Controlled one-pot fluorination for F, B, S or N tri-doping of graphene

Heteroatom doping of graphene effectively modifies surface charge, defect density, and electronic structure, with multi-heteroatom co-doping enhancing bond polarization, charge redistribution, and electrochemical performance for advanced energy storage, conversion, and other technological applications. In this work, we report a one-step synthesis of di- and tri-doped graphene via the simultaneous incorporation of fluorine and boron into pristine as well as S- and N-doped graphene, starting from commercially available N- or S-doped graphene. Mild gas–solid fluorination was performed using elemental fluorine diluted in an inert nitrogen atmosphere at controlled temperatures. The presence of a boron-containing precursor enables the in situ generation of BF 3 , which acts as an effective boron-doping agent during the fluorination process. This approach allows, for the first time, the controlled synthesis of F/B/S-, and F/B/N- -tri-doped graphene materials through a single-step reaction. The doping mechanisms and structural evolution were elucidated using complementary characterization techniques, including Fourier-transform infrared (FTIR) spectroscopy, solid-state nuclear magnetic resonance (NMR) spectroscopy ( 19 F, 11 B and 13 C), thermogravimetric analysis (TGA) coupled with mass spectrometry (MS) and infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and (scanning)transmission electron microscopy ((S)TEM). The results demonstrate that hexagonal boron nitride and molecular fluorine act as precursors for the in situ generation of BF 3 , which, together with F 2 , enables efficient and homogeneous incorporation of fluorine and boron into heteroatom-doped graphene carbon frameworks. • First demonstration of a one-step gas–solid synthesis for F/B/N- and F/B/S-tri-doped graphene architectures. • In situ BF 3 generation enables a synchronized F/B-doping mechanism that overcomes the thermodynamic barriers of sequential functionalization. • Multi-nuclear solid-state NMR ( 19 F, 11 B, 13 C) clarifies bonding configurations and ensures homogeneous heteroatom(s) distribution. • Multi-heteroatom interaction induces enhanced charge redistribution and bond polarization without collapsing the graphene framework. • A controllable tri-doping strategy that provides a scalable platform adaptable to diverse heteroatom-doped carbon systems.