MXene (Ti₃C₂) Vacancy-Confined Single-Atom Catalyst for Efficient Functionalization of CO₂

Abstract

A central topic in single-atom catalysis is building strong interactions between single atoms and the support for stabilization. Herein we report the preparation of stabilized single-atom catalysts via a simultaneous self-reduction stabilization process at room temperature using ultrathin two-dimensional Ti_{3- x}C₂T _yMXene nanosheets characterized by abundant Ti-deficit vacancy defects and a high reducing capability. The single atoms therein form strong metal-carbon bonds with the Ti_{3- x}C₂T _y support and are therefore stabilized onto the sites previously occupied by Ti. Pt-based single-atom catalyst (SAC) Pt₁/Ti_{3- x}C₂T _y offers a green route to utilizing greenhouse gas CO₂, via the formylation of amines, as a C₁ source in organic synthesis. DFT calculations reveal that, compared to Pt nanoparticles, the single Pt atoms on Ti_{3- x}C₂T _y support feature partial positive charges and atomic dispersion, which helps to significantly decrease the adsorption energy and activation energy of silane, CO₂, and aniline, thereby boosting catalytic performance. We believe that these results would open up new opportunities for the fabrication of SACs and the applications of MXenes in organic synthesis.