Fullerene Covalent Passivation of Black Phosphorus Nanosheets toward Enhanced Near-Infrared-II Photothermal Therapy

Photothermal therapy (PTT) triggered by near-infrared-II (NIR-II, 1000–1700 nm) light is developed as a potential tumor therapy technique with deeper tissue penetration capacity and higher allowable laser power density of the skin than NIR-I (750–1000 nm) biowindow. Black phosphorus (BP) with excellent biocompatibility and favorable biodegradability demonstrates promising applications in PTT but suffers from low ambient stability and limited photothermal conversion efficiency (PCE), and utilization of BP in NIR-II PTT is scarcely reported. Herein, we develop novel fullerene covalently modified few-layer BP nanosheets (BPNSs) with ∼9-layer thickness through an easy one-step esterification process (abbreviated BP-ester-C 60 ), bringing about the dramatically enhanced ambient stability of BPNSs due to bonding of the hydrophobic C 60 with high stability and the lone electron pair on the phosphorus atom. BP-ester-C 60 is then applied as a photosensitizer in NIR-II PTT, delivering a much higher PCE than the pristine BPNSs. Under 1064 nm NIR-II laser irradiation, in vitro and in vivo antitumor studies reveal that BP-ester-C 60 exhibits dramatically enhanced PTT efficacy with considerable biosafety relative to the pristine BPNSs. This is interpreted by the boost of NIR light absorption on account of the modulation of the band energy level resulting from intramolecular electron transfer from BPNSs to C 60 .