Tailoring Ultrashort Inter-Fullerene Spacing in a Continuous Fullerene Stacking Array to Enhance Electron Transport for Boosting Solar-Driven Hydrogen Production

Abstract

The efficiency of organic semiconductor photocatalysts is typically limited by their capability of photogenerated electron transport. Herein, a photocatalyst is proposed initially through the specific axial coordination interaction between imidazole-C₆₀ (ImC₆₀) and zinc tetraphenyl porphyrin (ZnTPP) named ImC₆₀-ZnTPP. Subsequently, detailed structural characterizations along with theoretical calculation reveal that the unique ImC₆₀-ZnTPP possesses head-to-tail stacking supra-structures, leading to the formation of a continuous array of C₆₀–C₆₀ with ultrashort spacing and ensuring strong π–π interactions and homogeneous electronic coupling, which could tremendously promote electron transport along the (−111) crystal facet of ImC₆₀-ZnTPP. Consequently, compared to other fullerene-based photocatalysts, ImC₆₀-ZnTPP shows exceptional photocatalytic hydrogen production activity, with an efficiency of up to 80.95 mmol g⁻¹ h⁻¹. This study provides a novel strategy to design highly efficient fullerene-based photocatalytic systems for solar-driven energy conversion and extend their artificial photosynthetic use.

Keywords

electron transport / fullerenes / photocatalytic hydrogen evolution / supramolecular photocatalyst / ultrashort π–π stacking spacing

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