Electrocatalysis – Iron and Cobalt Oxyhydroxides examined at BESSY II

Very soon, we need to become fossil free, not only in the energy sector, but as well in industry. Hydrocarbons or other raw chemicals can be produced in principle using renewable energy and abundant molecules such as water and carbon dioxide with the help of electrocatalytically active materials. But at the moment, those catalyst materials either consist of expensive and rare materials or lack efficiency.

Key reaction in water splitting

A team led by Dr. Prashanth W. Menezes (HZB/TU-Berlin) has now gained insights into the chemistry of one of the most active catalysts for the anodic oxygen evolution reaction (OER), which is a key reaction to supply electrons for the hydrogen evolution reaction (HER) in water splitting. The hydrogen can then be processed into further chemical compounds, e.g., hydrocarbons. Additionally, in the direct electrocatalytic carbon dioxide reduction to alcohols or hydrocarbons, the OER also plays a central role.

Electrocatalysts for the Oxygen Evolution Reaction

A highly promising class of electrocatalysts for OER are Cobalt-Iron Oxyhydroxides. The scientists analysed a series of LiFe_1-xCo_x borophosphates at BESSY II with different spectroscopy techniques to determine the oxidation states of the element Iron (Fe) in different configurations.

Iron: higher oxidation states  and shorter bond distances

“Fe plays an important role in Co-based OER catalysts. However, the exact reason for this is still under debate. Most studies assume/measure Fe in lower oxidation states (+3) as a part of the active structure. In our case, however, we could show Fe in oxidation states ≥ 4 and shortened bond distances which provide us a better understanding of the catalytically active species ”, Menezes points out.

Electrocatalysts facilitate the charge transfer from the substrate (here water) to the electrodes, which mostly involves a change of the transition metal oxidation states. However, these oxidation state changes are sometimes too quick to be detected, which makes it hard to understand the working principle of the catalyst especially when it contains two potentially active elements.

This work emphasizes the geometrical structure of the active sites and on the redox behaviour of the two participating elements (Co and Fe in the present case). Such an understanding helps to enable design guided development of catalysts on a molecular level. “We hope that the detailed electronic and structural description can substantially contribute to the improvement of OER catalysts”, Menezes says.

Note: The team involved scientists from the CatLab at Helmholtz-Zentrum Berlin, Technische Universität Berlin, and Freie Universität Berlin. The X-ray absorption spectroscopy was performed at beamline KMC-3 at BESSY II.

Journal: Advanced Energy Materials
DOI: 10.1002/aenm.202203886
Method of Research: Experimental study
Subject of Research: Not applicable
Article Title: In Situ Detection of Iron in Oxidation States ≥ IV in Cobalt-Iron Oxyhydroxide Reconstructed during Oxygen Evolution Reaction
Article Publication Date: 2-Feb-2023
COI Statement: none