Pt nanoparticle with high Pt-Pt coordination number and degenerate d
orbitals, has a strong affinity to naphtha and relevant intermediates,
leading to severe carbon deposition and catalyst deactivation during
naphtha reforming. The catalytic performance of Pt catalyst could be
finely tuned by tailoring its d-electron structure. Herein, we propose a
straightforward chlorinating strategy to transform PtOx nanoparticle
into Pt single atoms with a specific Cl-Pt-O coordination. The
adsorption of benzene on Pt is weakened with the Cl-Pt-O coordination,
which facilitates aromatics desorption and hampers carbon deposition.
Density functional theory (DFT) calculation indicates that the z-axis of
Pt 5d orbitals is occupied and selectively exposes xy-plane orbital (dxy
and dx2-y2), which weakens d-π hybridization between Pt 5d orbitals and
π orbital of benzene ring. The d-electron regulation through
chlorinating is a readily scalable strategy to synthesis single atom
catalysts, and optimize naphtha reforming catalytic performance.