# Water oxidation catalysis on reconstructed NaTaO$_3$ (001) surfaces

## TL;DR

This study uses DFT calculations to show that reconstructed NaTaO$_3$ (001) surfaces enhance water oxidation catalysis by lowering overpotentials and enabling new reaction pathways, with implications for photocatalytic applications.

## Contribution

It reveals how surface reconstruction of NaTaO$_3$ influences catalytic activity and introduces new low-overpotential reaction pathways not present on other surfaces.

## Key findings

- Reconstruction lowers overpotential from 0.88 V to 0.70 V.
- Ta sites become more active under photocatalytic conditions.
- Alternative reconstructions enable oxygen coupling with 0.52 V overpotential.

## Abstract

Polar perovskite oxide surfaces are subject to structural reconstruction as a possible stabilisation mechanisms, which changes the surface structure and hence the surface chemistry. To investigate this effect, we study the oxygen evolution reaction (OER) on the reconstructed (001) surface of NaTaO$_3$, by means of density functional theory (DFT) calculations and compare it with the non-polar (113) surface of the same material. For the clean surface the reconstruction has a beneficial effect on the catalytic activity, lowering the minimal overpotential from 0.88 V to 0.70 V while also changing the most active reaction site from Na to Ta. Under photocatalytic conditions, the Ta sites are covered by oxygen adsorbates, rendering a lattice oxygen site on the NaO terrace the most active with a very low overpotential of 0.32 V. An alternative surface reconstruction stable in contact with water leads to an oxygen coupling mechanism with an overpotential of 0.52 V. Our results show that terraced surface reconstructions enable novel reaction pathways with low overpotentials that do not exist on other non-polar NaTaO$_3$ surfaces nor on non-polar surfaces of chemically similar materials such as SrTaO$_2$N.