Phosphorus-substituted atomically dispersed Rh-N3P1 sites for efficient promotion in CO2 hydrogenation towards ethanol production.

Ethanol synthesis through CO 2 hydrogenation has shown great promise in contributing to carbon neutrality. Herein, we for the first time present the phosphorus-substitution of atomically dispersed Rh-N 4 sites for the title reaction. The as-formed Rh-N 3 P 1 sites enable the reaction product notably switching from nearly total methanol (91.3%) towards major ethanol (81.8%) with a high TOF of 420.7 h−1. This outstanding promotion in both ethanol formation and CO 2 conversion (69% higher) could be assigned to the donation of electron from P atom effectively weakening C-O bond in CH 3 OH* , facilitating its cleavage into CH 3 * , and enabling the coupling between CO* and CH 3 *. The presence of Rh-P site pair assists C-O bond activation with a longer bond length owing to a strong affinity of P atom to O atom in CH 3 OH*. This research underscores the importance of tuning the coordination and electronic environment of active metal sites for site pair synergistic catalysis. [Display omitted] • Switchable production from methanol towards ethanol by substituting N with P. • Rh-N 3 P 1 sites, at optimum conditions, achieved a high TOF of 420.7 h−1 for ethanol formation. • The Rh-P site pair synergistic catalysis for promoting C-O bond activation. [ABSTRACT FROM AUTHOR]