Title: Stabilizing the Meniscus for Operando Characterization of Platinum During the Electrolyte-Consuming Alkaline Oxygen Evolution Reaction

Abstract

Achieving a molecular-level understanding of interfacial (photo)electrochemical processes is essential in order to tailor novel and highly-performing catalytic systems. The corresponding recent development of in situ and operando tools has posed new challenges on experimental architectures. In this study, we use ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to probe the solid/liquid electrified interface of a polycrystalline Pt sample in contact with an alkaline electrolyte during hydrogen and oxygen evolution reactions. Using the “dip-and-pull” technique to probe the interface through a thin liquid layer generated on the sample surface, we observe that the electrolyte meniscus becomes unstable under sustained driving of an electrolyte-consuming reaction (such as water oxidation). The addition of an electrochemically inert supporting electrolyte mitigates this issue, maintaining a stable meniscus layer for prolonged reaction times. In contrast, for processes in which the electrolyte is replenished in the reaction pathway (i.e. water reduction in alkaline conditions), we find that the solid/liquid interface remains stable without addition of a secondary supporting electrolyte. The approach described in this work allows the extension of operando AP-XPS capabilities using the “dip-and-pull” method to a broader class of reactions consuming ionic species during complex interfacial faradaic processes.

Authors:

Stoerzinger, Kelsey A.  ^[1];

• Search DOE PAGES for author "Stoerzinger, Kelsey A."
• Search DOE PAGES for ORCID "0000-0002-3431-8290"

Favaro, Marco  ^[1];

• Search DOE PAGES for author "Favaro, Marco"
• Search DOE PAGES for ORCID "0000-0002-3502-8332"

Ross, Philip N. ^[1]; Hussain, Zahid ^[1]; Liu, Zhi ^[2]; Yano, Junko ^[1]; Crumlin, Ethan J.  ^[1]

• Search DOE PAGES for author "Crumlin, Ethan J."
• Search DOE PAGES for ORCID "0000-0003-3132-190X"

---

+ Show Author Affiliations

1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
2. Chinese Academy of Sciences (CAS), Beijing (China); Shanghai Tech Univ., Shanghai (China)

Publication Date:

Tue Oct 23 00:00:00 EDT 2018

Research Org.:

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC)

OSTI Identifier:

1580347

Grant/Contract Number:  

AC02-05CH11231

Resource Type:

Accepted Manuscript

Journal Name:

Topics in Catalysis

Additional Journal Information:

Journal Volume: 61; Journal Issue: 20; Journal ID: ISSN 1022-5528

Publisher:

Springer

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ambient pressure XPS; Electrocatalysis; Oxygen evolution reaction; Hydrogen evolution reaction; Solid/liquid interface stability