The effects of morphology, microstructure and mixed-valent states of MnO2 on the oxygen evolution reaction activity in alkaline anion exchange membrane water electrolysis

Abstract

In this work, we focused on the evaluation of oxygen evolution reaction (OER) activity of three different shapes of α-MnO2 nanowires (NWs), nanorods (NRs) and nanotubes (NTs) in alkaline anion exchange water electrolyser. We have attempted to separate the effect of shape, surface area, Mn3+ content and crystal facets on OER activity and stability. X-ray Photoelectron Spectroscopy (XPS) measurements showed that NTs had the highest surface concentration of Mn3+ on the as prepared samples with average Mn oxidation state of 3.33. However, after activation an increase in the average oxidation state of all three shapes to 3.9 was confirmed by XPS. X-Ray Diffraction (XRD) showed surface restructuring after testing. MnO2 NWs showed the highest OER mass activity of 60.6 A g−1 (10 mA cm−2 at 1.67 V (RHE)) due to the higher surface area of 72.2 m2 g−1. While NTs showed the highest specific activity due to highest content of 211 facet, high Mn3+ surface concentration/surface defects. Similar trend was observed in electrolyser testing with 2 mg cm−2 loading. Poor electronic conductivity of MnO2 resulted in decrease in performance with increased loading to 4 mg cm−2. All the studied shapes showed good stability over 36 h of electrolyser testing.