Synergistic Fluorine Doping and Oxygen Vacancy Formation in Hematite Photoanodes via Solid-State Thermite Defect Engineering.

Authors

Jiaxin Nie, Yanjun Yin, Jie Jiang, Yaqiong Zhang, Zhiyong Bao, Zili Ma

Published in

Langmuir : the ACS journal of surfaces and colloids. Jun 25, 2026. Epub Jun 25, 2026.

Abstract

Defect engineering such as doping is a crucial strategy to overcome the sluggish charge transfer kinetics of metal oxide photoanodes. Fluorine doping of metal oxide photoanodes, such as hematite (α-Fe₂O₃), conventionally relies on fluorine-containing solutions, which often causes severe surface etching. Herein, we report a solid-state thermite defect engineering strategy to simultaneously induce F-doping and oxygen vacancies in hematite using fluororubber-coated aluminum (Al@F2311). Upon heating to 400 °C, the decomposing fluororubber effectively strips the inert Al oxide shell, triggering a localized interfacial thermite reaction. This process extracts lattice oxygen and substitutes fluorine into the near-surface region without disrupting the bulk structure. The resulting dual-defect Hem-AlF photoanode achieves a photocurrent density of 1.13 mA cm^-2 at 1.23 V vs RHE, which is a 5.65-fold enhancement over pristine hematite. This improvement originates from a synergistically increased donor density, minimized interfacial charge transfer resistance, and reaction-induced surface hydrophilicity (contact angle of 49.7°). This solvent-free paradigm successfully pioneers the integration of energetic material kinetics into semiconductor defect engineering.

PMID:
42345190
Bibliographic data and abstract were imported from PubMed on 25 Jun 2026.

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