Spatially coupled CO2 activation and hydrogenation sites in 1 T′-MoS2 enable near-unity methanol selectivity

The development of efficient catalysts for CO2 hydrogenation to methanol is highly urgent but is hindered by maintaining precise control over intermediate transfer. Here we demonstrate that the oxidized 2D 1 T′-MoS2 uniquely integrates both CO2 activation and selective hydrogenation functions within a single material through its inherent 2D structural merit. The singular S-edge structure of 1 T′-MoS2 creates a uniform catalytic landscape where in-plane O-substituted sulfur defects and oxidized edges operate in concert. This spatially organized system achieves CO2 conversion of 23.0% with a methanol selectivity of 99.2% and the specific reaction rate reaches 0.91 ± 0.01 gmethanol/gcat/h at 210 °C. We reveal the complete reaction trajectory: (i) preferential CO2 dissociation at in-plane sites generates weakly adsorbed *CO intermediates that (ii) undergo directed desorption-retrapping to edge sites where (iii) the oxidized edge of 1 T′ phase uniquely stabilizes the C-O bond during hydrogenation. This work establishes the phase-engineered 1 T′-MoS2 as a paradigm for single-material tandem catalysis to demonstrate how the spatially coupled active sites boost the CO2 hydrogenation. Improving catalysts for CO₂-to-methanol conversion is limited by poor control of reaction intermediates. Here oxidized 2D 1 T′-MoS2 couples activation and hydrogenation sites to enable high methanol selectivity.