Triphasic synthesis of MXenes with uniform and controlled halogen terminations

Abstract

Surface terminations critically govern the properties of two-dimensional transition metal carbides and/or nitrides (MXenes), yet a universal strategy to obtain MXenes with uniform and controllable terminations remains elusive. Here we introduce a 'gas-liquid-solid' triphasic etching strategy that employs iodine vapour, halide molten salts and MAX phases to produce MXenes with pure and precisely tunable halogen terminations (Cl, Br, I or their combinations). In this process, halide molten salts dissolve iodine via interhalogen anion formation while efficiently transporting etching by-products. The resulting MXenes retain excellent structural integrity, yielding uniformly ordered surfaces. As a representative example, Ti3C2Cl2 shows a 160-fold enhancement in macroscopic conductivity and a 13-fold enhancement in terahertz conductivity relative to conventional Cl/O-terminated Ti3C2, attributed to minimized electron trapping and scattering. Beyond single-halogen terminations, the gas-liquid-solid approach enables dual- and triple-halogen termination control, providing a general platform for tailoring MXene surface chemistry towards advanced (opto)electronic applications.