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.

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A kinetic analysis of gas-phase cyclohexene epoxidation by H 2 O 2 over mesoporous TS-1 was performed. The production of cyclohexene oxide was very stable with high selectivity. Based on the kinetics analysis, the gas phase mechanism is proposed to be similar to that of the liquid phase reaction: an Eley-Rideal type mechanism, in which the reaction between a Ti-OOH intermediate and the physisorbed alkene is the rate-determining step. When the partial pressure of water or H 2 O 2 was varied, a compensation effect was observed. Based on the kinetics model, the compensation effect is attributed to variations in the surface coverage of intermediates, specifically the competitive adsorption of water and H 2 O 2 at the Ti active sites. A meaningful activation energy can only be obtained at high surface coverages of H 2 O 2 and was determined to be 40 ± 2 kJ/mol.