Highly photoactive MOFs can be engineered via various strategies for the purpose of extended visible light absorption, more efficient generation, separation and transfer of charge carriers, as well as good recyclability.

Porous materials with open metal sites have been investigated to separate various gas mixtures.H owever,o pen metal sites showt he limitation in the separation of some challenging gas mixtures,s uch as C 2 H 2 /CO 2 .H erein, we propose an ew type of ultra-strong C 2 H 2 nano-trap based on multiple binding interactions to efficiently capture C 2 H 2 molecules and separate C 2 H 2 /CO 2 mixture.T he ultra-strong acetylene nano-trap shows ab enchmark Q st of 79.1 kJ mol À1 for C 2 H 2 ,arecordh igh pure C 2 H 2 uptake of 2.54 mmol g À1 at 1 10 À2 bar,a nd the highest C 2 H 2 /CO 2 selectivity (53.6), making it as an ew benchmark material for the capture of C 2 H 2 and the separation of C 2 H 2 /CO 2 .T he locations of C 2 H 2 molecules within the MOF-based nanotrap have been visualized by the in situ single-crystal X-ray diffraction studies,which also identify the multiple binding sites accountable for the strong interactions with C 2 H 2 .

Herein, we show how the spatial environment in the functional pores of covalent organic frameworks (COFs) can be manipulated in order to exert control in catalysis. The underlying mechanism of this strategy relies on the placement of linear polymers in the pore channels that are anchored with catalytic species, analogous to outer‐sphere residue cooperativity within the active sites of enzymes. This approach benefits from the flexibility and enriched concentration of the functional moieties on the linear polymers, enabling the desired reaction environment in close proximity to the active sites, thereby impacting the reaction outcomes. Specifically, in the representative dehydration of fructose to produce 5‐hydroxymethylfurfural, dramatic activity and selectivity improvements have been achieved for the active center of sulfonic acid groups in COFs after encapsulation of polymeric solvent analogues 1‐methyl‐2‐pyrrolidinone and ionic liquid.

This work describes a facile approach to modify metal-organic frameworks (MOFs) with ionic liquids (ILs), rendering them as useful heterogeneous catalysts for CO chemical fixation. An amino-functionalized imidazolium-based ionic liquid is firmly grafted into the porous MOF, MIL-101-SOH by the acid-base attraction between positively charged ammonium groups on the IL and negatively charged sulfonate groups from the MOF. Analyses by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, H NMR, and N sorption experiments reveal the MOF-supported ionic liquid (denoted as IL@MOF) material remains intact while functioning as a recyclable heterogeneous catalyst that can efficiently convert CO and epichlorohydrin into chloropropene carbonate without the addition of a cocatalyst.

Methyl groups are introduced on the pore walls of a metal–organic framework to enhance the separation performance of C2H6/C2H4.

Atomically dispersed metal catalysts anchored on nitrogendoped (N-doped) carbons demand attention due to their superior catalytic activity relative to that of metal nanoparticle catalysts in energy storage and conversion processes. Herein, we introduce a simple and versatile strategy for the synthesis of hollow N-doped carbon capsules that contain one or more atomically dispersed metals (denoted as H−M−N x −C and H−M mix −N x −C, respectively, where M = Fe, Co, or Ni). This method utilizes the pyrolysis of nanostructured core−shell precursors produced by coating a zeolitic imidazolate framework core with a metal−tannic acid (M−TA) coordination polymer shell (containing up to three different metal cations). Pyrolysis of these core−shell precursors affords hollow N-doped carbon capsules containing monometal sites (e.g., Fe−N x , CoN x , or Ni−N x ) or multimetal sites (Fe/Co−N x , Fe/Ni−N x , Co/Ni−N x , or Fe/Co/Ni−N x ). This inventory allowed exploration of the relationship between catalyst composition and electrochemical activity for the oxygen reduction reaction (ORR) in acidic solution.and H−FeCoNi−N x −C were particularly efficient ORR catalysts in acidic solution. Furthermore, the H− Fe−N x −C catalyst exhibited outstanding initial performance when applied as a cathode material in a proton exchange membrane fuel cell. The synthetic methodology introduced here thus provides a convenient route for developing nextgeneration catalysts based on earth-abundant components.

This review article summarizes the recent progress in the pore surface engineering of covalent organic frameworks (COFs) for various applications.

Chemical functionalization or docking of transition-metal ions in covalent organic frameworks (COFs) is of importance for calibrating properties and widening potential applications. In this work, we demonstrate the successful decoration of COF with vanadium as exemplified in the context of post-synthetically modifying two-dimensional COF that features eclipsed stacking structure, large pores, hydroxyl functionalities, high thermal and chemical stability using vanadyl acetylacetonate. The potent catalytic behavior of vanadiumdecorated COF was systematically investigated in the reactions of Prins condensation and sulfide oxidation, which revealed its excellent catalytic performances in terms of efficacious activity, preservation of framework crystallinity and reusability. Our work not only contributes the first ever report of vanadium-decorated COF-catalyzed Prins reaction and sulfide oxidation but paves a new way for docking COF with metals for a broad range of applications.