  Introducing hierarchical pore structure to microporous materials such as
metal-organic frameworks (MOFs) can be beneficial for reactions where the rate
of reaction is limited by low rates of diffusion or high pressure drop. This
advantageous pore structure can be obtained by defect formation, mostly via
post-synthetic acid etching, which has been studied extensively on water-stable
MOFs. Here we show that a water-unstable HKUST-1 MOF can also be modified in a
corresponding manner by using phosphoric acid as a size-selective etching agent
and a mixture of dimethyl sulfoxide and methanol as a dilute solvent.
Interestingly, we demonstrate that the etching process which is time- and
acidity- dependent, can result in formation of defective HKUST-1 with extra
interconnected hexagonal macropores without compromising on the bulk
crystallinity. These findings suggest an intelligent scalable synthetic method
for formation of hierarchical porosity in MOFs that are prone to hydrolysis,
for improved molecular accessibility and diffusion for catalysis.
