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Influence of Redox-Inactive Cations on the Structure and Electrochemical Reactivity of Synthetic Birnessite, a Heterogeneous Analog for the Oxygen-Evolving Complex

Baricuatro, Jack H. and Saadi, Fadl H. and Carim, Azhar I. and Velazquez, Jesus M. and Kim, Youn-Geun and Soriaga, Manuel P. (2016) Influence of Redox-Inactive Cations on the Structure and Electrochemical Reactivity of Synthetic Birnessite, a Heterogeneous Analog for the Oxygen-Evolving Complex. Journal of Physical Chemistry C, 120 (29). pp. 15618-15631. ISSN 1932-7447. http://resolver.caltech.edu/CaltechAUTHORS:20151005-112626822

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Abstract

Electrochemical protocols were developed for the facile potentiostatic deposition of birnessite films, supported on Au substrates, to serve as a structural motif for oxygen evolution reaction electrocatalysts. The elimination of prolonged cation-exchange submersion dramatically reduced the synthesis time scale from days to minutes. The electrodeposited films were characterized using a combination of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, scanning tunneling microscopy, and X-ray photoelectron spectroscopy. The prepared birnessite films were crystalline, monophasic oxide materials that contained Mn^(3+), Mn^(4+), traces of Mn^(2+), and the intercalant of choice. Redox-inactive Na^+, Ca^(2+), Sr^(2+), Y^(3+), and Zn^(2+) cations showed minimal influence on the voltammetric behavior of birnessite in the presence of Mn^(2+)(aq). Slightly more significant effects emerged during potential cycling and chronopotentiometry of birnessite films in 0.1 M NaOH. The potential needed to sustain a current density of 10 mA cm^(–2) in 0.1 M NaOH increased according to the sequence Na^+ < Ca^(2+) < Sr^(2+) < Y^(3+) < Zn^(2+). The sequence, with slight inversions in the order, was reminiscent of the trend in the heterometal-dependent modulation of the half-wave potential of the redox couple Mn^(3+)Mn_2^(4+)/Mn_3^(4+) in nonaqueous solutions of heterometallic manganese–dioxido cluster systems. Unlike the case of the homogeneous cluster catalysts, the electrochemical reactivity of intercalated birnessite films did not vary linearly with the pK_a of the redox-inactive cations.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.jpcc.5b07028DOIArticle
http://pubs.acs.org/doi/10.1021/acs.jpcc.5b07028PublisherArticle
ORCID:
AuthorORCID
Saadi, Fadl H.0000-0003-3941-0464
Carim, Azhar I.0000-0003-3630-6872
Kim, Youn-Geun0000-0002-5936-6520
Soriaga, Manuel P.0000-0002-0077-6226
Additional Information:© 2015 American Chemical Society. Received: July 21, 2015, Revised: September 10, 2015, Publication Date (Web): September 30, 2015. This article is part of the Kohei Uosaki Festschrift special issue. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award DE-SC0004993.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Record Number:CaltechAUTHORS:20151005-112626822
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20151005-112626822
Official Citation:Influence of Redox-Inactive Cations on the Structure and Electrochemical Reactivity of Synthetic Birnessite, a Heterogeneous Analog for the Oxygen-Evolving Complex Jack H. Baricuatro, Fadl H. Saadi, Azhar I. Carim, Jesus M. Velazquez, Youn-Geun Kim, and Manuel P. Soriaga The Journal of Physical Chemistry C 2016 120 (29), 15618-15631 DOI: 10.1021/acs.jpcc.5b07028
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60755
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:05 Oct 2015 21:55
Last Modified:12 Oct 2017 17:15

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