Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces

The conversion of CO(2) into fuels and chemicals is an attractive option for mitigating CO(2) emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C–C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C–C coupling on a supported Ru/TiO(2) catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO(2) hydrogenation behavior of the Ru surface, significantly enhancing the C(2+) production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems.