title: Theoretical Modelling and Facile Synthesis of a Highly Active Boron-Doped Palladium Catalyst for the Oxygen Reduction Reaction.
abstract: A highly active alternative to Pt electrocatalysts for the oxygen reduction reaction (ORR), which is the cathode-electrode reaction of fuel cells, is sought for higher fuel-cell performance. Our theoretical modelling reveals that B-doped Pd (Pd-B) weakens the absorption of ORR intermediates with nearly optimal binding energy by lowering the barrier associated with O2 dissociation, suggesting Pd-B should be highly active for ORR. In fact, Pd-B, facile synthesized by an electroless deposition process, exhibits 2.2 times and 8.8 times higher specific activity and 14 times and 35 times less costly than commercial pure Pd and Pt catalysts, respectively. Another computational result is that the surface core level of Pd is negatively shifted by B doping, as confirmed by XPS, and implies that filling the density of states related to the anti-bonding of oxygen to Pd surfaces with excess electrons from B doping, weakens the O bonding to Pd and boosts the catalytic activity.
authors.affiliation: School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
authors.forename: Tat Thang
authors.initials: TT
authors.lastname: Vo Doan
authors.affiliation: School of Materials Science & Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
authors.forename: Jingbo
authors.initials: J
authors.lastname: Wang
authors.affiliation: School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
authors.forename: Kee Chun
authors.initials: KC
authors.lastname: Poon
authors.affiliation: School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
authors.forename: Desmond C L
authors.initials: DC
authors.lastname: Tan
authors.affiliation: Division of Chemistry & Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
authors.forename: Bahareh
authors.initials: B
authors.lastname: Khezri
authors.affiliation: Division of Chemistry & Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
authors.forename: Richard D
authors.initials: RD
authors.lastname: Webster
authors.affiliation: School of Materials Science & Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore. hbsu@ntu.edu.sg.
authors.forename: Haibin
authors.initials: H
authors.lastname: Su
authors.affiliation: School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore. hirosato@ntu.edu.sg.
authors.forename: Hirotaka
authors.initials: H
authors.lastname: Sato
keywords: density functional theory; electrocatalysts; nanoparticles; oxygen reduction reaction; palladium