Hierarchically porous metal–organic frameworks (HP‐MOFs) have attracted great attention owing to their advantages over microporous MOFs in some applications. Despite many attempts, the development of a facile approach to generate HP‐MOFs remains a challenge. Herein we develop a new strategy, namely the modulation of cation valence, to create hierarchical porosity in MOFs. Some of the CuII metal nodes in MOFs can be transformed into CuI via reducing vapor treatment (RVT), which partially changes the coordination mode and thus breaks coordination bonds, resulting in the formation of HP‐MOF based on the original microporous MOF. Both the experimental results and the first‐principles calculation show that it is easy to tailor the amount of CuI and subsequent hierarchical porosity by tuning the RVT duration. It is found that the resultant HP‐MOFs perform much better in the capture of aromatic sulfides than the original microporous MOF.
Metal–organic
frameworks (MOFs) have drawn much attention
for their highly promising applications, but the applications are
often obstructed by the congenitally hydrothermal instability of the
MOFs. Hybridizing the MOFs with other materials has been proved to
be effective to solve the hydrothermal problems. Herein, a vapor-induced
crystallization (VIC) method is employed for the first time to fabricate
the hybrid MOFs based on the Cu-BTC and the natural clay attapulgite
(NCA). Compared with the traditional solvothermal method for the hybridization,
the VIC one has the obvious advantages of both reducing the solvent
consumption and inducing the crystals self-repairing to generate perfect
crystals of the hybrid MOFs. With an appropriate content of the NCA,
the hybrid MOFs are proved to be highly stable even undergoing the
hot water vapor (90 °C) for 12 h. The hybrid MOFs also exhibit
the improved catalytic activity in catalyzing the styrene oxide ring-opening.
The molar conversion of the styrene oxide over the hybrid MOF reaches
93.8% within 20 min, even higher than that of the unadulterated Cu-BTC
(68.0%). These results indicate the promising application of the hybrid
MOFs as the hydrothermal-stable and highly active heterogeneous catalysts.
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