A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

Abstract

A majority of metal-organic frameworks (MOFs) fail to preserve their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, therefore limiting their practical applications in many areas. The strategy demonstrated herein is the design and synthesis of an organic ligand that behaves as a buffer to drastically boost the aqueous stability of a porous MOF (JUC-1000), which maintains its structural integrity at low and high pH values. The local buffer environment resulting from the weak acid-base pairs of the custom-designed organic ligand also greatly facilitates the performance of JUC-1000 in the chemical fixation of carbon dioxide under ambient conditions, outperforming a series of benchmark catalysts.

Isoreticular Expansion of Metal–Organic Frameworks via Pillaring of Metal Templated Tunable Building Layers: Hydrogen Storage and Selective CO2 Capture

“…Further Cu‐eea‐3 , with larger cages and channels compared to the other two, can capture 143 cm 3 g −1 of CO 2 which was found to be the highest among the present Cu‐ eea ‐MOFs (Figure ). The CO 2 uptake capacities for the present MOFs are comparable with some of the previously explored Cu‐based MOFs for CO 2 capture (e.g., JUC‐1000: 125 cm 3 g −1 ; Cu‐NTTA: 115.6 cm 3 g −1 ; LIFM‐10: 129.5 mL g −1 ; LIFM‐11: 129.5 mL g −1 ) . (Table S2, Supporting Information) The adsorption enthalpies ( Q st ) for CO 2 adsorption were found to be 27.5, 36 and 17.7 kJ mol −1 for Cu‐eea‐1 , Cu‐eea‐2 and Cu‐eea‐3 , respectively, at zero coverage.…”

“…Metal–organic frameworks (MOFs) have grown rapidly as effective porous materials in the last couple of decades due to their utility in various applications . The MOFs provide a unique advantage for the introduction of desired functionalities, and therefore properties, by the judicious selection of appropriate organic building block prior to assembly of the components.…”

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

“…For instance, their weakc oordination-type bonding, renders many MOFs unstable in the humid or harsh environments, seriously limiting their applicability in catalysis. As such, it is thought that the field could benefitf rom new work focused on developing universal ways to improveM OF stability, [85] which will certainly open doors to new catalytic reactions. Most reports on MOF and MOF-derived catalysts are also limited to small, lab-scale preparation.…”

Rational Construction of an Exceptionally Stable MOF Catalyst with Metal‐Adeninate Vertices toward CO2 Cycloaddition under Mild and Cocatalyst‐Free Conditions

“…MOFs have also been applied to CO 2 cycloaddition reaction but under high temperature and high CO 2 pressure . However, cocatalysts are required in most cases, which results in extra waste and environmental pollution . To date, some strategies have been explored for the introduction of cocatalyst into MOFs by guest capture, postmodified skeleton and functionalization of organic ligands .…”

“…[24][25][26][27][28][29][30] However,c ocatalysts are required in most cases, which results in extra waste and environmental pollution. [31][32][33][34] To date, some strategies have been explored for the introduction of cocatalyst into MOFs by guest capture, postmodified skeleton and functionalization of organic ligands. [35][36][37][38][39][40] For example,aflexible ionic polymer can be inserted into aM OF host, which will efficientlyf ixate CO 2 with epoxides to afford cyclic carbonates under mild and cocatalyst-free conditions.…”