CO2 thermoreduction to methanol on the F3-CNT catalyst: A DFT study

Carbon nanotubes (CNTs) have a unique hollow structure that can protect the atomic clusters inside them and prevent the catalyst from being poisoned. Meanwhile, fluorine, as the element with the highest electronegativity , has a unique impact on the properties of fluorine-containing materials. In this paper, the first-principles simulation was employed to study the carbon dioxide reduction reaction (CO 2 RR) on CNTs with fluorine atoms introduced on the inner surface. F3-CNT exhibits high formation energy of -5.976 eV and also shows high adsorption energy of -19.043 eV during the adsorption process of CO 2 . The CO 2 RR mainly involves the reverse water gas shift (RWGS) and CO hydrogenation processes . By comparing the Gibbs free energies corresponding to various reaction intermediates, the optimal pathway was determined as *CO 2 →*CO→*CHO→*CHOH→*CH 2 OH→CH 3 OH, ultimately verifying that the main product is methanol. The research indicates that the inner surface fluorinated carbon nanotubes are promising high-performance catalytic materials for the CO 2 reduction reaction.