Versatile Cu-II metal-organic framework exhibiting high gas storage capacity with selectivity for CO2: conversion of CO2 to cyclic carbonate and other catalytic abilities

TitleVersatile Cu-II metal-organic framework exhibiting high gas storage capacity with selectivity for CO2: conversion of CO2 to cyclic carbonate and other catalytic abilities
Publication TypeJournal Article
Year of Publication2016
AuthorsDe, D, Pal, TK, Neogi, S, Senthilkumar, S, Das, D, Gupta, SSen, Bharadwaj, PK
JournalChemistry-A European Journal
Volume22
Issue10
Pagination3387-3396
Date PublishedMAR
ISSN0947-6539
Keywordsclick reactions, CO2 absorption, cyclic carbonate, heterogeneous catalysis, metal-organic frameworks
Abstract

A linear tetracarboxylic acid ligand, H4L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) L-M (M=Zn-II, Cu-II). Framework L-Cu can also be obtained from L-Zn by post- synthetic metathesis without losing crystallinity. Compared with L-Zn, the L-Cu framework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, L-Cu. At 77K, L-Cu absorbs 2.57wt% of H-2 at 1bar, which increases significantly to 4.67wt% at 36bar. The framework absorbs substantially high amounts of methane (238.38cm(3)g(-1), 17.03wt%) at 303K and 60bar. The CH4 absorption at 303K gives a total volumetric capacity of 166cm(3)(STP)cm(-3) at 35bar (223.25cm(3)g(-1), 15.95wt%). Interestingly, the NH2 groups in the linker, which decorate the channel surface, allow a remarkable 39.0wt% of CO2 to be absorbed at 1bar and 273K, which comes within the dominion of the most famous MOFs for CO2 absorption. Also, L-Cu shows pronounced selectivity for CO2 absorption over CH4, N-2, and H-2 at 273K. The absorbed CO2 can be converted to value-added cyclic carbonates under relatively mild reaction conditions (20bar, 120 degrees C). Finally, L-Cu is found to be an excellent heterogeneous catalyst in regioselective 1,3-dipolar cycloaddition reactions (click reactions) and provides an efficient, economic route for the one-pot synthesis of structurally divergent propargylamines through three-component coupling of alkynes, amines, and aldehydes.

DOI10.1002/chem.201504747
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)5.771
Divison category: 
Chemical Engineering & Process Development