Hydrogen-Bonded Mesoporous Frameworks with Tunable Pore Sizes and Architectures from Nanocluster Assembly Units

Construction of mesoporous frameworks by noncovalent bonding still remains a great challenge. Here, we report a micelle-directed nanocluster modular self-assembly approach to synthesize a novel type of two-dimensional (2-D) hydrogen-bonded mesoporous frameworks (HMFs) for the first time based on nanoscale cluster units (1.0-3.0 nm in size). In this 2-D structure, a mesoporous cluster plate with ∼100 nm in thickness and several micrometers in size can be stably formed into uniform hexagonal arrays. Meanwhile, such a porous plate consists of several (3-4) dozens of layers of ultrathin mesoporous cluster nanosheets. The size of the mesopores can be precisely controlled from 11.6 to 18.5 nm by utilizing the amphiphilic diblock copolymer micelles with tunable block lengths. Additionally, the pore configuration of the HMFs can be changed from spherical to cylindrical by manipulating the concentration of the micelles. As a general approach, various new HMFs have been achieved successfully via a modular self-assembly of nanoclusters with switchable configurations (nanoring, Keggin-type, and cubane-like) and components (titanium-oxo, polyoxometalate, and organometallic clusters). As a demonstration, the titanium-oxo cluster-based HMFs show efficient photocatalytic activity for hydrogen evolution (3.6 mmol g^-1h^-1), with a conversion rate about 2 times higher than that of the unassembled titanium-oxo clusters (1.5 mmol g^-1h^-1). This demonstrates that HMFs exhibited enhanced photocatalytic activity compared with unassembled titanium-oxo clusters units.