Effect of Interlayer Spacing on the Activity of Layered Manganese Oxide Bilayer Catalysts for the Oxygen Evolution Reaction

Qing Kang; Loranne Vernisse; Richard C Remsing; Akila C Thenuwara; Samantha L Shumlas; Ian G McKendry; Michael L Klein; Eric Borguet; Michael J Zdilla; Daniel R Strongin

doi:10.1021/jacs.6b09184

Effect of Interlayer Spacing on the Activity of Layered Manganese Oxide Bilayer Catalysts for the Oxygen Evolution Reaction

J Am Chem Soc. 2017 Feb 8;139(5):1863-1870. doi: 10.1021/jacs.6b09184. Epub 2017 Jan 30.

Authors

Qing Kang^{1

2}, Loranne Vernisse^{1

2}, Richard C Remsing^{1

2

3}, Akila C Thenuwara^{1

2}, Samantha L Shumlas^{1

2}, Ian G McKendry^{1

2}, Michael L Klein^{1

2

3}, Eric Borguet^{1

2}, Michael J Zdilla^{1

2}, Daniel R Strongin^{1

2}

Affiliations

¹ Department of Chemistry, Temple University , Beury Hall, 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.
² Center for the Computational Design of Functional Layered Materials (CCDM), Temple University , Philadelphia, Pennsylvania 19122, United States.
³ Institute for Computational Molecular Science, Temple University , SERC, 1925 North 12th Street, Philadelphia, Pennsylvania 19122, United States.

PMID: 28085268
DOI: 10.1021/jacs.6b09184

Abstract

We investigated the dependence of the electrocatalytic activity for the oxygen evolution reaction (OER) on the interlayer distance of five compositionally distinct layered manganese oxide nanostructures. Each individual electrocatalyst was assembled with a different alkali metal intercalated between two nanosheets (NS) of manganese oxide to form a bilayer structure. Manganese oxide NS were synthesized via the exfoliation of a layered material, birnessite. Atomic force microscopy was used to determine the heights of the bilayer catalysts. The interlayer spacing of the supported bilayers positively correlates with the size of the alkali cation: NS/Cs⁺/NS > NS/Rb⁺/NS > NS/K⁺/NS > NS/Na⁺/NS > NS/Li⁺/NS. The thermodynamic origins of these bilayer heights were investigated using molecular dynamics simulations. The overpotential (η) for the OER correlates with the interlayer spacing; NS/Cs⁺/NS has the lowest η (0.45 V), while NS/Li⁺/NS exhibits the highest η (0.68 V) for OER at a current density of 1 mA/cm². Kinetic parameters (η and Tafel slope) associated with NS/Cs⁺/NS for the OER were superior to that of the bulk birnessite phase, highlighting the structural uniqueness of these nanoscale assemblies.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.