A highly crystalline perylene imide polymer (Urea‐PDI) photocatalyst is successfully constructed. The Urea‐PDI presents a wide spectrum response owing to its large conjugated system. The Urea‐PDI performs so far highest oxygen evolution rate (3223.9 µmol g−1 h−1) without cocatalysts under visible light. The performance is over 107.5 times higher than that of the conventional PDI supramolecular photocatalysts. The strong oxidizing ability comes from the deep valence band (+1.52 eV) which is contributed by the covalent‐bonded conjugated molecules. Besides, the high crystallinity and the large molecular dipoles of the Urea‐PDI contribute to a robust built‐in electric field promoting the separation and transportation of photogenerated carriers. Moreover, the Urea‐PDI is very stable and has no performance attenuation after 100 h continuous irradiation. The Urea‐PDI polymer photocatalyst provides with a new platform for the use of photocatalytic water oxidation, which is expected to contribute to clean energy production.

No abstract

No abstract

No abstract

Mechanically interlocked molecules (MIMs) with discrete molecular components linked through a mechanical bond in space can be harnessed for the operation of molecular switches and machines, which shows huge potential to imitate the dynamic response of natural enzymes. In this work, rotaxane compounds were adopted as building monomers for the synthesis of a crown-ether ring mechanically intercalated covalence organic framework (COF). This incorporation of MIMs into open architecture implemented large amplitude motions, whose wheel slid along the axle in response to external stimulation. After impregnation with Zn 2+ ions, the relative locations of two zinc active sites (crown-ether coordinated Zn(II) and bipyridine coordinated Zn(II)) are endowed with great flexibility to fit the conformational transformation of an organophosphorus agent during the hydrolytic process. Notably, the resulting self-adaptive binuclear zinc center in a crown-ether-threaded COF network is endowed with a record catalytic ability, with a rate over 85.5 μM min –1 for organophosphorus degradation. The strategy of synthesis for porous artificial enzymes through the introduction of mechanically bound crown ether will enable significant breakthroughs and new synthetic concepts for the development of advanced biomimetic catalysts.

High-efficiency photocatalysts based on metalorganic frameworks (MOFs) are often limited by poor charge separation and slow charge-transfer kinetics. Herein, a novel MOF photocatalyst is successfully constructed by encapsulating C 60 into a nano-sized zirconium-based MOF, NU-901. By virtue of host-guest interactions and uneven charge distribution, a substantial electrostatic potential difference is set-up in

The insufficient charge separation and sluggish exciton transport severely limit the utilization of polymeric photocatalysts. To resolve the above issues, we incorporate bountiful carboxyl substituents within a novel benzodiimidazole oligomer and assemble it into a crystalline semiconductor. The photocatalyst is polar, hydrophilic, short-range crystalline, and capable of both hydrogen and oxygen evolution. The introduction of carboxyl side-groups adds asymmetry to the local structure and increases the built-in electric field. Further, accelerated carrier transfer is enabled via the short-range crystallinity. The superior hydrogen and oxygen production rates of 18.63 and 2.87 mmol g À 1 h À 1 represent one of the best performances ever reported among dual-functional polymeric photocatalysts. Our work initiates studies on high-performance oligomer photocatalysts, opening a new frontier to produce solar fuel.

Abstract The rapid, complete, targeted, and safe treatment for tumors remains a key issue in cancer therapy. A novel treatment of solid tumors by supramolecular photocatalyst Nano-SA-TCPP with the irradiation of 600–700 nm wavelength is established. The solid tumors (100 mm3) can be eliminated within 10 min. The 50-day mouse survival rate was increased from 0% to 100% after the photocatalytic therapy. The breakthrough was owing to the cell membrane rupture and the cytoplasmic loss caused by photogenerated holes inside cancer cells. The porphyrin-based photocatalysts can be targetedly internalized by cancer cells due to the size selection effect without entering the normal cells. The therapy has no toxicity and side effects for normal cells and organisms. Moreover, the photocatalytic therapy is effective for a variety of cancer cell lines. Because of its high efficiency, safety, and universality, the photocatalytic therapy provides us with a new lancet to conquer the tumor.