title: Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles.
abstract: The mechanism of nitric oxide electroreduction on Pt(111) is investigated using a combination of first principles calculations and electrokinetic rate theories. Barriers for chemical cleavage of N-O bonds on Pt(111) are found to be inaccessibly high at room temperature, implying that explicit electrochemical steps, along with the aqueous environment, play important roles in the experimentally observed formation of ammonia. Use of explicit water models, and associated determination of potential-dependent barriers based on Bulter-Volmer kinetics, demonstrate that ammonia is produced through a series of water-assisted protonation and bond dissociation steps at modest voltages (<0.3 V). In addition, the analysis sheds light on the poorly understood formation mechanism of nitrous oxide (N2 O) at higher potentials, which suggests that N2 O is not produced through a Langmuir-Hinshelwood mechanism; rather, its formation is facilitated through an Eley-Rideal-type process.
authors.affiliation: Department of Chemistry, Nanoscience Center, University of Jyväskylä, Survontie 9C, Jyväskylä (Finland).
authors.forename: Andre
authors.initials: A
authors.lastname: Clayborne
authors.affiliation: School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN (USA).
authors.forename: Hee-Joon
authors.initials: HJ
authors.lastname: Chun
authors.affiliation: Department of Chemical Engineering, Villanova University, White Hall, 800 Lancaster Avenue, Villanova, PA (USA).
authors.forename: Rees B
authors.initials: RB
authors.lastname: Rankin
authors.affiliation: School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN (USA). jgreeley@purdue.edu.
authors.forename: Jeff
authors.initials: J
authors.lastname: Greeley
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D008958:Models, Molecular; D009569:Nitric Oxide / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*
chemical_list: D009569:Nitric Oxide; D010984:Platinum; D000641:Ammonia
keywords: NO reduction; ammonia; density functional theory; electrocatalysis; nitrous oxide