Competitive Coordination Strategy to Finely Tune Pore Environment of Zirconium-Based Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are a class of crystalline porous materials with reticular architectures. Precisely tuning pore environment of MOFs has drawn tremendous attention but remains a great challenge. In this work, we demonstrate a competitive coordination approach to synthesize a series of zirconium-metalloporphyrinic MOFs through introducing H2O and monocarboxylic acid as modulating reagents, in which well-ordered mesoporous channels could be observed clearly under conventional transmission electron microscopy. Owing to plenty of unsaturated Lewis acid catalytic sites exposed in the visualized mesoporous channels, these structures exhibit outstanding catalytic activity and excellent stability in the chemical fixation of carbon dioxide to cyclic carbonates. The zirconium-based MOFs with ordered channel structures are expected to pave the way to expand the potential applications of MOFs.