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Metal organic frameworks (MOFs) have drawn wide attention as potential catalysts, offering high densities of catalytic sites in high-area porous solids, some with stabilities at high temperatures. The field is at an early stage, characterized by numerous discoveries and novel demonstrations of catalytic properties associated with the crystalline structures of MOFs, but applications of MOFs as catalysts are still lacking. In this perspective we summarize advantages and limitations of MOFs as catalysts and fundamental issues to be addressed about their potential applications. MOF framework compositions and pore structures can strongly influence catalytic performance, allowing, for example, shape-selective and bifunctional catalysis, but research is needed to quantify reaction/transport processes in MOFs, identify catalytic sites, and determine intrinsic catalytic reaction rates. Progress is hindered by the lack of understanding of the heterogeneity of MOFs, with catalytic sites sometimes being in structures such as defects not determined by X-ray diffraction crystallography. Determination of the dynamics of MOFs and their catalytic sites, as well as the intrinsic kinetics of catalytic reactions, will help to advance guidelines for synthesizing optimum catalysts. Further, MOFs present challenges related to stability and regeneration as catalysts, some associated with the unique nature of MOFs, such as the node–linker bonds, which can break during catalysis. There are opportunities to understand these matters in depth and to find conditions of catalytic operation that minimize the processes leading to deactivation.

Our aim in this review is to assess key recent findings that point to atomically dispersed noble metals as catalytic sites on solid supports, which may be viewed as ligands bonded to the metal. Both zeolites and open metal oxide supports are considered; the former offer the advantages of uniform, crystalline structures to facilitate fundamental understanding, and the latter offer numerous advantages in applications. The notion of strong interactions between metals and supports has resurfaced in the recent literature to explain how subnanometer clusters and even atoms of noble metals such as platinum and gold survive under often harsh reaction conditions on some supports, such as ceria and perovskites. Individual cations of platinum, palladium, rhodium, or other metals anchored to supports through M-O bonds can be formed on these supports in configurations that are stable and catalytically active for several reactions illustrated here, notably, oxidation and reduction. The development of effective synthesis methods and the identification of suitable stabilizers and promoters are expected to lead to the increasing application of atomically dispersed noble metal catalysts for practical processes characterized by efficient resource utilization and cost savings.

X-ray absorption near-edge spectra and temperature-programmed oxidation and reduction data demonstrate that Au(I) and Au(0) are both present in working MgO-supported gold catalysts for CO oxidation. EXAFS data indicate gold clusters with essentially the same average diameter (about 30 A) in each catalyst sample. Thus, the results provide no evidence of an effect of gold cluster size on the catalytic activity, but both the catalytic activity and the surface concentration of Au(I) were found to decrease with increasing CO partial pressure (as Au(0) was increasingly formed), demonstrating that the catalytic sites incorporate Au(I).