# First‐Principles Investigation of Adsorption of Ethene on a Twice Oxidized NiF2 (001) Surface: A Model for the Simons Process

## TL;DR

This study uses computational methods to explore how ethene reacts on a nickel fluoride surface during a fluorination process, revealing possible reaction pathways.

## Contribution

This is one of the first computational studies of the Simons process, offering insights into fluorination mechanisms on nickel surfaces.

## Key findings

- Adsorption of ethene on a twice oxidized NiF2 (001) surface leads to multiple fluorinated products.
- Structural outcomes include 1,2-difluoroethane, fluoroethene, and 1,2-difluoroethene.
- The study identifies the catalytic role of higher valent nickel in fluorination reactions.

## Abstract

Electrochemical fluorination on a nickel anode (Simons process) is an important process for producing fluorinated compounds. Despite its success, the mechanism is still under debate. Here a first‐principles study is presented of fluorination of ethene on a model fluorinated (001) NiF surface, which is chosen because it is stabilized under the external potential close to that at which the Simons cell operates and because it has a readily available [F2]− unit providing fluorine source to aid fluorination reactions. The adsorption of the simplest double bond containing hydrocarbon on this surface is investigated. It is placed on the surface in different orientation, leading to six distinct structural outcomes upon relaxation. These include formation of 1,2‐difluoroethane, fluoroethene, and 1,2‐difluoroethene, alongside other fluorinated products as well as monocarbon fragments. This is one of the first computational studies of the catalytic Simons‐type fluorination and can, despite its simplicity, offers some insight into reaction pathways and surface interactions.

A density functional theory study of ethene adsorption on a twice oxidized NiF2 (001) surface reveals multiple fluorination pathways, providing insight into the catalytic role of the higher valent nickel surface in the Simons process (electrochemical fluorination on a nickel anode).© 2026 WILEY‐VCH GmbH