General Bottom-Up Colloidal Synthesis of Nano-Monolayer Transition-Metal Dichalcogenides with High 1T′-Phase Purity

Phase engineering of nanomaterials provides a promising way to explore the phase-dependent physicochemical properties and various applications of nanomaterials. A general bottom-up synthesis method under mild conditions has always been challenging globally for the preparation of the semimetallic phase-transition-metal dichalcogenide (1T′-TMD) monolayers, which are pursued owing to their unique electrochemical property, unavailable in their semiconducting 2H phases. Here, we report the general scalable colloidal synthesis of nanosized 1T′-TMD monolayers, including 1T′-MoS₂, 1T′-MoSe₂, 1T′-WS₂, and 1T′-WSe₂, which are revealed to be of high phase purity. Moreover, the surfactant-reliant stacking-hinderable growth mechanism of 1T′-TMD nano-monolayers was unveiled through systematic experiments and theoretical calculations. As a proof-of-concept application, the 1T′-TMD nano-monolayers are used for electrocatalytic hydrogen production in an acidic medium. The 1T′-MoS₂nano-monolayers possess abundant in-plane electrocatalytic active sites and high conductivity, coupled with the contribution of the lattice strain, thus exhibiting excellent performance. Importantly, the catalyst shows impressive endurability in electroactivity. Our developed general scalable strategy could pave the way to extend the synthesis of other broad metastable semimetallic-phase TMDs, which offer great potential to explore novel crystal phase-dependent properties with wide application development for catalysis and beyond.