers produce isoreticular frameworks that define pores with new shapes and chemical environments. The recent scalable synthesis of cubane-1,4-dicarboxylic acid (1,4-H2cdc) allows the first opportunity to explore its application in leading reticular architectures. Herein we describe the use of 1,4-H2cdc to construct [Zn4O(1,4-cdc)3], referred to as CUB-5. Isoreticular with MOF-5, CUB-5 adopts a cubic architecture but features aliphatic, rather than aromatic, pore surfaces. Methine units point directly into the pores, delivering new and unconventional adsorption locations. Our results show that CUB-5 is capable of selectively adsorbing high amounts of benzene at low partial pressures, promising for future investigations into the industrial separation of benzene from gasoline using aliphatic MOF materials. These results present an effective design strategy for the generation of new MOF materials with aliphatic pore environments and properties previously unattainable in conventional frameworks.

A New Structural Family of Gas-Sorbing Coordination Polymers Derived from Phenolic Carboxylic Acids.

The structure of Li(inox)⋅2/3 DMF (inox(-) =the N-oxide of the isonicotinate anion) consists of a 3D framework with solvent-filled, square cross-section channels of approximate dimensions 5.5×5.5 Å. Unfortunately, the Li(inox) framework is unstable upon removal of DMF from the channels. When the structurally related 4-hydroxybenzoic acid (H2 hba) was used in place of Hinox, and Zn(2+) in place of the Li(+) , a structurally similar but more robust network, Zn(hba), was obtained; the isostructural compound, Co(hba), may also be prepared. Longer ligands with phenolate and carboxylate functional groups at opposite ends, such as the dianions of 4-coumaric acid (H2 cma) and 4'-hydroxy-4-biphenylcarboxylic acid (H2 hbpc), in combination with Zn(2+) yield Zn(cma) and Zn(hbpc) frameworks, respectively, with the same PtS topology but with larger channels. The coordination polymers remain intact after desolvation and exhibit microporosity, showing the ability to sorb significant quantities of CO2 , CH4 , and H2 .

Phosphoric acid loaded azo (-N═N-) based covalent organic framework for proton conduction.

Two new chemically stable functional crystalline covalent organic frameworkds (COFs) (Tp-Azo and Tp-Stb) were synthesized using the Schiff base reaction between triformylphloroglucinol (Tp) and 4,4'-azodianiline (Azo) or 4,4'-diaminostilbene (Stb), respectively. Both COFs show the expected keto-enamine form, and high stability toward boiling water, strong acidic, and basic media. H3PO4 doping in Tp-Azo leads to immobilization of the acid within the porous framework, which facilitates proton conduction in both the hydrous (σ = 9.9 × 10(-4) S cm(-1)) and anhydrous state (σ = 6.7 × 10(-5) S cm(-1)). This report constitutes the first emergence of COFs as proton conducting materials.

Porous aromatic frameworks impregnated with fullerenes for enhanced methanol/water separation.

Molecular simulation techniques have revealed that the incorporation of fullerenes within porous aromatic frameworks (PAFs) remarkably enhances methanol uptake while inhibiting water uptake. The highest selectivity of methanol over water is found to be 1540 at low pressure (1 kPa) and decreases gradually with increasing pressure. The adsorption of water is very small compared to methanol, a useful material property for membrane and adsorbent-based separations. Grand canonical Monte Carlo (GCMC) simulations are utilized to calculate the pure component and mixture adsorption isotherms. The water and methanol mixture simulations show that water uptake is further inhibited above the pure component results because of the dominant methanol adsorption. Molecular dynamics (MD) simulations confirm that water diffusivity is also inhibited by strong methanol adsorption in the mixture. Overall, this study reveals profound hydrophobicity in C60@PAF materials and recommends C60@PAFs as suitable applicants for adsorbent and membrane-based separations of methanol/water mixtures and other alcohol/water separation applications.

Topological control in paddlewheel metal-organic cages via ligand length variation.

Varying the length of phenanthrene-derived ligands switches the selective assembly of MIInLn metal-organic cages (MOCs, n = 6 or 8) between tetrahedral, square, or triangular architectures. The limit of this approach is explored for both Cu2 and Rh2 paddlewheel MOCs, and supported by solution, solid-state and computational analysis.

Metal-Organic Frameworks for Enhanced Hydrogen Generation from Syngas: A Density Functional Theory Approach.

Although methane poses environmental concerns, it is employed in hydrogen production processes such as steam-methane reforming (SMR), which has an issue of by-products released. Initiatives are being pursued to address CO and CO2 emissions using carbon capture methods, with the goal of minimizing environmental harm while improving pure hydrogen generation from syngas. In this study, porous coordination network (PCN-250) has been studied for its selective adsorption property towards CO, CO2 and H2O as syngas mixture to obtain pure hydrogen. For this purpose, the trimetallic cluster node Fe2M (where Fe2 represents the 3+ oxidation state and M is Cr(II), Mn(II), Fe(II), Co(II), Ni(II), and Zn(II)) has been considered. Fe(III) in combination with metal atoms like Cr(II), Co(II), or Ni(II) has been found to exhibit enhanced adsorption properties towards CO, CO2 and H2O. The molecule with the strongest interaction was found to be H2O over Fe(III)2Zn(II) cluster and weakest interaction was found between H2 and Fe(III)2Ni(II). Charge transfer, natural bond orbital (NBO) and spin density analyses reveal the electronic structural properties of this combination, leading to enhanced adsorption of CO and CO2.

Surface Electronic Properties-Driven Electrocatalytic Nitrogen Reduction on Metal-Conjugated Porphyrin 2D-MOFs.

Two-dimensional (2D) metal organic framework (MOF) or metalloporphyrin nanosheets with a stable metal-N4 complex unit present the metal as a single-atom catalyst dispersed in the 2D porphyrin framework. First-principles calculations on the 3d-transition metals in M-TCPP are investigated in this study for their surface-dependent electronic properties including work function and d-band center. Crystal orbital Hamiltonian population (-pCOHP) analysis highlights a higher contribution of the bonding state in the M-N bond and antibonding state in the N-N bond to be essential for N-N bond activation. A linear relationship between ΔGmax and surface electronic properties, N-N bond strength, and Bader charge has been found to influence the rate-determining potential for nitrogen reduction reaction (NRR) in M-TCPP MOFs. 2D Ti-TCPP MOF, with a kinetic energy barrier of 1.43 eV in the final protonation step of enzymatic NRR, shows exclusive NRR selectivity over competing hydrogen reduction (HER) and nitrogenous compounds (NO and NO2). Thus, Ti-TCPP MOF with an NRR limiting potential of -0.35 V in water solvent is proposed as an attractive candidate for electrocatalytic NRR.

A Heterogeneous Acid-Base Organocatalyst For Cascade Deacetalisation-Knoevenagel Condensations.

Multifunctional heterogeneous catalysts are an effective strategy to drive chemical cascades, with attendant time, resource and cost efficiencies by eliminating unit operations arising in normal multistep processes. Despite advances in the design of such catalysts, the fabrication of proximate, chemically antagonistic active sites remains a challenge for inorganic materials science. Hydrogen-bonded organocatalysts offer new opportunities for the molecular level design of multifunctional structures capable of stabilising antagonistic active sites. We report the catalytic application of a charge-assisted, hydrogen-bonded crystalline material, bis(melaminium)adipate (BMA), synthesised from melamine and adipic acid, which possesses proximate acid-base sites. BMA exhibits high activity for the cascade deacetalisation-Knoevenagel condensation of dimethyl acetals to form benzylidenemalononitriles under mild conditions in water; BMA is amenable to large-scale manufacture and recycling with minimal deactivation. Computational modelling of the melaminium cation in protonated BMA explains the observed catalytic reactivity, and identifies the first demethoxylation step as rate-limiting, in good agreement with time-dependent 1H NMR and kinetic experiments. A broad substrate scope for the cascade transformation of aromatic dimethyl acetals is demonstrated.

Purification of Waste-Generated Biogas Mixtures Using Covalent Organic Framework's High CO2 Selectivity.

Development of crystalline porous materials for selective CO2 adsorption and storage is in high demand to boost the carbon capture and storage (CCS) technology. In this regard, we have developed a ß-keto enamine-based covalent organic framework (VM-COF) via the Schiff base polycondensation technique. The as-synthesized VM-COF exhibited excellent thermal and chemical stability along with a very high surface area (1258 m2 g-1) and a high CO2 adsorption capacity (3.58 mmol g-1) at room temperature (298 K). The CO2/CH4 and CO2/H2 selectivities by the IAST method were calculated to be 10.9 and 881.7, respectively, which were further experimentally supported by breakthrough analysis. Moreover, theoretical investigations revealed that the carbonyl-rich sites in a polymeric backbone have higher CO2 binding affinity along with very high binding energy (-39.44 KJ mol-1) compared to other aromatic carbon-rich sites. Intrigued by the best CO2 adsorption capacity and high CO2 selectivity, we have utilized the VM-COF for biogas purification produced by the biofermentation of municipal waste. Compared with the commercially available activated carbon, VM-COF exhibited much better purification ability. This opens up a new opportunity for the creation of functionalized nanoporous materials for the large-scale purification of waste-generated biogases to address the challenges associated with energy and the environment.

Post-synthetic structural processing in a metal-organic framework material as a mechanism for exceptional CO2/N2 selectivity.

Here we report the synthesis and ceramic-like processing of a new metal-organic framework (MOF) material, [Cu(bcppm)H2O], that shows exceptionally selective separation for CO2 over N2 (ideal adsorbed solution theory, S(ads) = 590). [Cu(bcppm)H2O]·xS was synthesized in 82% yield by reaction of Cu(NO3)2·2.5H2O with the link bis(4-(4-carboxyphenyl)-1H-pyrazolyl)methane (H2bcppm) and shown to have a two-dimensional 4(4)-connected structure with an eclipsed arrangement of the layers. Activation of [Cu(bcppm)H2O] generates a pore-constricted version of the material through concomitant trellis-type pore narrowing (b-axis expansion and c-axis contraction) and a 2D-to-3D transformation (a-axis contraction) to give the adsorbing form, [Cu(bcppm)H2O]-ac. The pore contraction process and 2D-to-3D transformation were probed by single-crystal and powder X-ray diffraction experiments. The 3D network and shorter hydrogen-bonding contacts do not allow [Cu(bcppm)H2O]-ac to expand under gas loading across the pressure ranges examined or following re-solvation. This exceptional separation performance is associated with a moderate adsorption enthalpy and therefore an expected low energy cost for regeneration.

Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination.

A series of five thermally and chemically stable functionalized covalent organic frameworks (COFs), namely, TpPa-NO2, TpPa-F4, TpBD-(NO2)2, TpBD-Me2, and TpBD-(OMe)2 were synthesized by employing the solvothermal aldehyde-amine Schiff base condensation reaction. In order to complete the series, previously reported TpPa-1, TpPa-2, and TpBD have also been synthesized, and altogether, eight COFs were fully characterized through powder X-ray diffraction (PXRD), Fourier transform IR (FT-IR) spectroscopy, (13)C solid-state NMR spectroscopy, and thermogravimetric analysis. These COFs are crystalline, permanently porous, and stable in boiling water, acid (9 N HCl), and base (3 N NaOH). The synthesized COFs (all eight) were successfully delaminated using a simple, safe, and environmentally friendly mechanical grinding route to transform into covalent organic nanosheets (CONs) and were well characterized via transmission electron microscopy and atomic force microscopy. Further PXRD and FT-IR analyses confirm that these CONs retain their structural integrity throughout the delamination process and also remain stable in aqueous, acidic, and basic media like the parent COFs. These exfoliated CONs have graphene-like layered morphology (delaminated layers), unlike the COFs from which they were synthesized.