Advancing Membrane Technology: Ordered Macroporous ZIF-67 as a Filler in Mixed Matrix Membranes for Enhanced Propylene/Propane Separation.

Conventional separation technologies for valuable commodities require substantial energy, accounting for 10%-15% of global consumption. Mixed-matrix membranes (MMMs) offer a promising solution by combining processable polymers with selective inorganic fillers. Here, the potential of using ordered microporous structured materials is demonstrated as MMM fillers. The use of ordered macroporous ZIF-67 in combination with the well-known 6FDA-DAM polymer leads to superior performance in the important separation of propylene from propane. The enhanced performance can be rationalized with the help of advanced microscopy, which demonstrates that the polymer is able to penetrate the macroporous network around which the MOF (Metal-Organic Framework) is synthesized, resulting in a much better interphase between the two components and the homogeneous distribution of the filler, even at high loadings.

Enabling the Methanol Economy: Opportunities and Challenges for Heterogeneous Catalysis in the Production of Liquid Fuels via Methanol.

ConspectusThirty years ago, George A. Olah proposed the concept of the methanol economy, where methanol replaces fossil fuels as a means of energy storage, ground transportation fuel, and raw material for the manufacture of other carbon-based products. Over the years, with rising global warming concerns, the concept has evolved. A special interest is devoted to the development of catalytic processes that allow the transformation of carbon dioxide, via methanol, into CO2 neutral liquid hydrocarbons. These products could replace the oil-based fuels currently used by combustion engines. The rapid depletion of such fuels would avoid a considerable amount of CO2 emissions during the current energy transition.Over the past decade, we have focused on different key processes that should allow for maximal atom efficiency and, therefore, minimal energy consumption in a field, CO2 valorization, that can easily become a zero-sum game. In this Account, we highlight the importance of catalyst design to overcome the process challenges in the production of liquid fuels from methanol. Additionally, progress in multifunctional catalysts able to directly convert, in one single reactor, CO2 to liquid fuels is also discussed in detail. This integrated option is of particular interest since it allows an important decrease in operational units while increasing throughput by converting, in situ, a thermodynamically limited intermediate.

Pore-Networked Gels: Permanently Porous Ionic Liquid Gels with Linked Metal-Organic Polyhedra Networks.

Porous liquids (PLs) are attractive materials because of their capability to combine the intrinsic porosity of microporous solids and the processability of liquids. Most of the studies focus on the synthesis of PLs with not only high porosity but also low viscosity by considering their transportation in industrial plants. However, a gap exists between PLs and solid adsorbents for some practical cases, where the liquid characteristics and mechanical stability without leakage are simultaneously required. Here, we fill in this gap by demonstrating a new concept of pore-networked gels, in which the solvent phase is trapped by molecular networks with accessible porosity. To achieve this, we fabricate a linked metal-organic polyhedra (MOPs) gel, followed by exchanging the solvent phase with a bulky liquid such as ionic liquids (ILs); the dimethylformamide solvent trapped inside the as-synthesized gel is replaced by the target IL, 1-butyl-3-methylimidazolium tetrafluoroborate, which in turn cannot enter MOP pores due to their larger molecular size. The remaining volatile solvents in the MOP cavities can then be removed by thermal activation, endowing the obtained IL gel (Gel_IL) with accessible microporosity. The CO2 capacities of the gels are greatly enhanced compared to the neat IL. The exchange with the IL also exerts a positive influence on the final gel performances such as mechanical properties and low volatility. Besides ILs, various functional liquids are shown to be amenable to this strategy to fabricate pore-networked gels with accessible porosity, demonstrating their potential use in the field of gas adsorption or separation.

Mixed Matrix Membranes with Surface Functionalized Metal-Organic Framework Sieves for Efficient Propylene/Propane Separation.

Membrane technology, regarded as an environmentally friendly and sustainable approach, offers great potential to address the large energy penalty associated with the energy-intensive propylene/propane separation. Quest for molecular sieving membranes for this important separation is of tremendous interest. Here, a fluorinated metal-organic framework (MOF) material, known as KAUST-7 (KAUST: King Abdullah University of Science and Technology) with well-defined narrow 1D channels that can effectively discriminate propylene from propane based on a size-sieving mechanism, is successfully incorporated into a polyimide matrix to fabricate molecular sieving mixed matrix membranes (MMMs). Markedly, the surface functionalization of KAUST-7 nanoparticles with carbene moieties affords the requisite interfacial compatibility, with minimal nonselective defects at polymer-filler interfaces, for the fabrication of a molecular sieving MMM. The optimal membrane with a high MOF loading (up to 45 wt.%) displays a propylene permeability of ≈95 barrer and a mixed propylene/propane selectivity of ≈20, far exceeding the state-of-the-art upper bound limits. Moreover, the resultant membrane exhibits robust structural stability under practical conditions, including high pressures (up to 8 bar) and temperatures (up to 100 °C). The observed outstanding performance attests to the importance of surface engineering for the preparation and plausible deployment of high-performance MMMs for industrial applications.

Designing a Multifunctional Catalyst for the Direct Production of Gasoline-Range Isoparaffins from CO2.

The production of carbon-neutral fuels from CO2 presents an avenue for causing an appreciable effect in terms of volume toward the mitigation of global carbon emissions. To that end, the production of isoparaffin-rich fuels is highly desirable. Here, we demonstrate the potential of a multifunctional catalyst combination, consisting of a methanol producer (InCo) and a Zn-modified zeolite beta, which produces a mostly isoparaffinic hydrocarbon mixture from CO2 (up to ∼85% isoparaffin selectivity among hydrocarbons) at a CO2 conversion of >15%. The catalyst combination was thoroughly characterized via an extensive complement of techniques. Specifically, operando X-ray absorption spectroscopy (XAS) reveals that Zn (which plays a crucial role of providing a hydrogenating function, improving the stability of the overall catalyst combination and isomerization performance) is likely present in the form of Zn6O6 clusters within the zeolite component, in contrast to previously reported estimations.

The Current Status of MOF and COF Applications.

The amalgamation of different disciplines is at the heart of reticular chemistry and has broadened the boundaries of chemistry by opening up an infinite space of chemical composition, structure, and material properties. Reticular design has enabled the precise prediction of crystalline framework structures, tunability of chemical composition, incorporation of various functionalities onto the framework backbone, and as a consequence, fine-tuning of metal-organic framework (MOF) and covalent organic framework (COF) properties beyond that of any other material class. Leveraging the unique properties of reticular materials has resulted in significant advances from both a fundamental and an applied perspective. Here, we wish to review the milestones in MOF and COF research and give a critical view on progress in their real-world applications. Finally, we briefly discuss the major challenges in the field that need to be addressed to pave the way for industrial applications.

Solution processable metal-organic frameworks for mixed matrix membranes using porous liquids.

The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.

Metal-Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives.

More than 95% (in volume) of all of today's chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic research field. In this regard, metal-organic frameworks (MOFs) offer great opportunities for the rational design of new catalytic solids, as highlighted by the unprecedented number of publications appearing over the past decade. In this review, the recent advances in the application of MOFs in heterogeneous catalysis are discussed. MOFs with intrinsic thermocatalytic activity, as hosts for the incorporation of metal nanoparticles, as precursors for the manufacture of composite catalysts and those active in photo- and electrocatalytic processes are critically reviewed. The review is wrapped up with our personal view on future research directions.

A Titanium Metal-Organic Framework with Visible-Light-Responsive Photocatalytic Activity.

The one-step synthesis and characterization of a new and robust titanium-based metal-organic framework, ACM-1, is reported. In this structure, which is based on infinite Ti-O chains and 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge-separation lifetimes. The suitable energies for band gap and conduction band minimum (CBM) offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates.

Molecular-Scale Hybrid Membranes Derived from Metal-Organic Polyhedra for Gas Separation.

The preparation and the performance of mixed matrix membranes based on metal-organic polyhedra (MOPs) are reported. MOP fillers can be dispersed as discrete molecular units (average 9 nm in diameter) when low filler cargos are used. In spite of the low doping amount (1.6 wt %), a large performance enhancement in permeability, aging resistance, and selectivity can be achieved. We rationalize this effect on the basis of the large surface to volume ratio of the filler, which leads to excellent dispersion at low concentrations and thus alters polymer packing. Although membranes based only on the polymer component age quickly with time, the performance of the resulting MOP-containing membranes meets the commercial target for postcombustion CO2 capture for more than 100 days.

Revisiting Nitrogen Species in Covalent Triazine Frameworks.

Covalent triazine frameworks (CTFs) are porous organic materials promising for applications in catalysis and separation due to their high stability, adjustable porosity, and intrinsic nitrogen functionalities. CTFs are prepared by ionothermal trimerization of aromatic nitriles; however, multiple side reactions also occur under synthesis conditions, and their influence on the material properties is still poorly described. Here we report the systematic characterization of nitrogen in CTFs using X-ray photoelectron spectroscopy. With the use of model compounds, we could distinguish several types of nitrogen species. By combining these data with textural properties, we unravel the influence that the reaction temperature, the catalyst, and the monomer structure and composition have on the properties of the resulting CTF materials.

Facile Method for the Preparation of Covalent Triazine Framework coated Monoliths as Catalyst Support: Applications in C1 Catalysis.

A quasi chemical vapor deposition method for the manufacture of well-defined covalent triazine framework (CTF) coatings on cordierite monoliths is reported. The resulting supported porous organic polymer is an excellent support for the immobilization of two different homogeneous catalysts: (1) an IrIIICp*-based catalyst for the hydrogen production from formic acid and (2) a PtII-based catalyst for the direct activation of methane via Periana chemistry. The immobilized catalysts display a much higher activity in comparison with the unsupported CTF operated in slurry because of improved mass transport. Our results demonstrate that CTF-based catalysts can be further optimized by engineering at different length scales.

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes.

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.