Mechanistic Insight into the Catalytic NO Oxidation by the MIL-100 MOF Platform: Toward the Prediction of More Efficient Catalysts

Through density functional theory calculations, we unravel a microscopic picture of the catalytic NO oxidation activity of the MIL-100 MOF platform. By systematically varying the nature of the coordinatively unsaturated metal sites (Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ru), we demonstrate the relative energy of the metal–oxygen intermediate species to be a reliable descriptor to anticipate the catalytic activity of this family of MOFs. These conclusions are first validated by experimental data on MIL-100(Fe)/MIL-100(Fe,Mn) and further used as guidelines to develop a ruthenium-based MIL-100 with even better catalytic performance.