In Situ Transformation of an Amorphous Supramolecular Coating to a Hydrogen-Bonded Organic Framework Membrane to Trigger Selective Gas Permeation.

We introduce a "solution-processing-transformation" strategy, deploying solvent vapor as scaffolds, to fabricate high-quality hydrogen-bonded organic framework (HOF) membranes. This strategy can overcome the mismatch in processing conditions and crystal growth thermodynamics faced during the facile solution processing of the membrane. The procedure includes the vapor-trigged in situ transformation of dense amorphous supramolecules to crystalline HOF-16, with HOF-11 as the transient state. The mechanism involves a vapor-activated dissolution-precipitation equilibrium shifting and hydrogen bonding-guided molecule rearrangement, elucidated through combined experimental and theoretical analysis. Upon removal of the molecular scaffolds, the resulting HOF-16 membranes showcase significant improvement in hydrogen separation performance over their amorphous counterparts and previously reported HOF membranes. The method's broad applicability is evidenced by successfully extending it to other substrates and HOF structures. This study provides a fundamental understanding of guest-induced ordered supramolecular assembly and paves the way for the advanced manufacture of high-performance HOF membranes for gas separation processes.

Precise Pore Engineering of Zirconium Metal-Organic Cages for One-Step Ethylene Purification from Ternary Mixtures.

One-step purification of ethylene from ternary mixtures (C2H2, C2H4, and C2H6) can greatly reduce the energy consumption of the separation process, but it is extremely challenging. Herein, we use crystal engineering and reticular chemistry to introduce unsaturated bonds (ethynyl and alkyne) into ligands, and successfully design and synthesized two novel Zr-MOCs (ZrT-1-ethenyl and ZrT-1-alkyne). The introduction of carbon-carbon unsaturated bonds provides abundant adsorption sites within the framework while modulating the pore window size. Comprehensive characterization techniques including single crystal and powder X-ray diffraction, as well as electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) confirm that ZrT-1-ethenyl and ZrT-1-alkyne possess an isostructural framework with ZrT-1 and ZrT-1-Me, respectively. Adsorption isotherms and breakthrough experiments combined with theoretical calculations demonstrate that ZrT-1-ethenyl can effectively remove trace C2H2 and C2H6 in C2H4 and achieve separation of C2H2 from C2H4 and CO2. ZrT-1-ethenyl can also directly purify C2H4 in liquid solutions. This work provides a benchmark for MOCs that one-step purification of ethylene from ternary mixtures.

Confined Assembly of Hydrated Vanadium Oxide into Hollow Mesoporous Carbon Nanospheres for Fast and Stable K+ Storage Capability.

The rational structural design of the electrode materials is significant to enhance the electrochemical performance for potassium ion storage, benefiting from the shortened ion diffusion distance, increased conductivity, and pseudo-capacitance promotion. Herein, hydrated vanadium oxide (HVO) nanosheets with enriched oxygen defects are well confined into hollow mesoporous carbon spheres (HMCS), producing Od -VOH@C nanospheres through one-step hydrothermal reaction. Attributed to the restricted growth in the HMCS, the HVO nanosheets are loosely packed, generating abundant interfacial boundaries and large specific areas. As a result, Od -VOH@C nanospheres show increased reaction kinetics and well buffer the volume effects for the K+ storage. Od -VOH@C delivers stable capacities of 138 mAh g-1 at 2.0 A g-1 over 10 000 cycles in half-cells attributed to the high pseudo-capacitance contribution. The K+ storage mechanism of insertion and conversion reaction is confirmed by ex situ X-ray diffraction, Raman, and X-ray photoelectron spectroscopy analyses. Moreover, the symmetric potassium-ion capacitors of Od -VOH@C//Od -VOH@C deliver a high energy density of 139.6 Wh kg-1 at the power density of 948.3 W kg-1 .

Guest-Stimulated Nonplanar Porphyrins in Flexible Metal-Organic Frameworks.

Nonplanar porphyrins with out-of-plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest-stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules. Here, a series of porphyrinic zirconium metal-organic frameworks (MOFs) is reported that exhibit guest-stimulated breathing behavior. X-Ray diffraction analysis and skeleton deviation plots confirm that the material suffers from porphyrin distortion to form a ruffled geometry under the desorption of guest molecules. Further investigation reveals that not only the degree of nonplanarity can be precisely manipulated but also the partial distortion of porphyrin in a single crystal grain can be readily achieved. As Lewis acidic catalyst, the MOF with nonplanar Co-porphyrin exhibits active properties in catalyzing CO2 /propylene oxide coupling reactions. This porphyrin distortion system provides a powerful tool for manipulating nonplanar porphyrins in MOFs with individual distortion profiles for various advanced applications.

Fe-MOF with U-Shaped Channels for C2H2/CO2 and C2H2/C2H4 Separation.

The development of high-performance adsorbents is critical for the low-energy separation of acetylene. Herein, we synthesized an Fe-MOF (MOF, metal-organic framework) with U-shaped channels. The adsorption isotherms of C2H2, C2H4, and CO2 show that the adsorption capacity of acetylene is significantly larger than that of the other two gases. Meanwhile, the actual separation performance was verified by breakthrough experiments, indicating the potential to separate C2H2/CO2 and C2H2/C2H4 mixtures at normal temperatures. Grand Canonical Monte Carlo (GCMC) simulation demonstrates that the framework with U-shaped channels interacts more strongly with C2H2 than with C2H4 and CO2. The high C2H2 uptake and low adsorption enthalpy highlight Fe-MOF as a promising candidate for C2H2/CO2 separation with a low regeneration energy.

Engineering Double Sulfur-Vacancy in CoS1.097@MoS2 Core-Shell Heterojunctions for Hydrogen Evolution in a Wide pH Range.

Heterostructured nanomaterials have arisen as electrocatalysts with great potential for hydrogen evolution reaction (HER), considering their superiority in integrating different active components but are plagued by their insufficient active site density in a wide pH range. In this report, double sulfur-vacancy-decorated CoS1.097@MoS2 core-shell heterojunctions are designed, which contain a primary structure of hollow CoS1.097 nanocubes and a secondary structure of ultrathin MoS2 nanosheets. Taking advantage of the core-shell type heterointerfaces and double sulfur-vacancy, the CoS1.097@MoS2 catalyst exhibits pH-universal HER performance, achieving the overpotentials at 10 mA cm-2 of 190, 139, and 220 mV in 0.5 M H2SO4, 1.0 M KOH, and 1.0 M PBS, respectively. Systematic theoretical results show that the double sulfur-vacancy can endow the CoS1.097@MoS2 core-shell heterojunctions with promoted electron/mass transfer and enhanced reactive kinetics, thus boosting HER performance. This work clearly demonstrates an indispensable role of double sulfur-vacancy in enhancing the electrocatalytic HER performance of core-shell type heterojunctions under a wide pH operating condition.

Self-Assembly of Metal-Organic Frameworks on Graphene Oxide Nanosheets and In Situ Conversion into a Nickel Hydroxide/Graphene Oxide Battery-Type Electrode.

Graphene oxide (GO) has been widely reported as a supercapacitor electrode. Especially, GO is usually utilized to composite with electrochemical active materials, such as transition-metal oxide/hydroxide/sulfide, due to its considerable conductivity and mechanical strength. However, the ideal design and treatment for compositing GO with active materials are still challenging. Herein, an Ni-metal-organic framework (MOF) was self-assembled on GO nanosheets via the solvothermal method and was subsequently etched into the Ni(OH)2-GO composite electrode material through a gentle hydrolysis strategy. The GO support enables fast electron transport within the composite material, and the nickel hydroxide growth on GO nanosheets can prevent their aggregation, guaranteeing rapid ion migration. The improved Ni(OH)2-GO battery-type electrode features outstanding stability (capacity retention of 108% at 8000 cycles) and a considerable specific capacity (SC) of 1007.5 C g-1 at a current density of 0.5 A g-1. Compared with MOF-derived Ni(OH)2 obtained through hydrolysis, Ni(OH)2-GO only contains 7.41% wt GO, while its SC is almost 50% higher. An asymmetric supercapacitor has an energy density of 65.22 W h kg-1 and a power density of 395.27 W kg-1 utilizing p-phenylenediamine-functional reduced GO as the negative electrode, and it can maintain 73.08% capacity during 8000 cycles at a current density of 5 A g-1.

Scalable crystalline porous membranes: current state and perspectives.

Crystalline porous materials (CPMs) with uniform and regular pore systems show great potential for separation applications using membrane technology. Along with the research on the synthesis of precisely engineered porous structures, significant attention has been paid to the practical application of these materials for preparation of crystalline porous membranes (CPMBs). In this review, the progress made in the preparation of thin, large area and defect-free CPMBs using classical and novel porous materials and processing is presented. The current state-of-the-art of scalable CPMBs with different nodes (inorganic, organic and hybrid) and various linking bonds (covalent, coordination, and hydrogen bonds) is revealed. The advances made in the scalable production of high-performance crystalline porous membranes are categorized according to the strategies adapted from polymer membranes (interfacial assembly, solution-casting, melt extrusion and polymerization of CPMs) and tailored based on CPM properties (seeding-secondary growth, conversion of precursors, electrodeposition and chemical vapor deposition). The strategies are compared and ranked based on their scalability and cost. The potential applications of CPMBs have been concisely summarized. Finally, the performance and challenges in the preparation of scalable CPMBs with emphasis on their sustainability are presented.

Optimizing Fe-Based Metal-Organic Frameworks through Ligand Conformation Regulation for Efficient Dye Adsorption and C2 H2 /CO2 Separation.

Regulating the structure of metal-organic frameworks (MOFs) by adjusting the ligands reasonably is expected to enhance the interaction of MOFs on special molecules/ions, which has significant application value for the selective adsorption of guest molecules. Herein, two tricarboxylic ligands H3 L-Cl and H3 L-NH2 were designed and synthesized based on the ligand H3 TTCA by replacing part of the benzene rings with C=C bonds and modifying the chlorine and amino groups on the 4-position of the benzene ring. Two 3D Fe-MOFs (UPC-60-Cl and UPC-60-NH2 ) with the new topology types were constructed. As the C=C bonds of the ligands have flexible torsion angles, UPC-60-Cl features three types of irregular 2D channels, while UPC-60-NH2 has a cage with two types of windows on the surface. The synergistic effect of unique channels and modification of functional groups endows UPC-60-Cl and UPC-60-NH2 with high adsorption capacity for organic dyes. Compound UPC-60-Cl shows high adsorption capacity for CV (147.2 mg g-1 ), RHB (100.3 mg g-1 ), and MO (220.9 mg g-1 ), whereas UPC-60-NH2 exhibits selective adsorption of MO (158.7 mg g-1 ). Meanwhile, based on the diverse pore structure and modification of active sites, UPC-60-Cl and UPC-60-NH2 show the selective separation of equimolar C2 H2 /CO2 . Therefore, reasonable regulation of organic ligands plays a significant role in guiding the structure diversification and performance improvement of MOFs.

Conversion of Amorphous MOF Microspheres into a Nickel Phosphate Battery-Type Electrode Using the "Anticollapse" Two-Step Strategy.

Metal-organic frameworks (MOFs) have attracted great attention as templates for preparation of functional porous materials owing to their adjustable structures, rich porosity, and controllable components. However, collapsed templates during the conversion process hinder their application and synthesis of derivatives. In this study, we demonstrate a novel two-step etching strategy during which amorphous MOF microspheres are initially transformed into nickel hydroxide and then subsequently transformed into microspherical nickel phosphates. Through this strategy, the prepared nickel phosphates maintain the microspherical morphology of MOFs but with no MOF residuals, exhibiting ultrahigh specific surface area, uniform pore size, and good structural robustness. Examined as a supercapacitor electrode, they show an outstanding specific capacity of 820 C g-1 at 0.5 A g-1 and remarkable cycling stability of 88% capacity retention after 10 000 cycles. Moreover, an asymmetric supercapacitor constructed utilizing reduced graphene cross-linked with p-phenylenediamine oxide (PPD-rGO) as the cathode displays a preeminent energy density of 64.56 Wh kg-1 at a power density of 507 W kg-1. This strategy has important significance in guiding the preparation of high-performance MOF-derived electrodes.

Constructing Porous Carbon Electrocatalysts from Cobalt Complex-Decorated Micelles of Mesoporous Silica for Oxygen Reduction/Evolution Reaction.

The construction of a porous carbon structure with a high specific surface area is conducive to enhanced electrocatalytic activity due to the accessibility of active sites and improvement of the mass transfer. Herein, we explored the possibility of using micelles of mesoporous silica (MCM-48) as the carbon source to generate porous carbon under the confinement of MCM-48 channels. The complexes formed by Co2+ and 4,4'-bipyridine were in situ incorporated into the micelles to derive Co-related active sites (Co-Nx, Co, and Co3O4) for catalyzing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). After pyrolysis in the N2 atmosphere and subsequent removal of the MCM-48 skeleton, the target porous carbon electrocatalyst was obtained, which exhibited promising performance for both ORR and OER and has great potential as the cathode material for Zn-air battery application. This work not only confirms the effectiveness of using the micelles of MCM-48 as the carbon source for preparing the porous carbon materials, but also provides a new platform for design and synthesis of structurally controllable materials for energy-related electrocatalytic applications.

Tetrazole-Functionalized Zirconium Metal-Organic Cages for Efficient C2 H2 /C2 H4 and C2 H2 /CO2 Separations.

Isoreticular functionalization is a well-elucidated strategy for pore environment tuning and the basis of gas separation performance in extended frameworks. The extension of this approach to discrete porous molecules such as metal-organic cages (MOCs) is conceptually straightforward but hindered by synthetic complications, especially stability concerns. We report the successful isoreticular functionalization of a zirconium MOC with tetrazole moiety by bottom-up synthesis. The title compound (ZrT-1-tetrazol) shows promising C2 H2 /CO2 and C2 H2 /C2 H4 separation performance, as demonstrated by adsorption isotherms, breakthrough experiments, and density functional theory calculations. The design analogy between MOFs and highly stable MOCs may guide the synthesis of novel porous materials for challenging separation applications.

One-step Ethylene Purification from an Acetylene/Ethylene/Ethane Ternary Mixture by Cyclopentadiene Cobalt-Functionalized Metal-Organic Frameworks.

The separation of ethylene (C2 H4 ) from a mixture of ethane (C2 H6 ), ethylene (C2 H4 ), and acetylene (C2 H2 ) at normal temperature and pressure is a significant challenge. The sieving effect of pores is powerless due to the similar molecular size and kinetic diameter of these molecules. We report a new modification method based on a stable ftw topological Zr-MOF platform (MOF-525). Introduction of a cyclopentadiene cobalt functional group led to new ftw-type MOFs materials (UPC-612 and UPC-613), which increase the host-guest interaction and achieve efficient ethylene purification from the mixture of hydrocarbon gases. The high performance of UPC-612 and UPC-613 for C2 H2 /C2 H4 /C2 H6 separation has been verified by gas sorption isotherms, density functional theory (DFT), and experimentally determined breakthrough curves. This work provides a one-step separation of the ternary gas mixture and can further serve as a blueprint for the design and construction of function-oriented porous structures for such applications.

Optimizing Multivariate Metal-Organic Frameworks for Efficient C2H2/CO2 Separation.

Adsorptive separation of acetylene (C2H2) from carbon dioxide (CO2) promises a practical way to produce high-purity C2H2 required for industrial applications. However, challenges exist in the pore environment engineering of porous materials to recognize two molecules due to their similar molecular sizes and physical properties. Herein, we report a strategy to optimize pore environments of multivariate metal-organic frameworks (MOFs) for efficient C2H2/CO2 separation by tuning metal components, functionalized linkers, and terminal ligands. The optimized material UPC-200(Al)-F-BIM, constructed from Al3+ clusters, fluorine-functionalized organic linkers, and benzimidazole terminal ligands, demonstrated the highest separation efficiency (C2H2/CO2 uptake ratio of 2.6) and highest C2H2 productivity among UPC-200 systems. Experimental and computational studies revealed the contribution of small pore size and polar functional groups on the C2H2/CO2 selectivity and indicated the practical C2H2/CO2 separation of UPC-200(Al)-F-BIM.

Okra-Like Fe7 S8 /C@ZnS/N-C@C with Core-Double-Shelled Structures as Robust and High-Rate Sodium Anode.

Core-multishelled structures with controlled chemical composition have attracted great interest due to their fascinating electrochemical performance. Herein, a metal-organic framework (MOF)-on-MOF self-templated strategy is used to fabricate okra-like bimetal sulfide (Fe7 S8 /C@ZnS/N-C@C) with core-double-shelled structure, in which Fe7 S8 /C is distributed in the cores, and ZnS is embedded in one of the layers. The MOF-on-MOF precursor with an MIL-53 core, a ZIF-8 shell, and a resorcinol-formaldehyde (RF) layer (MIL-53@ZIF-8@RF) is prepared through a layer-by-layer assembly method. After calcination with sulfur powder, the resultant structure has a hierarchical carbon matrix, abundant internal interface, and tiered active material distribution. It provides fast sodium-ion reaction kinetics, a superior pseudocapacitance contribution, good resistance of volume changes, and stepwise sodiation/desodiation reaction mechanism. As an anode material for sodium-ion batteries, the electrochemical performance of Fe7 S8 /C@ZnS/N-C@C is superior to that of Fe7 S8 /C@ZnS/N-C, Fe7 S8 /C, or ZnS/N-C. It delivers a high and stable capacity of 364.7 mAh g-1 at current density of 5.0 A g-1 with 10 000 cycles, and registers only 0.00135% capacity decay per cycle. This MOF-on-MOF self-templated strategy may provide a method to construct core-multishelled structures with controlled component distributions for the energy conversion and storage.

Accurately Regulating the Electronic Structure of Nix Sey @NC Core-Shell Nanohybrids through Controllable Selenization of a Ni-MOF for pH-Universal Hydrogen Evolution Reaction.

N-doped carbon-encapsulated transition metal selenides (TMSs) have garnered increasing attention as promising electrocatalysts for hydrogen evolution reaction (HER). Accurately regulating the electronic structure of these nanohybrids to reveal the underlying mechanism for enhanced HER performances is still challenging and thus requires deep excavation. Herein, a series of pomegranate-like Nix Sey @NC core-shell nanohybrids (including Ni0.85 Se @ NC, NiSe2 @NC, and NiSe@NC) through controllable selenization of a Ni-MOF precursor is reported. The component of the nanohybrids can be fine-tuned by tailoring the selenization temperature and feed ratio, through which the electronic structure can be synchronously regulated. Among these nanohybrids, the Ni0.85 Se @ NC exhibits the optimum pH-universal HER performance with overpotentials of 131, 135, and 183 mV in 0.5 m H2 SO4 , 1.0 m KOH, and 1.0 m PBS, respectively, at 10 mA cm-2 , which are attributed to the increased partial density of state at the Fermi level and effective van der Waals interactions between Ni0.85 Se and NC matrix explained by density functional theory calculations.

Fabrication of (4, 10) and (4, 12)-Connected Multifunctional Zirconium Metal-Organic Frameworks for the Targeted Adsorption of a Guest Molecule.

Following the principle of a topology guide, a zirconium MOF (PCN-207) based on the H4TPTA ligand (tetramethyl(4,4',4″,4‴-(pyrazine-2,3,5,6-tetrayl))tetrabenzoic acid) with C2 symmetry and an 8-connected Zr6(µ3-OH)8(OH)8]8+ cluster with D4h symmetry has been synthesized. PCN-206 can also be obtained by modulating the benzoic acid usage to change the flexibility of the H4TPTA ligand. The unique positions of 8-connected Zr6 clusters in the flu and scu networks and the flexibility of the tetratopic primary linker enable the precise insertion of fumarate (FA), 1,4-benzenedicarboxylic acid (H2BDC), and even 2,6-naphthalenedicarboxylic acid (H2NDC) in a one-pot reaction. Auxiliary linkers are used to generate new MOF structures or topologies or to split the pore spaces, which may significantly change the porosity and chemical and physical properties of scaffold MOFs. The results provide a successful strategy for the rational design of multicomponent Zr-MOFs. Because of differences in composition and configuration between structures, PCN-207 shows the highest separation capability of light hydrocarbons; moreover, PCN-206 exhibits the highest adsorption capacity of 2,4-D and DCF among MOFs at present.

Sequential Solid-State Transformations Involving Consecutive Rearrangements of Secondary Building Units in a Metal-Organic Framework.

Solid-state transformations in metal-organic framework (MOF) systems are important phenomena and have led to the creation of new MOF structures. Solid-state transformations from interpenetrated to non-interpenetrated networks involving rearrangement of secondary building units (SBUs) in a single-crystal-to-single-crystal (SCSC) fashion have not been explored to date. Herein, we report the sequential, thermally stimulated solid-state transformations in a barium-organic framework ( UPC-600 ). The two-fold interpenetrated framework of  UPC-600  is converted at 373 K to UPC-601 , a non-interpenetrated framework. This proceeds in a SCSC fashion and involves the rearrangement of two proximate rod-shaped SBUs in different nets to generate a new rod-shaped SBU. At 473 K, a continuous solid-state transformation involving a second rearrangement occurred,  UPC-601  converted to UPC-602  by the rearrangement of the 1D rod-shaped SBU to a 2D layer SBU. This is the first example of such a thermally-driven stepwise transformation involving simultaneous cleavage and regeneration of multiple bonds. This result will enable detailed studies of solid-state transformations, and encourages a deep understanding of the role of solid-state transformations in the synthesis of MOF materials.

Sequential Solid-State Transformations Involving Consecutive Rearrangements of Secondary Building Units in a Metal-Organic Framework (MOF).

Solid-state transformations in metal-organic frameworks (MOFs) are important and have led to the creation of new MOF structures. Solid-state transformations from interpenetrated to non-interpenetrated networks involving rearrangement of secondary building units (SBUs) in a single-crystal-to-single-crystal (SCSC) fashion have not been explored to date. Herein, we report the sequential, thermally stimulated solid-state transformations in a barium-organic framework (UPC-600). The two-fold interpenetrated framework of UPC-600 is converted at 373 K into UPC-601, a non-interpenetrated framework. This proceeds in a SCSC fashion and involves the rearrangement of two proximate rod-shaped SBUs in different nets to generate a new rod-shaped SBU. At 473 K, a continuous solid-state transformation involving a second rearrangement occurred, UPC-601 converted into UPC-602 by the rearrangement of the 1D rod-shaped SBU to a 2D layer SBU. This is the first example of such a thermally driven stepwise transformation involving simultaneous cleavage and regeneration of multiple bonds.

Cross-Linking between Sodalite Nanoparticles and Graphene Oxide in Composite Membranes to Trigger High Gas Permeance, Selectivity, and Stability in Hydrogen Separation.

Thin membranes (900 nm) were prepared by direct transformation of infiltrated amorphous precursor nanoparticles, impregnated in a graphene oxide (GO) matrix, into hydroxy sodalite (SOD) nanocrystals. The amorphous precursor particles rich in silanols (Si-OH) enhanced the interactions with the GO, thus leading to the formation of highly adhesive and stable SOD/GO membranes via strong bonding. The cross-linking of SOD nanoparticles with the GO in the membranes promoted both the high gas permeance and enhanced selectivity towards H2 from a mixture containing CO2 and H2 O. The SOD/GO membranes are moisture resistance and exhibit steady separation performance (H2 permeance of about 4900 GPU and H2 /CO2 selectivity of 56, with no degradation in performance during the test of 50 h) at high temperature (200 °C) under water vapor (4 mol %).