Strain-Induced Self-Assembly at Interface of Two-Dimensional Heterostructures Boosts CO 2 Reduction to Methanol by H 2 O.

CO 2 conversion with pure H 2 O into CH 3 OH and O 2 driven by solar energy can supply fuels and life-essential substances for extraterrestrial exploration. However, the effective production of CH 3 OH is significantly challenging. Here we report an organozinc complex/MoS 2 heterostructure linked by well-defined zinc-sulfur covalent bonds derived by the structural deformation and intensive coupling of d x 2  -  y 2 (Zn)-p(S) orbitals at the interface, resulting in distinctive charge transfer behaviors and excellent redox capabilities as revealed by experimental characterizations and first-principle calculations. The synthesis strategy is further generalized to more organometallic compounds, achieving various heterostructures for CO 2 photoreduction. The optimal catalyst delivers a promising CH 3 OH yield of 2.57 mmol g cat -1 h -1 and selectivity of more than 99.5%. The reverse water gas shift mechanism is identified for methanol formation. Meanwhile, energy-unfavorable adsorption of methanol on MoS 2 , where the photogenerated holes accumulate, ensures the selective oxidation of water over methanol.