Identification of PdPt alloys for preferential C₆ olefin hydrogenation over aromatic hydrocarbons through density functional theory and microkinetic modeling

Abstract

Pd3Pt1 is identified with high selectivity (low aromatic depletion), while Pd1Pt1 and Pd1Pt3 are more active for olefin hydrogenation. The PdPt alloys present superior sulfur tolerance compared to Pd.

Discovery of Alloy Catalysts Beyond Pd for Selective Hydrogenation of Reformate via First‐Principle Screening with Consideration of H‐Coverage

“…The process is exothermic, and the consumed H atoms can be refilled quickly from the H 2 dissociation adsorption. According to our previous study, [18] the rate-determining steps (RDS) of C 2 H 4 hydrogenation and C 3 H 4 hydrogenation are both the first hydrogenation step for PdPt alloys. Therefore, we performed microkinetic model on C 2 H 4 and C 3 H 4 hydrogenation by only considering first hydrogenation step as RDS, where free energy profiles are shown in Figure S7, and compared the rate of C 2 H 4 and C 3 H 4 hydrogenation with those along complete reaction pathways.…”

Discovery of Alloy Catalysts Beyond Pd for Selective Hydrogenation of Reformate via First‐Principle Screening with Consideration of H‐Coverage

“…Details of calculations about kinetic H coverage and microkinetic modeling of hydrogenation; the Gibbs adsorption free energies of H as a function of H coverage on various surfaces; the flow chart about the process of H coverage self‐consisting iteration; the simplification process and energy profiles of olefin hydrogenation calculation; the relationship between H coverage and H adsorption energy; the scaling relations between energies of different states in olefin hydrogenation; the experimental and calculated catalytic properties of partial models and candidates and the character of Zn 3 Ir 1 . The authors have cited additional references within the Supporting Information [25a–d,18, 25e−g] …”