Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

Abstract

Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of coordinatively unsaturated metal sites in their crystalline lattice that can act as Lewis acid sites promoting organic transformations, including aerobic oxidation reactions of various substrates such as hydrocarbons, alcohols, and sulfides. This review article summarizes the existing Co-based MOFs for oxidation reactions organized according to the nature of substrates like hydrocarbon, alcohol, olefin, and water. Both aerobic conditions and peroxide oxidants are discussed. Emphasis is placed on comparing the advantages of using MOFs as solid catalysts with respect to homogeneous salts in terms of product selectivity and long-term stability. The final section provides our view on future developments in this field.

Water-Driven Structural Transformation in Cobalt Trimesate Metal-Organic Frameworks

“…All the patterns reported in Figure 1a,b were equivalent, and they were all different from the patterns reported for other metal trimesates. The structures used for the comparison were obtained by search in articles collection databases [24,[35][36][37][38][39][40][41][42][43][44][45][46]48,[51][52][53][54] and in the Cambridge Structural Database (CCSD, [55]) using as a query in ConQuest one cobalt atom bound to one oxygen atom of a BTC linker and coordinated to two additional oxygen atoms through a single bond. The most intense reflection of the pattern was centered at 10.2 • , corresponding with a d-spacing of 8.7 Å.…”

“…Future investigations should be aimed at the determination of the KCL-102 structure and surface area and to its testing for the several energy-related applications where cobaltbased MOFs are known to be excellent in regard to water harvesting, heat exchangers, oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and CO and other oxidation reactions [54].…”

“…This transformation is very quick in direct contact with water. Furthermore, unlike several other MOFs, KCL-102 does not become amorphous upon hydration, but it is converted to a well-known crystalline phase, Co Future investigations should be aimed at the determination of the KCL-102 structure and surface area and to its testing for the several energy-related applications where cobaltbased MOFs are known to be excellent in regard to water harvesting, heat exchangers, oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and CO and other oxidation reactions [54].…”

MOF-Derived Co3O4 Nanoparticles Catalyzing Hydrothermal Deoxygenation of Fatty Acids for Alkane Production

“…As shown in Figure S1a , the diffraction peaks appear at 15.2, 17.7, 18.9, 27.1, 32.8, 34.0, and 35.7° for Co-BTC can be ascribed to [Co 3 (BTC) 2 (H 2 O) 12 ], 20 , 22 , 23 which indicates that MOF precursors Co-BTC are assuredly synthesized. As depicted in Figure S1b , obvious diffraction peaks of C, Co, and Co 3 O 4 appear in the XRD patterns.…”

Enhancing the electrocatalytic activities of metal organic frameworks for the oxygen evolution reaction with bimetallic groups

“…The presence of these two metals with these two oxidation states could also be another contributing factor to the enhanced activity exhibited by this bimetallic MOF toward the OER, as shown by Dhakshinamoorthy et al for related bimetallic MOFs (named Co x Ni 3− x (HAB) 2 MOF-2) towards the OER. 37 The partial electron transfer from the Ni 2+ to Co 3+ sites in the material was also reported to be responsible for enhancing the electrocatalytic performance exhibited by these bimetallic MOFs toward the OER.…”