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First-Principles Analysis of Coverage, Ensemble, and Solvation Effects on Selectivity Trends in NO Electroreduction on Pt3Sn Alloys
journal contribution
posted on 2020-08-05, 19:12 authored by Siddharth Deshpande, Jeffrey GreeleyContamination
of groundwater by runoff of NOx species
from agricultural land is a growing problem with increasingly
negative consequences for public health. Among other technologies,
denitrification of runoff streams via electrocatalysis is a promising
solution, but a lack of fundamental insights into the relevant reaction
mechanisms and a limited understanding of the molecular-level factors
that control selectivity to desired products have hindered progress.
Previous work suggests that, while Pt electrocatalysts produce primarily
undesirable ammonium (NH4+) products from electrochemical
NOx reduction at room temperature, addition
of promoters such as Sn may tune the solution-phase product selectivity
to yield a mixture of hydroxylamine (NH3OH+)
and ammonium. To elucidate the atomic-scale features responsible for
this significant selectivity shift, we investigate the reaction mechanism
for NO electroreduction on Pt3Sn(111) surfaces using periodic
density functional theory calculations combined with detailed treatments
of surface ensemble, coverage, and solvation effects. High coverages
of NO* on the catalyst surface (up to 5/9 ML) are explicitly considered
to mimic experimental reaction conditions and to ascertain the effect
of adsorbate–adsorbate interactions on the reaction mechanism.
Activation barriers for electrochemical reduction and N–O cleavage
in adsorbed NO* and subsequent reaction intermediates, as well as
chemical N–O bond breaking in similar species, are determined
using a combination of transition state search algorithms and explicit
electrochemical double-layer models. The resulting reaction free energy
landscape highlights the importance of both interactions between the
adsorbed reaction intermediates and NO* and solvation effects in promoting
hydroxylamine production over ammonium on Pt-Sn alloys. Such effects
lead to enhanced stability of the HNO* reaction intermediate, in comparison
to pure Pt, and to its subsequent conversion to hydroxylamine. The
results provide a compact interpretation of how Sn alters the product
selectivity during NO electroreduction on Pt and point to design principles
by which selectivity may be controlled in denitrification and related
electrocatalytic processes.