Porous Bimetallic Ti-MOFs for Photocatalytic Oxidation of Amines in Air.

Abstract

A family of microporous titanium-containing metal-organic frameworks (denoted as M2Ti-CPCDC, M = Mn, Co, Ni) has been synthesized by using a bimetallic [M2Ti(μ3-O)(COO)6] cluster and a tritopic carbazole-based organic ligand H3CPCDC. M2Ti-CPCDC are stable and display permanent porosity for N2 and CO2 uptake, ranking among the most porous titanium-based metal-organic frameworks. M2Ti-CPCDC crystals exhibit n-type semiconductor behavior. Further catalytic studies demonstrate that all M2Ti-CPCDC materials are applicable for triggering photo-oxidative reactions of amines in air. More specifically, amines with electron-donating groups afford the aldehydes as the main products, while amines bearing electron-withdrawing groups give rise to imines as the main product. Among them, Mn2Ti-CPCDC exhibit the best photocatalytic activity, with conversion of benzylamine up to 99% and selectivity of 99%. Mn2Ti-CPCDC could be recycled in at least three runs while retaining crystallinity and catalytic activity. The reaction mechanism indicates that photoinduced hole (h+), superoxide radical anion (O2·-), and singlet oxygen (1O2) are the main active species involved in the photo-oxidation process.