Elucidation of C–N bond cleavage mechanism in quinoline hydrodenitrogenation over Pt-based catalysts.

[Display omitted] • TiO 2 acts as an electron additive to change the electronic state of the Pt. • Ti3+-Ptδ− site enables hydrogen heterolytic cleavage to produce protons. • Ti3+-Ptδ− sites change the reactant adsorption and bond cleavage energy barriers. • The mechanism of C-N bond breaking is first protonation and then β-elimination. • Four-fold increase in durability of deposited TiO 2 catalysts. C–N bond breaking is a difficult but crucial step in the quinoline removal of coal-based liquids. Noble metal catalysts have higher C–N bond breaking activity, but their surface bond breaking mechanism is unclear. Atomic layer deposition creates more metal-oxide sites and generates different active species, which facilitates the mechanism study. For this reason, we used atomic layer deposition to deposit TiO 2 on the catalyst surface and suggested a more complete C–N bond breaking mechanism in this study. The particle size and pore structure of the catalyst did not change significantly after the deposition, and the hydrogen adsorption was reduced when there were too many layers deposited and the surface Pt sites were occupied to a high degree. TiO 2 is extremely susceptible to reduction to Ti3+ under hydrogen, and can change the nature of the electron density of Pt through oxygen vacancies, creating Ti3+-Ptδ− sites that are prone to protonation reactions. That means, the occurrence of these protonation reactions not only easily breaks the C–N bond, but also accelerates the rate of C–N bond cleavage due to the increased H coverage on the surface of the xcTi-PtAl catalysts. And the Ti3+-Ptδ− sites in catalyst had a stronger adsorption effect on the nitrogen-containing compounds, which in turn lowered the energy barriers of bond cleavage. It is concluded that protonation is a necessary step before the C–N bond can be broken. The subsequent steps were showed by the DFT calculations that the nitrogen-containing compounds adsorbed on the Ti3+-Ptδ− sites undergo β-H fracture after the protonation reaction, with the elimination reaction cleaving the C–N bond. The xcTi-PtAl catalysts by atomic layer deposition of Ti not only improve the C–N bond breaking performance, but also improve bond breaking stability by a factor of four compared to the Pt/Al 2 O 3 catalysts. [ABSTRACT FROM AUTHOR]