State of the Art and Prospects in Metal–Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis

Abstract

Metal–organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability and richness of their structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple and selective heterogeneous interactions and activations in these MOF-based nanocatalysts. Pyrolysis of MOF-nanoparticle composites forms highly porous N- or P-doped graphitized MOF-derived nanomaterials that are increasingly used as efficient catalysts especially in electro- and photocatalysis. This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years. The major parts are catalysis of organic and molecular reactions, electrocatalysis, photocatalysis, and views of prospects. Major challenges of our society are addressed using these well-defined heterogeneous catalysts in the fields of synthesis, energy, and environment. In spite of the many achievements, enormous progress is still necessary to improve our understanding of the processes involved beyond the proof-of-concept, particularly for selective methane oxidation, hydrogen production, water splitting, CO2 reduction to methanol, nitrogen fixation, and water depollution.

CO2 controls the oriented growth of metal-organic framework with highly accessible active sites

“…etal-organic frameworks (MOFs) are a new type of crystalline porous materials that are self-assembled by the coordination of metal cations/clusters with organic linkers 1 , which have broad applications in gas storage and separation [2][3][4] , catalysis 5 , sensor 6 , drug delivery 7 , etc. Particularly, MOFs have exhibited promising catalytic potentials towards many kinds of reactions owing to their designable metal-oxo clusters bridging organic linkers, modifiable structure, and intrinsic porosities 8 .…”

Metal–Organic Frameworks Based Electrocatalysts for the Oxygen Reduction Reaction

“…Thes ynthesis of MOFs possessing strong metal-ligand coordination bond, redox activity,donor-acceptor interactions,a nd mixed valency,i so fg reat necessity.T he coordination between the metal centers and organic ligands determines largely the stability,w hile other factors determine the conductivity. [30,38,39,130,131] Along this line,s ome MOFs such as porphyrin MOFs,p hthalocyanine-based conjugated MOFs and UiO family (UiO = Universitetet iO slo) show great promise as pristine electrocatalysts towards ORR. ii)C ovalent organic frameworks,w ith complete organic skeletons,p rovide great opportunities to facilely construct porous pure carbon materials with the precise control over heteroatom doping.…”

“…Fore xample,p ostsynthetic modifications of metal nodes and ligands of MOFs,s uch as multi-metal coordination and solventassisted ligand incorporation, should be used to enrich the types of MOFs. [131,135] Constructing more MOF composites (MOFs with metal clusters,p olyoxometallates,N Ps,s emiconductors,a nd polymers) and postprocessing of derivatives are the other two popular ways. [19,47,57] iv) In-situ characterization techniques would be very helpful to understand the evolution of the electrocatalyst and the mechanism of the electrocatalytic reaction.…”

Easy Processing of Metal–Organic Frameworks into Pellets and Membranes

“…Metal-Organic Frameworks (MOFs) are a versatile and broad class of crystalline materials with high porosity and a massive internal surface area [1][2][3]. These properties and the extraordinary diversity of their organic and inorganic building units make MOFs highly relevant in applications such as catalysis, sensors, batteries, biomedicine, and food safety [4][5][6][7][8]. Due to their synthetic versatility, long-range order, rich host-guest chemistry, uniform pore size, and high surface area, MOFs are particularly well-suited for the adsorption of a wide range of anthropogenic hazardous pollutants including NOx, SOx, CO, H 2 S, NH 3 , HCN, volatile organic compounds (VOCs), and polycyclic aromatic compounds (PAHs).…”