Functionalisation of MUF-15 enhances CO2/CH4 selectivity in mixed-matrix membranes.

MUF-15 (MUF = Massey University Framework) is a metal-organic framework with pores that can be tuned by ligand functionalisation. Crystallites of MUF-15 and derivatives were blended with the organic polymer 6FDA-DAM to produce mixed-matrix membranes (MMMs). At a loading of 30 wt%, membranes with MUF-15-F, MUF-15 with an appended fluoro group, exhibited a CO2 permeability of 1300 Barrer and CO2/CH4 selectivity of 37.1. These values surpass membranes with the parent MUF-15 and exceed the Robeson upper bound.

µ-1,6-Dioxo-1,6-di-phenyl-hexane-3,4-diolato-bis-[(2,2'-bi-pyridine)-chlorido-copper(II)] dihydrate.

The reaction of CuCl2 with 1,6-diphenyl-1,3,5,6-hexa-netetrone and 2,2'-bi-pyridine (bipy) in ethanol gave crystals of the corresponding bimetallic complex, [Cu2(C18H12O4)Cl2(C10H8N2)2]·2H2O. The mol-ecule is centrosymmetric with each CuII ion coordinated to two oxygen atoms from the tetronediate, two nitro-gen atoms from a bipy ligand and one coordinated chloride ion. A water mol-ecule of crystallization forms hydrogen bonds to the chloride ions, linking the mol-ecules into a chain parallel to the bc-face diagonal.

Hetero-interpenetrated metal-organic frameworks.

Interpenetrated metal-organic frameworks (MOFs) comprise two or more lattices that are mutually entangled. Interpenetration can be used to tune the structures and pore architectures of MOFs to influence, for example, their stability or interactions with guest molecules. The interpenetrating sublattices are typically identical, but hetero-interpenetrated MOFs, which consist of sublattices that are different from one another, have also been serendipitously produced. Here we describe a strategy for the deliberate synthesis of hetero-interpenetrated MOFs. We use the cubic α-MUF-9 framework as a host sublattice to template the growth of a second sublattice within its pores. Three different secondary sublattices are grown-two of which are not known as standalone MOFs-leading to three different hetero-interpenetrated MOFs. This strategy may serve to combine different properties into one material. We produce an asymmetric catalysis by allocating separate roles to the interpenetrating sublattices in a hetero-interpenetrated MOF: an achiral secondary amine on one sublattice provides the catalytic activity, while the chiral α-MUF-10 host imparts asymmetry to aldol and Henry reactions.

Multicomponent Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are constructed from metal ions or clusters and organic linkers. Typical MOFs are rather simple, comprising just one type of joint and linker. An additional degree of structural complexity can be introduced by using multiple different components that are assembled into the same framework In the early days of MOF chemistry, conventional wisdom held that attempting to prepare frameworks starting from such a broad set of components would lead to multiple different phases. However, this review highlights how this view was mistaken and frameworks comprising multiple different components can be deliberately designed and synthesized. When coupled to structural order and periodicity, the presence of multiple components leads to exceptional functional properties that can be understood at the atomic level.

Synergistic Effect of Redox Dual PdO x /MnO x Cocatalysts on the Enhanced H2 Production Potential of a SnS/α-Fe2O3 Heterojunction via Ethanol Photoreforming.

In the quest for optimal H2 evolution (HE) through ethanol photoreforming, a dual cocatalyst-modified heterocatalyst strategy is utilized. Tin(II) sulfide (SnS) was hybridized with α-Fe2O3 to form the heterocatalyst FeOSnS with a p-n heterojunction structure as confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV-vis diffusive reflectance spectroscopy (UV-vis DRS), and Brunauer-Emmett-Teller (BET) techniques. PdO x and PdO x /MnO x cocatalysts were loaded onto the FeOSnS heterocatalyst through the impregnation method, as verified by high-resolution transform electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and elemental mapping. Photocatalytic ethanol photoreforming resulted in the production of H2 as the main product with a selectivity of 99% and some trace amounts of CH4. The FeOSnS2-PdO x 2%/MnO x 1% photocatalyst achieved the highest HE rate of 1654 µmol/g, attributed to the synergistic redox contribution of the PdO x and MnO x species.

Tuning the Stereoselectivity of an Intramolecular Aldol Reaction by Precisely Modifying a Metal-Organic Framework Catalyst.

We report the catalysis of an enantioselective, intramolecular aldol reaction accelerated by an organocatalyst embedded in a series of multicomponent metal-organic frameworks. By precisely programming the pore microenvironment around the site of catalysis, we show how important features of an intramolecular aldol reaction can be tuned, such as the substrate consumption, enantioselectivity, and degree of dehydration of the products. This tunability arises from non-covalent interactions between the reaction participants and modulator groups that occupy positions in the framework remote from the catalytic site. Further, the catalytic moiety can be switched form one framework linker to another. Deliberately building up microenvironments that can influence the outcome of reaction processes in this way is not possible in conventional homogenous catalysts but is reminiscent of enzymes.

Photoinduced Electron Transfer in Multicomponent Truxene-Quinoxaline Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) can respond to light in a number of interesting ways. Photochromism is observed when a structural change to the framework is induced by the absorption of light, which results in a color change. In this work, we show that introducing quinoxaline ligands to MUF-7 and MUF-77 (MUF = Massey University Framework) produces photochromic MOFs that change color from yellow to red upon the absorption of 405 nm light. This photochromism is observed only when the quinoxaline units are incorporated into the framework and not for the standalone ligands in the solid state. Electron paramagnetic resonance (EPR) spectroscopy shows that organic radicals form upon irradiation of the MOFs. The EPR signal intensities and longevity depend on the precise structural details of the ligand and framework. The photogenerated radicals are stable for long periods in the dark but can be switched back to the diamagnetic state by exposure to visible light. Single-crystal X-ray diffraction analysis reveals bond length changes upon irradiation that are consistent with electron transfer. The multicomponent nature of these frameworks allows the photochromism to emerge by allowing through-space electron transfer, precisely positioning the framework building blocks, and tolerating functional group modifications to the ligands.

In Situ Investigation of Multicomponent MOF Crystallization during Rapid Continuous Flow Synthesis.

Access to the potential applications of metal-organic frameworks (MOFs) depends on rapid fabrication. While there have been advances in the large-scale production of single-component MOFs, rapid synthesis of multicomponent MOFs presents greater challenges. Multicomponent systems subjected to rapid synthesis conditions have the opportunity to form separate kinetic phases that are each built up using just one linker. We sought to investigate whether continuous flow chemistry could be adapted to the rapid formation of multicomponent MOFs, exploring the UMCM-1 and MUF-77 series. Surprisingly, phase pure, highly crystalline multicomponent materials emerge under these conditions. To explore this, in situ WAXS was undertaken to gain an understanding of the formation mechanisms at play during flow synthesis. Key differences were found between the ternary UMCM-1 and the quaternary MUF-7, and key details about how the MOFs form were then uncovered. Counterintuitively, despite consisting of just two ligands UMCM-1 proceeds via MOF-5, whereas MUF-7 consists of three ligands but is generated directly from the reaction mixture. By taking advantage of the scalable high-quality materials produced, C6 separations were achieved in breakthrough settings.

Functionalized Iron-Nitrogen-Carbon Electrocatalyst Provides a Reversible Electron Transfer Platform for Efficient Uranium Extraction from Seawater.

Uranium extraction from seawater provides an opportunity for sustainable fuel supply to nuclear power plants. Herein, an adsorption-electrocatalysis strategy is demonstrated for efficient uranium extraction from seawater using a functionalized iron-nitrogen-carbon (Fe-Nx -C-R) catalyst, comprising N-doped carbon capsules supporting FeNx single-atom sites and surface chelating amidoxime groups (R). The amidoxime groups bring hydrophilicity to the adsorbent and offer surface-specific binding sites for UO2 2+ capture. The site-isolated FeNx centres reduce adsorbed UO2 2+ to UO2 + . Subsequently, through electrochemical reduction of the FeNx sites, unstable U(V) ions are reoxidized to U(VI) in the presence of Na+ resulting in the generation of solid Na2 O(UO3 ·H2 O)x , which can easily be collected. Fe-Nx -C-R reduced the uranium concentration in seawater from ≈3.5 ppb to below 0.5 ppb with a calculated capacity of ≈1.2 mg g-1 within 24 h. To the best of the knowledge, the developed system is the first to use the adsorption of uranyl ions and electrodeposition of solid Na2 O(UO3 .H2 O)x for the extraction of uranium from seawater. The important discoveries guide technology development for the efficient extraction of uranium from seawater.

Trisequential Postsynthetic Modification of a Tagged IRMOF-9 Framework.

Tailoring the pore environments of metal-organic frameworks (MOFs) is key to improving their performance and expanding their applicability. Postsynthetic methods, wherein an already synthesized MOF undergoes further chemical reactions, present many advantages for such tailoring and lead to much interesting new chemistry. However, this method has seldom been pushed farther than two reaction steps on the organic component. Here we report a three-step sequence starting from an alkenyl group on the biphenyl backbone of an IRMOF-9 analogue. The alkene is converted to an oxirane group and subsequently to a 1,2-azidoalcohol. The ultimate product is a framework functionalized with an aziridine ring. The reaction efficiency of each step is high, which suppresses the formation of undesired functional groups and the buildup of unintended multivariate frameworks. The synthesis of each framework was attempted via a direct synthetic method employing the appropriately functionalized biphenyldicarboxylate ligand. In general, this met with failure, which demonstrates the power and utility of postsynthetic methods for preparing new materials.

An upper bound visualization of design trade-offs in adsorbent materials for gas separations: alkene/alkane adsorbents.

The last 20 years has seen an explosion in the number of publications investigating porous solids for gas adsorption and separation. The combination of external drivers such as anthropogenic climate change and industrial efficiency has been coupled with discovery of new materials such as synthetic zeolites, metal-organic frameworks, covalent organic frameworks, and non-porous adsorbents. Numerous reviews catalogue these materials and their properties. However, the field lacks a unifying resource to visually compare and analyse materials properties with regard to their utility as a scientific advance and potential for industrial use. In the related field of membrane science, the 'Robeson upper bound' empirically describes the trade-off between gas permeability and selectivity and has become a ubiquitous tool for comparing membrane materials. In this article, we propose upper and lower bounds that empirically correlate the trade-offs encountered when designing adsorbent materials for gas separation, specifically: capacity, selectivity, and heat of adsorption. We apply bound visualizations to adsorbents studied for light alkene/alkane separations and highlight their use in identifying candidate materials for examination within process models and for guiding insights to the most effective materials design strategies. Furthermore, we note the limitations of upper and lower bound visualizations and provide links to a database resource for researchers to produce and download bound visualization plots. We anticipate that introducing bound visualizations to the field of adsorbents for gas separations will allow researchers to provide context for the importance of new materials discoveries, understand trade-offs in adsorbent design, and connect process engineers with candidate materials.

MUF-16: A Robust Metal-Organic Framework for Pre- and Post-Combustion Carbon Dioxide Capture.

One of the most critical environmental issues of our age is the escalating release of CO2 into the atmosphere. Separation technologies with low energy footprints may be an effective way to capture CO2 and prevent its accumulation. Metal-organic frameworks (MOFs) can meet separation challenges due to their tailored structures and tunable pore surfaces. However, obstacles to their deployment can include the energy consumed by regeneration, a lack of long-term structural stability, and their production on large scales. Herein, we report on MUF-16 ([Co(Haip)2], H2aip = 5-aminoisophthalic acid), a hydrogen-bonded water-stable microporous material that combines high CO2 adsorption with a low affinity for other gases. MUF-16 is built up from inexpensive starting reagents in a scalable process. It can be easily regenerated at room temperature by purging with inert gas, and it maintains its performance over multiple adsorption/desorption cycles. MUF-16 features one-dimensional channels that trap CO2 guest molecules by a raft of attractive electrostatic interactions and size complementarity. It rejects H2 and N2 molecules around room temperature. This was verified by simulated and experimental breakthrough separation measurements on CO2/N2 and CO2/H2 mixtures. MUF-16 can be pelletized by coating with polymeric poly(vinylidene difluoride) (PVDF) to render it compatible with large-scale applications.

Selective capture of carbon dioxide from hydrocarbons using a metal-organic framework.

Efficient and sustainable methods for carbon dioxide capture are highly sought after. Mature technologies involve chemical reactions that absorb CO2, but they have many drawbacks. Energy-efficient alternatives may be realised by porous physisorbents with void spaces that are complementary in size and electrostatic potential to molecular CO2. Here, we present a robust, recyclable and inexpensive adsorbent termed MUF-16. This metal-organic framework captures CO2 with a high affinity in its one-dimensional channels, as determined by adsorption isotherms, X-ray crystallography and density-functional theory calculations. Its low affinity for other competing gases delivers high selectivity for the adsorption of CO2 over methane, acetylene, ethylene, ethane, propylene and propane. For equimolar mixtures of CO2/CH4 and CO2/C2H2, the selectivity is 6690 and 510, respectively. Breakthrough gas separations under dynamic conditions benefit from short time lags in the elution of the weakly-adsorbed component to deliver high-purity hydrocarbon products, including pure methane and acetylene.

Second-order programming the synthesis of metal-organic frameworks.

Herein we report a new second-order coordinate-covalent programming strategy for metal-organic framework synthesis. We show controlled heterofunctional copolymerisation turns on 'in lattice' linking to deliver highly porous frameworks in a single step process.

Overcoming Fundamental Limitations in Adsorbent Design: Alkene Adsorption by Non-porous Copper(I) Complexes.

Purifying alkenes from alkanes requires cryogenic distillation. This consumes energy equivalent to countries of ca. 5 million people. Replacing distillation with adsorption processes would significantly increase energy efficiency. Trade-offs between kinetics, selectivity, capacity, and heat of adsorption have prevented production of an optimal adsorbent. We report adsorbents that overcome these trade-offs. [Cu-Br]3 and [Cu-H]3 are air-stable trinuclear complexes that undergo reversible solid-state inter-molecular rearrangements to produce dinuclear [Cu-Br⋅(alkene)]2 and [Cu-H⋅(alkene)]2 . The reversible solid-state rearrangement, confirmed in situ using powder X-ray diffraction, allows adsorbent design trade-offs to be overcome, coupling low heat of adsorption (-10 to -17 kJ mol-1alkene ), high alkene:alkane selectivity (47; 29), and uptake capacity (>2.5 molalkene mol-1Cu3 ). Most remarkably, [Cu-H]3 displays fast uptake and regenerates capacity within 10 minutes.

Probing Nonuniform Adsorption in Multicomponent Metal-Organic Frameworks via Segmental Dynamics by Solid-State Nuclear Magnetic Resonance.

The guest adsorption phenomena in multicomponent metal-organic frameworks (MOFs) are intricate due to their structural complexities. In this work, we studied two members of the isostructural series of MUF-77 frameworks that consist of long or short alkyl groups. The adsorption of methanol, N,N-dimethylaniline (DMA) and acridine orange (AO) in two structures of MUF-77 has been investigated. 2H solid-state nuclear magnetic resonance (SSNMR) and two-dimensional 1H-13C NMR spectroscopy were used to probe the dynamics of various compartments of MUF-77. Through the analyses of dynamic behavior by SSNMR and molecular dynamics simulations, we elucidate the spatial distribution of guest molecules are nonuniform around different chemical components, in different pore structures, and across different parts of MOF lattice. In addition, we reveal that the framework flexibility of MUF-77 with short alkyl groups is reduced upon guest adsorption yet the framework flexibility of MUF-77 with long alkyl groups increases upon loading with methanol.

Thermal Elimination of Ethylene from Cyclobutyl Groups Characterized by X-ray Crystallography in a Metal-Organic Framework Matrix.

Methods to synthesize and characterize aromatic molecules with vinyl substituents are sought after yet limited in the literature. Here, we introduce cyclobutyl groups into a metal-organic framework (MOF) matrix that are poised to produce ethylene upon heating. The expulsion of ethylene produces vinyl groups on an aromatic core, which are isolated by the crystalline matrix of the framework. This enables full characterization of the thermolysis by single-crystal X-ray diffraction. Further, we modify the vinyl groups by a bromine addition reaction. Importantly, the two transformations happen in a single-crystal-to-single-crystal manner without changing the overall network structure of the parent framework. New insights into the structural and synthetic chemistry of this important class of compound are generated. Installing reactive vinyl tags in materials by the high temperature thermolysis of cyclobutyl groups is a powerful strategy for altering their physicochemical characteristics.

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.

Highly efficient electrocatalytic hydrogen evolution promoted by O-Mo-C interfaces of ultrafine ß-Mo2C nanostructures.

Optimizing interfacial contacts and thus electron transfer phenomena in heterogeneous electrocatalysts is an effective approach for enhancing electrocatalytic performance. Herein, we successfully synthesized ultrafine ß-Mo2C nanoparticles confined within hollow capsules of nitrogen-doped porous carbon (ß-Mo2C@NPCC) and found that the surface layer of molybdenum atoms was further oxidized to a single Mo-O surface layer, thus producing intimate O-Mo-C interfaces. An arsenal of complementary technologies, including XPS, atomic-resolution HAADF-STEM, and XAS analysis clearly reveals the existence of O-Mo-C interfaces for these surface-engineered ultrafine nanostructures. The ß-Mo2C@NPCC electrocatalyst exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) in water. Theoretical studies indicate that the highly accessible ultrathin O-Mo-C interfaces serving as the active sites are crucial to the HER performance and underpinned the outstanding electrocatalytic performance of ß-Mo2C@NPCC. This proof-of-concept study opens a new avenue for the fabrication of highly efficient catalysts for HER and other applications, whilst further demonstrating the importance of exposed interfaces and interfacial contacts in efficient electrocatalysis.

Evolution of Zn(II) single atom catalyst sites during the pyrolysis-induced transformation of ZIF-8 to N-doped carbons.

The pyrolysis of zeolitic imidazolate frameworks (ZIFs) is becoming a popular approach for the synthesis of catalysts comprising porphyrin-like metal single atom catalysts (SACs) on N-doped carbons (M-N-C). Understanding the structural evolution of M-N-C as a function of ZIF pyrolysis temperature is important for realizing high performance catalysts. Herein, we report a detailed investigation of the evolution of Zn single atom catalyst sites during the pyrolysis of ZIF-8 at temperatures ranging from 500 to 900 °C. Results from Zn L-edge and Zn K-edge X-ray absorption spectroscopy studies reveal that tetrahedral ZnN4 centers in ZIF-8 transform to porphyrin-like ZnN4 centers supported on N-doped carbon at temperatures as low as 600 °C. As the pyrolysis temperature increased in the range 600-900 °C, the Zn atoms moved closer to the N4 coordination plane. This subtle geometry change in the ZnN4 sites alters the electron density on the Zn atoms (formally Zn2+), strongly impacting the catalytic performance for the peroxidase-like decomposition of H2O2. The catalyst obtained at 800 °C (Zn-N-C-800) offered the best performance for H2O2 decomposition. This work provides valuable new insights about the evolution of porphyrin-like single metal sites on N-doped carbons from ZIF precursors and the factors influencing SAC activity.