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Introducing hierarchical pore structure to microporous materials such asmetal-organic frameworks (MOFs) can be beneficial for reactions where the rateof reaction is limited by low rates of diffusion or high pressure drop. Thisadvantageous pore structure can be obtained by defect formation, mostly viapost-synthetic acid etching, which has been studied extensively on water-stableMOFs. Here we show that a water-unstable HKUST-1 MOF can also be modified in acorresponding manner by using phosphoric acid as a size-selective etching agentand a mixture of dimethyl sulfoxide and methanol as a dilute solvent.Interestingly, we demonstrate that the etching process which is time- andacidity- dependent, can result in formation of defective HKUST-1 with extrainterconnected hexagonal macropores without compromising on the bulkcrystallinity. These findings suggest an intelligent scalable synthetic methodfor formation of hierarchical porosity in MOFs that are prone to hydrolysis,for improved molecular accessibility and diffusion for catalysis.

Defective hierarchical porous copper-based metal-organic frameworks synthesised via facile acid etching strategy