A surfactant‐stabilized coordination strategy is used to make two‐dimensional (2D) single‐atom catalysts (SACs) with an ultrahigh Pt loading of 12.0 wt %, by assembly of pre‐formed single Pt atom coordinated porphyrin precursors into free‐standing metal–organic framework (MOF) nanosheets with an ultrathin thickness of 2.4±0.9 nm. This is the first example of 2D MOF‐based SACs. Remarkably, the 2D SACs exhibit a record‐high photocatalytic H2 evolution rate of 11 320 μmol g−1 h−1 via water splitting under visible light irradiation (λ>420 nm) compared with those of reported MOF‐based photocatalysts. Moreover, the MOF nanosheets can be readily drop‐casted onto solid substrates, forming thin films while still retaining their photocatalytic activity, which is highly desirable for practical solar H2 production.

Vesicular photothermal therapy agents (PTAs) are highly desirable in photothermal therapy (PTT) for their excellent light-harvesting ability and versatile hollow compartments. However, up to now, the reported vesicular PTAs are generally self-assembled from small molecules like liposomes, and polymer vesicles have seldom been used as PTAs due to the unsatisfactory photothermal conversion efficiency resulting from the irregular packing of chromophores in the vesicle membranes. Here we report a nano-sized polymer vesicle from hyperbranched polyporphyrins with favorable photothermal stability and extraordinarily high photothermal efficiency (44.1%), showing great potential in imaging-guided PTT for tumors through in vitro and in vivo experiments. These excellent properties are attributed to the in situ supramolecular polymerization of porphyrin units inside the vesicle membrane into well-organized 1D monofilaments driven by π-π stacking. We believe the supramolecular polymerization-enhanced self-assembly process reported here will shed a new light on the design of supramolecular materials with new structures and functions.

The intrinsic relationship between the properties of green fluorescent protein (GFP) and its encapsulated small molecular light machine has spurred many biomimicking studies, aiming at revealing the detailed mechanism and further promoting its wide applications in different disciplines. However, how to build a similar confined microenvironment to mimic the cavity of βbarrel and the fluorescence turn-on process is a fundamental challenge for both chemists and biologists. Herein, two distinct exoand endo-functionalized tetraphenylethylene (TPE)-based M 12 L 24 nanospheres with precise distribution of anchored TPE moieties and unique photophysical properties were constructed by means of a coordination-driven self-assembly strategy. Under dilute conditions, the nanospheres fluoresce stronger than the corresponding TPE subcomponents. Meanwhile, the endo-functionalized sphere is able to induce a higher local concentration and more restrained motion of the enclosed 24 TPE units compared with that of exo-functionalized counterpart and thus induce much stronger emission due to the restriction of the rotation of the pendant TPE units. The biomimetic methodology developed here represents a promising way to understand and construct artificial GFP materials on the platforms of supramolecular coordination complexes.

Conversion of clean solar energy to chemical fuels is one of the promising and up-and-coming applications of metal–organic frameworks. However, fast recombination of photogenerated charge carriers in these frameworks remains the most significant limitation for their photocatalytic application. Although the construction of homojunctions is a promising solution, it remains very challenging to synthesize them. Herein, we report a well-defined hierarchical homojunction based on metal–organic frameworks via a facile one-pot synthesis route directed by hollow transition metal nanoparticles. The homojunction is enabled by two concentric stacked nanoplates with slightly different crystal phases. The enhanced charge separation in the homojunction was visualized by in-situ surface photovoltage microscopy. Moreover, the as-prepared nanostacks displayed a visible-light-driven carbon dioxide reduction with very high carbon monooxide selectivity, and excellent stability. Our work provides a powerful platform to synthesize capable metal–organic framework complexes and sheds light on the hierarchical structure-function relationships of metal–organic frameworks.

Owning triply periodic minimal surfaces and three-dimensional (3D) interconnected pores, bicontinuous porous materials have drawn enormous attention due to their great academic interest and potential applications in many fields including energy and catalysis. However, their synthesis has remained a great challenge. Here, we demonstrate the synthesis of a bicontinuous porous organic semiconductor photocatalyst, which involves the preparation of SiO 2 with a shifted double diamond (DD) structure through solvent evaporation-induced self-assembly of a polystyrene-block-poly(ethylene oxide) diblock copolymer and tetraethyl orthosilicate, followed by SiO 2templated self-condensation of melamine monomers in a vacuum. Strikingly, the resultant DD-structured graphitic carbon nitride (g-CN) possesses two sets of 3D continuous mesopores with a mean diameter of 14 nm, which afford a high specific surface area of 131 m 2 g −1 and an optical band gap of 2.8 eV. Being a visible-light-driven photocatalyst, the bicontinuous mesoporous g-CN exhibits high catalytic activity for water splitting to generate H 2 (6831 μmol g −1 h −1 ) with excellent cycling stability. This study provides a protocol for the construction of ordered mesoporous materials containing 3D continuous channels, which holds promise for catalysis applications.