Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation

Abstract

The origin of selectivity and activity of the CO₂ hydrogenation reaction on single-atom catalysts composed of three adjacent 3d transition metals (Fe, Co, and Ni) supported on N-doped graphene quantum dots were systematically investigated and compared using density functional theory (DFT) calculations, natural bond orbital (NBO), and quantum theory of atoms in molecules (QTAIM) analysis. This study reveals that π-backbonding between the metal and CO₂* does not occur and [CO₂]^δ+ species drive the reaction. The CO₂* reacts with H₂ via the Eley-Rideal (ER) mechanism by using the synergistic effects of the N site. The higher the partial positive charge on the C atom, the lower the Ea of the reaction. Subsequently, a tautomerization reaction, which is facilitated by hydrogen bonding, occurs and hydrogen is transferred to HCOO* resulting in the formation of CHOOH*. This study shows the selective formation of formic acid from CO₂ is accessible on these SACs and Fe-SAC is the best one between these three catalysts. Although CO₂ is more inert than formic acid the H₂ molecule reacts with the adsorbed formic acid more difficult than the adsorbed CO₂. It is because the hydrogenation of formic acid causes C-H bond formation resulting in failure of the coordinated O atom's octet and the unstable H₂COOH* is formed. This step is the rate-determining step of HOCH₂OH formation from CO₂, with Ea of 1.94, 2.03, and 2.23 eV for Fe, Co, and Ni, respectively. Finally, the system undergoes another tautomerization reaction resulting in the formation of HOCH₂OH (formaldehyde monohydrate).