Post-synthetic metalation of metal–organic frameworks

Abstract

Post-synthetic metalation (PSMet) offers expansive scope for a targeted approach to tailoring the properties of MOFs. Numerous methods for carrying-out PSMet chemistry have been reported, however, these can be categorized into three general strategies: (a) addition to coordinating groups; (b) counter-ion exchange in charged frameworks; or, (c) host-guest encapsulation of metal-containing entities within the pores of the framework. PSMet has been applied to enhance the performance characteristics of parent MOFs for gas storage and separation, and catalysis. Notably, PSMet is a prominent strategy in the field of MOF catalysis as it offers a route to design size-selective catalysts, based on the premise of reticular chemistry in MOFs and the ability to incorporate a range of catalytically-active metal centres. Other applications for materials produced via or utilising PSMet strategies include enhancing gas storage or molecular separations, the triggered release of drugs, sensing and tunable light emission for luminescent materials. This review surveys seminal examples of PSMet to highlight the broad scope of this technique for enhancing the performance characteristics of MOFs and to demonstrate how the PSMet concept can be developed for future applications.

Electrocatalytic Metal–Organic Frameworks for Energy Applications

“…[101][102][103] (MAF-X27-OH). [104] MAF-X27-Cl displayed poor OER activity.F ollowingt he replacement of Cl À with HO À ,M AF-X27-OH, deposited on GCEs using Nafion as ab inder,e xhibitede nhanced OER activity and achieves 10 mA cm À2 at an overpotential of 387 mV in 1.0 m KOH.…”

Photochemical Hydrogen Production with Metal–Organic Frameworks

“…Metal-nanoparticles [31] and molecular catalysts that would not withstand the harsh synthesis conditions of MOFs have to be installed postsynthetically. A large number of methods for post-synthetic modifications on parent MOFs that contain for example amino groups [17,32] or open coordination sites [33][34][35] have been developed throughout recent years. Another way is to perform a post-synthetic ligand exchange (PSE) (also referred to as solvent-assisted linker exchange = SALE) with a linker that matches the topology of the linkers in the parent framework, [36] and that carries the desired functionality.…”

A Sr 2+ -metal–organic framework with high chemical stability: synthesis, crystal structure and photoluminescence property

“…However, the unsatisfactory stability of MOFs, particularly poor water tolerance, limits their practical applications in many fields, such as proton conduction, aqueousphase catalysis, ethanol-water separation, drug delivery in organisms and water desalination. Meanwhile, many MOFs with low thermal stability are also hindered in gas adsorption and separation [6,7]. This situation inspires scientists to explore novel MOFs with exceptional thermal and chemical stability [8][9][10], which however still remains a great challenge [11][12][13].…”