Zr‐Metal‐Organic Framework Catalysts for Oxidative Desulfurization and Their Improvement by Postsynthetic Ligand Exchange. Issue 12 (26th August 2018) - Fu, Guangxia
Abstract: Two types of Zr6 ‐based metal‐organic frameworks (MOF), {Zr6 O4 (OH)4 (C6 H3 (COO)3 )2 (HCOO)6 } (MOF‐808) and {Zr6 O4 (OH)4 (C24 H15 (COO)3 )2 (HCOO)6 } (UMCM‐309) are investigated as heterogeneous catalysts in oxidative desulfurization reactions. Postsynthetic approaches targeting the removal of the coordinating formate ligands are applied to further improve the MOFs' catalytic activity, resulting in the formation of additional Zr IV open sites. Thus, three modified MOFs, namely MOF‐808‐M, UMCM‐309‐M1, and UMCM‐309‐M2, are synthesized with larger numbers of open sites, as shown by CD3 CN chemisorption monitored by Fourier‐transform infrared spectroscopy (FTIR), leading to higher catalytic activity. Even at low catalyst loading, MOF‐808‐M exhibits high catalytic activity in the oxidation of sulfur compounds as well as high selectivity and reusability. Abstract : Zr‐metal organic frameworks (MOF), MOF‐808 and UMCM‐309, are investigated as catalysts for oxidative desulfurization. The 3D MOF‐808 exhibits higher catalytic activity than the 2D UMCM‐309, resulting from the larger number of accessible open sites on MOF‐808. Formic acid ligands on these MOFs are removed by exchange with methanol to create more open sites, resulting in improved catalytic activity.