Rhodium Hydrogenation Catalysts Supported in Metal Organic Frameworks: Influence of the Framework on Catalytic Activity and Selectivity

Abstract

The cationic rhodium complexes (dppe)­Rh­(COD)­BF4 and (MeCN)2Rh­(COD)­BF4 have been supported in metal–organic frameworks bearing anionic nodes (ZJU-28) and anionic linkers (MIL-101-SO3) via ion exchange. These MOF-supported Rh species serve as recyclable catalysts for the hydrogenation of both the terminal alkene substrate 1-octene and the internal alkene substrate 2,3-dimethylbutene. The nature of the MOF support impacts various aspects of catalysis, including: (i) the rate of 1-octene hydrogenation, (ii) the activity and recyclability of the catalyst in 2,3-dimethylbutene hydrogenation, and (iii) the size selectivity of hydrogenation with alkene substrates appended to calixarenes.

Multishelled Ni x Co3- x O4 Hollow Microspheres Derived from Bimetal-Organic Frameworks as Anode Materials for High-Performance Lithium-Ion Batteries

“…An effective strategy for the building of desirable MTMOs or multishelled hollow architectures is using metal–organic frameworks (MOFs) as self‐sacrificial templates or precursors. MOFs, a class of crystalline porous materials prepared by the self‐assembly of metal cations or metal clusters with bridging organic ligands, featured with diversified topological architectures and well‐defined pore structures, have represented great promise for a wide variety of applications in catalysis, gas storage/separation, sensing, and drug delivery . Inspired by their fascinating configurations, MOFs are considered to be versatile templates and precursors for the preparation of novel porous nanostructured materials with high surface area and hierarchical pore distribution, basically via thermolysis .…”

Rational Design of Catalytic Centers in Crystalline Frameworks

“…This strategy has been widely applied in frameworks comprising pyridine or derivative units, amine groups, thiocatechol groups, or phosphine ligands, which have high affinity for metal ions. With such a postsynthetic strategy, a variety of metal precursors, such as Pt, Pd, Ru, Rh, Ir, Au, Mn, Ni, Co, Cr, Ga, and Cu, based species, have been introduced into MOFs or COFs to create catalytically active sites. For example, our group reported the construction of a bi‐functional MOF (MOF‐253‐Pt) photocatalyst by immobilizing a platinum complex in 2,2′‐bipyridine‐based MOF (MOF‐253) .…”

“…The tunable pore size facilitates the selection of substrate and/or product molecules in catalytic reactions to achieve high selectivity. Table 5 lists the typical examples of single site catalysts encapsulated in pores of MOFs or COFs for catalytic applications.…”

Encapsulation of Crabtree's Catalyst in Sulfonated MIL‐101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment

“…Thec ations within 1-SO 3 H can be partially exchanged with Ag + [18] or [Rh(cod)-(dppe)] + [dppe = 1,2-bis(diphenylphosphino)ethane]. [19] To increase the number of exchangeable Na + cations, 1-SO 3 H was treated with AcONa/AcOH buffer solution (pH 4.7), forming [H y Na 2Ày ][Cr 3 (m 3 -O)(BDC-SO 3 ) 3 ]( 1-SO 3 Na, y = 0.2 AE 0.1, Table S1).…”