Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis

Abstract

Recent progress in the synthesis and characterization of metal–organic frameworks (MOFs) has opened the door to an increasing number of possible catalytic applications. The great versatility of MOFs creates a large chemical space, whose thorough experimental examination becomes practically impossible. Therefore, computational modeling is a key tool to support, rationalize, and guide experimental efforts. In this outlook we survey the main methodologies employed to model MOFs for catalysis, and we review selected recent studies on the functionalization of their nodes. We pay special attention to catalytic applications involving natural gas conversion.

Identifying promising metal–organic frameworks for heterogeneous catalysis via high‐throughput periodic density functional theory

“…Due in part to the large unit cells of many MOFs, the most common approach when modeling MOFs for any catalytic reaction is to crop and terminate the periodic structure to create a finite‐sized cluster model of the proposed active site, often consisting of no more than a few dozen atoms . An appropriate choice of where to artificially terminate the MOF unit cell is often not immediately obvious, and this approach is therefore not amenable to HT screening of MOFs with widely varying topologies.…”

Switching in Metal–Organic Frameworks

“…As the MOF synthetic toolkit expands, the realization of MOFs with targeted designs becomes increasingly facile . Moreover, owing to the regularity and crystallinity of MOF structures, computational studies have been successful, and recent high‐throughput screening studies have helped in effectively guiding experimentalists . In situ or post‐synthetic modification, structural and pendant ligands, primary and auxiliary metals and metal clusters, as well as pore sizes, shape, acidity, and hydrophobicity modifications can direct the uptake capacities, selectivity, sensitivity, and mobility of MOFs and MOF components .…”

“…[20,28] Moreover,o wing to the regularity and crystallinity of MOF structures,c omputational studies have been successful, and recent high-throughput screening studies have helped in effectively guiding experimentalists. [29][30][31][32][33] In situ or post-synthetic modification, structural and pendant ligands,p rimary and auxiliary metals and metal clusters,a s well as pore sizes,s hape,a cidity,a nd hydrophobicity modifications can direct the uptake capacities,selectivity,sensitivity,and mobility of MOFs and MOF components. [20,28] MOFs have greater surface areas and higher degrees of tunability than other porous materials,s uch as zeolites,e ssential for applications including selective catalysis and low density,high capacity gas storage.C ompared to porous polymers,M OF crystallinity,p eriodicity,a nd permanent porosity makes characterization by X-ray diffraction techniques more amenable.Finally,while covalent organic frameworks (COFs) are often lighter and have larger pore structures that are more stable than in MOF counterparts,M OFs boast more diverse synthetic conditions and the additional tunability provided by the metal structural building unit (SBU)c an permit facile incorporation of photochemical properties,c atalytic centers, and gas sorption sites.…”

Biotechnological Application of Surface Modified Cerium Oxide Nanoparticles

“…Such an approach for enzyme immobilization speaks for high enzyme activity without modification and distortion of the active site of the enzyme. As the active site is hindered least by the nanomatrix, such steric accessibility ensures greater access of incoming substrate as well as outgoing products (Bernales et al, 2018). Other advantages involved with the use of enzymes immobilized on surface-modified nanoparticles include enhanced stability, continuous operations, catalyst recycling and improvement in their catalytic action (Samui et al, 2016;Zhang et al, 2017).…”