4 years ago

Heat-Treatment of Defective UiO-66 from Modulated Synthesis: Adsorption and Stability Studies

Heat-Treatment of Defective UiO-66 from Modulated Synthesis: Adsorption and Stability Studies
Ryan P. Lively, Souryadeep Bhattacharyya, David S. Sholl, Yang Liu, Yang Jiao, Krista S. Walton, Julian T. Hungerford, Guanghui Zhu
Defect engineering in metal–organic frameworks (MOFs) is an emerging strategy that can be used to control physical or chemical characteristics of MOFs, including adsorption behavior and textural, mechanical, and conductive properties. Understanding the impact of defects on textural properties and chemical stability of MOFs is imperative to the development of MOFs with tunable defect sites. In this work, systematic adsorption measurements were performed with three adsorbate molecules (SO2, benzene, and cyclohexane) to investigate changes in the pore size of defective UiO-66. Compared to the parent UiO-66, the defective UiO-66 shows significant changes in adsorption capacities among the selected adsorbate molecules, demonstrating that pore size is significantly enlarged by the missing cluster defects. BET surface area analysis and DFT calculations were also performed to interrogate the chemical stability of the defective MOFs after exposure to water and acidic environments. This work shows that pore size can be tuned as a function of defect concentration. Further, it is shown that the structural incorporation of trifluoroacetate groups in defective UiO-66 leads to an increase in average pore size without sacrificing chemical stability toward water and acidic species. The results of this work advance the understanding of textural properties and chemical stability of defect-engineered MOFs and also suggest a preparation method for synthesizing defective but stable MOFs.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b07772

DOI: 10.1021/acs.jpcc.7b07772

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