Electrosynthesis of an Improbable Directly Bonded Phosphorene‐Fullerene Heterodimensional Hybrid toward Boosted Photocatalytic Hydrogen Evolution

Phosphorene and fullerene are representative two‐dimensional (2D) and zero‐dimensional (0D) nanomaterials respectively, constructing their heterodimensional hybrid not only complements their physiochemical properties but also extends their applications via synergistic interactions. This is however challenging because of their diversities in dimension and chemical reactivity, and theoretical studies predicted that it is improbable to directly bond C60 onto the surface of phosphorene due to their strong repulsion. Here, we develop a facile electrosynthesis method to synthesize the first phosphorene‐fullerene hybrid featuring fullerene surface bonding via P−C bonds. Few‐layer black phosphorus nanosheets (BPNSs) obtained from electrochemical exfoliation react with C602− dianion prepared by electroreduction of C60, fulfilling formation of the “improbable” phosphorene‐fullerene hybrid (BPNS‐s‐C60). Theoretical results reveal that the energy barrier for formation of [BPNS‐s‐C60]2− intermediate is significantly decreased by 1.88 eV, followed by an oxidization reaction to generate neutral BPNS‐s‐C60 hybrid. Surface bonding of C60 molecules not only improves significantly the ambient stability of BPNSs, but also boosts dramatically the visible light and near‐infrared (NIR) photocatalytic hydrogen evolution rates, reaching 1466 and 1039 μmol h−1 g−1 respectively, which are both the highest values among all reported BP‐based metal‐free photocatalysts. Phosphorene‐fullerene hybrid with fullerene directly bonded onto the surface (basal plane) of phosphorene via P−C bonds was theoretically predicted “improbable” due to the strong repulsion between phosphorene and neutral fullerene.It is now synthesized by an electrosynthesis method involving C602− dianion as an intermediate generated by electroreduction of C60, significantly improving the stability and visible light/near‐infrared (NIR) photocatalytic hydrogen evolution rates of phosphorene.