Hypercrosslinked Metal-Organic Polyhedra Electrolyte with High Transference Number and Fast Conduction of Li Ions.

Solid-state electrolytes (SSEs) with high Li-ion transference numbers and fast ionic conductivity are urgently needed for technological innovations in lithium-metal batteries. To promote the dissociation of ion pairs and overcome the mechanical brittleness and interface defects caused by traditional fillers in polymeric electrolytes, we designed and fabricated a cationic hypercrosslinking metal-organic polyhedra (HCMOPs) polymer as SSE. Benefiting a three-component synergistic effect: cationic MOPs, branched polyethyleneimine macromonomer and polyelectrolyte units, the Li-HCMOP electrolyte possesses a high Li-ion conductivity, a high Li-ion transference number and a low activation energy.

Bottom-Up Synthesis of Covalent Organic Frameworks with Quasi-Three-Dimensional Integrated Architecture via Interlayer Cross-Linking.

Developing strategies to enhance the structural robustness of covalent organic frameworks (COFs) is of great importance. Here, we rationally design and synthesize a class of cross-linked COFs (COFs), in which the two-dimensional (2D) COF layers are anchored and connected by polyethylene glycol (PEG) or alkyl chains through covalent bonds. The bottom-up fabrication of these COFs is achieved by the condensation of cross-linked aldehyde monomers and tritopic amino monomers.

Highly Robust Microporous Metal-Organic Frameworks for Efficient Ethylene Purification under Dry and Humid Conditions.

Two C H -selective metal-organic framework (MOF) adsorbents with ultrahigh stability, high surface areas, and suitable pore size have been designed and synthesized for one-step separation of ethane/ethylene (C H /C H ) under humid conditions to produce polymer-grade pure C H . Experimental results reveal that these two MOFs not only adsorb a high amount of C H but also display good C H /C H selectivity verified by fixed bed column breakthrough experiments. Most importantly, the good water stability and hydrophobic pore environments make these two MOFs capable of efficiently separating C H /C H under humid conditions, exhibiting the benchmark performance among all reported adsorbents for separation of C H /C H under humid conditions.

Rationally Fabricating Three-Dimensional Covalent Organic Frameworks for Propyne/Propylene Separation.

Efficient propyne/propylene separation to obtain polymer-grade propylene is a crucial and challenging process in industrial production, but it has not yet been realized in the covalent organic framework (COF) field. Addressing this challenge, we synthesize two three-dimensional COF adsorbents via a [8 + 4] construction approach based on an octatopic aldehyde monomer. Upon using the continuous rotation electron diffraction technique and structural simulation, both COFs are successfully determined as rare topology.

Bottom-Up Synthesis of 8-Connected Three-Dimensional Covalent Organic Frameworks for Highly Efficient Ethylene/Ethane Separation.

Developing cost-/energy-efficient separation techniques for purifying ethylene from an ethylene/ethane mixture is highly important but very challenging in the industrial process. Herein, using a bottom-up [8 + 2] construction approach, we rationally designed and synthesized three three-dimensional covalent organic frameworks (COFs) with 8-connected networks, which can selectively remove ethane from an ethylene/ethane mixture with high efficiency. These COF materials, which are fabricated by the condensation reaction of a customer-designed octatopic aldehyde monomer with linear diamino linkers, possess high crystallinity, good structural robustness, and high porosity.

A Class of Rigid-Flexible Coupling Crystalline Crosslinked Polymers as Vapomechanical Actuators.

Fabricating mechanically responsive actuators that can efficiently convert external stimuli into mechanical work is of great significance for real-world applications. Herein, we rationally design a class of rigid-flexible coupling crystalline crosslinked polymers (CCPs) to fabricate vapomechanically responsive actuators. Interfacial condensation reactions of flexible macromers with rigid monomers afford a series of freestanding CCP membranes.

Fabrication of Biomolecule-Covalent-Organic-Framework Composites as Responsive Platforms for Smart Regulation of Fermentation Application.

Exploration of novel material platforms to protect biological preservatives and realize intelligent regulation during fermentation is of great significance in industry. Herein, we established an intelligent responsive platform by introducing antimicrobial biomolecules (nisin) into rationally designed covalent organic frameworks (COFs), resulting in a new type of "smart formulation", which could responsively inhibit microbial contamination and ensure the orderly progression of the fermentation process. The encapsulated biomolecules retained their activity while exhibiting enhanced stability and pH-responsive releasing process (100% bacteriostatic efficiency at a pH of 3), which can ingeniously adapt to the environmental variation during the fermentation process and smartly fulfill the regulation needs.

Tethering Flexible Polymers to Crystalline Porous Materials: A Win-Win Hybridization Approach.

Crystalline porous materials (CPMs) have been widely studied over the past few decades due to their well-defined, customizable, and porous structures. However, the limited stability and machinability restrict their particle applications. Recently, a new trend to use hybrid strategies to bridge the gap between CPMs and flexible polymers has emerged as an effective solution to tackle the above issues.

Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes.

A new homochiral was prepared by a new chiral organic linker of ()-4,4'-(6,6'-dichloro-2,2'-diethoxyl-[1,1'-binaphthalene]-4,4'-diyl)dibenzoic acid () and ZrCl under solvothermal conditions. Its structure was determined by Pawley refinement on the basis of the measured PXRD pattern determined for , and it showed that the obtained chiral MOF crystallized in the 2 space group with the same topological structure as that of UiO-66. The obtained can be a very active catalyst to catalyze aldehyde cyanosilylation.

Dual Heterogeneous Catalyst Pd-Au@Mn(II)-MOF for One-Pot Tandem Synthesis of Imines from Alcohols and Amines.

A new Mn(II) metal-organic framework (MOF) 1 was synthesized by the combination of 4,4,4-trifluoro-1-(4-(pyridin-4-yl)phenyl)butane-1,3-dione (L) and Mn(OAc) in solution. 1 features a threefold-interpenetrating NbO net containing honeycomb-like channels, in which the opposite Mn(II)···Mn(II) distance is 23.5075(10) Å.

Au@Cu(II)-MOF: Highly Efficient Bifunctional Heterogeneous Catalyst for Successive Oxidation-Condensation Reactions.

A new composite Au@Cu(II)-MOF catalyst has been synthesized via solution impregnation and full characterized by HRTEM, SEM-EDS, XRD, gas adsorption-desorption, XPS, and ICP analysis. It has been shown here that the Cu(II)-framework can be a useful platform to stabilize and support gold nanoparticles (Au NPs). The obtained Au@Cu(II)-MOF exhibits a bifunctional catalytic behavior and is able to promote selective aerobic benzyl alcohol oxidation-Knoevenagel condensation in a stepwise way.

Pd@Cu(II)-MOF-Catalyzed Aerobic Oxidation of Benzylic Alcohols in Air with High Conversion and Selectivity.

A new 3D porous Cu(II)-MOF (1) was synthesized based on a ditopic pyridyl substituted diketonate ligand and Cu(OAc)2 in solution, and it features a 3D NbO motif which is determined by the X-ray crystallography. Furthermore, the Pd NPs-loaded hybrid material Pd@Cu(II)-MOF (2) was prepared based on 1 via solution impregnation, and its structure was confirmed by HRTEM, SEM, XRPD, gas adsorption-desorption, and ICP measurement. 2 exhibits excellent catalytic activity (conversion, 93% to >99%) and selectivity (>99% to benzaldehydes) for various benzyl alcohol substrates (benzyl alcohol and its derivatives with electron-withdrawing and electron-donating groups) oxidation reactions in air.