Superior Activity of Isomorphously Substituted MOFs with MIL-100(M=Al, Cr, Fe, In, Sc, V) Structure in the Prins Reaction: Impact of Metal Type.

The catalytic behavior of isomorphously substituted MIL-100(M) (M=Al, Cr, Fe, In, Sc, V) is investigated for the synthesis of nopol through the Prins condensation of β-pinene with paraformaldehyde. The large mesoporous cages of the metal-organic frameworks provide a sustainable confinement for the formation of the target product (100 % selectivity for nopol over all materials studied). MIL-100(Sc) and MIL-100(V) exhibit the highest yields (up to 90 %) of nopol after just 20 min from the beginning of the reaction, owing to their high concentrations of accessible Lewis sites possessing intermediate acidity.

Metal-Organic Frameworks M-MOF-74 and M-MIL-100: Comparison of Textural, Acidic, and Catalytic Properties.

The impact of the metal nature and framework type on the textural, acidic, and catalytic properties of M-MOF-74 (M=Co, Cu, Mg, Ni) and M-MIL-100 (M=Al, Cr, Sc, V) materials was evaluated. Both metal-organic framework (MOF) families showed 100 % selectivity to the tetrahydropyranyl ether for all alcohols (methanol, 1-propanol, 1-octanol, 2-adamantanol, 1-octadecanol) applied. Independently of the metal employed in the synthesis of M-MOF-74, the conversions were lower than those obtained with M-MIL-100.