Si-substituted MAX phases and in situ formation of Si-coated MXene composites via chlorosilane etching

We report a gas-phase SiCl₄ etching strategy to synthesize Si-substituted MAX phases (M_n+1SiX_n, where M = Ti, V, Nb, Ta, and Cr and X = C or N) and Cl-terminated MXenes from Al-based MAX precursors. By tuning the SiCl₄ concentration, the reaction pathway is precisely controlled: stoichiometric conditions lead to the formation of Si-MAX phases with tunable A-site vacancies (up to 50%) due to the tetravalent nature of Si⁴⁺, whereas excess SiCl₄ drives complete etching to produce in situ Si-coated MXene composites in one step. This approach not only expands the family of Si-based MAX phases, but also provides a scalable platform for designing MXene-based hybrid materials.