Ice‐Assisted Synthesis of Black Phosphorus Nanosheets as a Metal‐Free Photocatalyst: 2D/2D Heterostructure for Broadband H2 Evolution

By Qingzhe Zhang, Shengyun Huang, Jiujun Deng, Deepak Thrithamarassery Gangadharan, Fan Yang, Zhenhe Xu, G. Giorgi, M. Palummo, M. Chaker, D. Ma. Advanced Functional Materials, 2019

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A 2D/2D heterojunction of black phosphorous (BP)/graphitic carbon nitride (g‐C3N4) is designed and synthesized for photocatalytic H2 evolution. The ice‐assisted exfoliation method developed herein for preparing BP nanosheets from bulk BP, leads to high yield of few‐layer BP nanosheets (≈6 layers on average) with large lateral size at reduced duration and power for liquid exfoliation. The combination of BP with g‐C3N4 protects BP from oxidation and contributes to enhanced activity both under λ > 420 nm and λ > 475 nm light irradiation and to long‐term stability. The H2 production rate of BP/g‐C3N4 (384.17 µmol g−1 h−1) is comparable to, and even surpasses that of the previously reported, precious metal‐loaded photocatalyst under λ > 420 nm light. The efficient charge transfer between BP and g‐C3N4 (likely due to formed NP bonds) and broadened photon absorption (supported both experimentally and theoretically) contribute to the excellent photocatalytic performance. The possible mechanisms of H2 evolution under various forms of light irradiation is unveiled. This work presents a novel, facile method to prepare 2D nanomaterials and provides a successful paradigm for the design of metal‐free photocatalysts with improved charge‐carrier dynamics for renewable energy conversion.

Subfields: Materials Chemistry, Renewable Energy, Sustainability and the Environment

View Paper: https://www.semanticscholar.org/paper/888a396ba8956012eb0fedf030ca14dfc207e031