Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework

Abstract

Metal-organic frameworks (MOFs) have received attention for a myriad of potential applications including catalysis, gas storage, and gas separation. Coordinatively unsaturated metal ions often enable key functional behavior of these materials. Most commonly, MOFs have been metalated from the condensed phase (i.e., from solution). Here we introduce a new synthetic strategy capable of metallating MOFs from the gas phase: atomic layer deposition (ALD). Key to enabling metalation by ALD In MOFs (AIM) was the synthesis of NU-1000, a new, thermally stable, Zr-based MOF with spatially oriented -OH groups and large 1D mesopores and apertures.

Metal–Organic Framework Nodes as Nearly Ideal Supports for Molecular Catalysts: NU-1000- and UiO-66-Supported Iridium Complexes

“…We selected Zr 6 -based UiO-66 and NU-1000 frameworks because of their exceptional thermal stability and well-defined structures. 16,18 UiO-66 is composed of [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 ] 12+ nodes, each linked to 12 carboxylates of terephthalate ligands to form tetrahedral and octahedral cages; however, there are many defects from missing linkers in this MOF, with the resulting otherwise open metal sites occupied by hydroxo ligands. 18−20 The node topology of NU-1000 has been determined to be [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 4 (OH 2 ) 4 ] 8+ , 21 and it is coordinated to eight tetratopic linkers of 1,3,6,8-tetrakis(p-benzoic-acid)pyrene (H 4 TBAPy) to form triangular and hexagonal pores.…”

Chemical principles for electroactive metal–organic frameworks

“…Thus, organic functionalization can be used to modify the chemistry of the band edges 20,14 and the physical properties of the material 21 . Alternatively, the chemically inert ZrO 2 -based node found in UiO-66 and compositionally similar analogues such as NU-1000 22 can be used to anchor catalytically active metals, providing access to heterogeneous catalysts 23 . Similar metal anchoring is possible through ligand substitutions that boast coordinating functionality (e.g.…”

Design and Construction of Chemically Stable Metal-Organic Frameworks

“…Typical examples include the syntheses of UiO-66, 18 PCN-22X (X = 2, 3, 4, 5, 8), 20 NU-1000. 21 Without modulating agents, only amorphous precipitates or crystalline products with high defect ratio can be generated. By contrast, with modulating agents, big single crystals or almost defect-free products can be obtained.…”

“…21 The primary structural difference between NU-1000 and PCN-222 is that the tetratopic ligand in NU-1000 is not TCPP but 1,3,6,8-tetrakis( p-benzoic acid)pyrene (H 4 TBAPy) ( Figure 8). Though there is no detailed experimental data, NU-1000 is still presumed to be chemically stable and has been studied for metalation and catalysis.…”

“…Though there is no detailed experimental data, NU-1000 is still presumed to be chemically stable and has been studied for metalation and catalysis. 21 It is worth mentioning that not all chemically stable MOFs are discovered by deliberately soaking the material in certain solutions. Sometimes, they are found along the process of postsynthetic modification of pristine MOFs.…”