Mechanism of the electrochemical hydrogenation of graphene

TL;DR

This study uncovers the mechanism behind electrochemical hydrogenation of graphene, revealing a rapid, reversible process involving proton adsorption and H2 formation, with implications for electronic property control in 2D materials.

Contribution

It elucidates the reaction mechanism, demonstrates the process's speed and reversibility, and shows how lattice modifications and isotope substitution influence hydrogenation.

Findings

Hydrogenation proceeds via a reduction reaction with proton adsorption and H2 formation.

Electrochemical hydrogenation is up to 10^6 times faster than other methods.

Nanoscale lattice corrugations enhance proton reduction rate; deuterons lower hydrogenation potentials.

Abstract

The electrochemical hydrogenation of graphene induces a robust and reversible conductor-insulator transition, of strong interest in logic-and-memory applications. However, its mechanism remains unknown. Here we show that it proceeds as a reduction reaction in which proton adsorption competes with the formation of H2 molecules via an Eley-Rideal process. Graphene's electrochemical hydrogenation is up to $10^6$ times faster than alternative hydrogenation methods and is fully reversible via the oxidative desorption of protons. We demonstrate that the proton reduction rate in defect-free graphene can be enhanced by an order of magnitude by the introduction of nanoscale corrugations in its lattice, and that the substitution of protons for deuterons results both in lower potentials for the hydrogenation process and in a more stable compound. Our results pave the way to investigating the chemisorption of ions in 2D materials at high electric fields, opening a new avenue to control these materials' electronic properties.