Semi-hydrogenation of α,β-unsaturated aldehydes over sandwich-structured nanocatalysts prepared by phase transformation of thin-film Al2O3 to Al-TCPP

Abstract

The semi-hydrogenation of α,β-unsaturated aldehydes to the desired unsaturated alcohols with both high conversion and high selectivity remains a big challenge. Herein, we designed a sandwich-structured nanocatalyst for the highly selective hydrogenation of various α,β-unsaturated aldehydes (e.g., cinnamaldehyde, furfural, crotonaldehyde, and 3-methyl-2-butenal) to the targeted unsaturated alcohols. Highly accessible platinum nanoparticles were sandwiched between a metal–organic framework (MOF) core (i.e., MIL-88B(Fe)) and a MOF shell (i.e., Al-TCPP). In particular, the growth of the Al-TCPP shell was achieved by atomic layer deposition (ALD) of thin-film Al₂O₃ followed by phase transformation with a tetrakis(4-carboxyphenyl)porphyrin (H₄TCPP) linker. The thickness of the Al-TCPP shell can be finely controlled by adjusting the cycle number of alumina ALD and the concentration of the H₄TCPP linker during the phase transformation of Al₂O₃ to Al-TCPP. It was proven that the permeable MOF shells could serve as selectivity regulators for the activation of the CO bonds in α,β-unsaturated aldehydes (in preference to the CC bonds), leading to higher selectivity towards unsaturated alcohols as compared to the conventional surface supported Pt catalysts. Mechanistic insights showed that the enhanced catalytic performance was attributed to (i) the modified electronic state of sandwiched Pt nanoparticles by the two MOF layers and (ii) the steric hindrance effect on substrate diffusion through the sandwich-structured catalysts.