Electrocatalytic Mechanisms in Metal Nanostructures

Electrocatalytic mechanisms in metal nanostructures underpin a wide array of energy conversion and storage technologies, from water splitting to fuel cells and hydrogen production. At the nanoscale, metals exhibit size-dependent electronic structures and high surface-to-volume ratios, enabling tailored adsorption and reaction kinetics. Key parameters such as surface strain, ligand effects and support interactions modulate the binding energies of reaction intermediates, thus influencing activity and selectivity. Morphological control achieved through electrodeposition, atomic layer deposition and template methods allows precise tuning of feature size, porosity and composition. In situ characterisation techniques, including liquid cell transmission electron microscopy and synchrotron-based spectroscopies, have revealed dynamic structural transformations under operational conditions and clarified the roles of surface oxides, alloy formation and interface energetics. Understanding these fundamental processes is essential for the rational design of robust, high-performance electrocatalysts with optimised reaction pathways and long-term stability.

Research from Nature Portfolio

Recent investigations into platinum electrodeposition on tin substrates have shown that surface oxide layers strongly inhibit nucleation, whereas direct Pt–Sn alloy formation during deposition yields catalysts with enhanced activity for carbon monoxide oxidation. By analysing deposition in borate buffer with platinum precursors, researchers demonstrated that controlling oxide coverage is critical to uniform alloy growth and that in situ alloying at the metal interface promotes superior electrocatalytic performance. These insights inform strategies for designing durable catalysts on non-noble supports suitable for fuel cell and electrolyser applications.

Electrocatalytic Mechanisms in Metal Nanostructures publication trend

The graph below shows the total number of articles in electrocatalytic mechanisms in metal nanostructures across all publications each year (not limited to Nature Index journals).

Technical terms

Electrocatalysis: Acceleration of electrochemical reactions at electrode surfaces by a catalyst, involving charge transfer with reactants in solution.

Underpotential deposition (UPD): Electrochemical deposition of a metal monolayer onto a substrate at potentials more positive than its standard reduction potential due to substrate–metal interactions.

Overpotential: Additional potential beyond the thermodynamic equilibrium potential required to drive an electrochemical reaction at a measurable rate.

Volmer–Heyrovsky mechanism: A two-step pathway for hydrogen evolution involving proton adsorption (Volmer step) followed by electrochemical desorption of hydrogen molecules (Heyrovsky step).

In situ characterisation: Analytical techniques that probe structural or compositional changes of materials under operational or reactive conditions.

Adsorption energy: Energy change associated with the binding of reaction intermediates to the catalyst surface, influencing reaction kinetics and selectivity.

References

1. Understanding the Growth of Electrodeposited PtNi Nanoparticle Films Using Correlated In Situ Liquid Cell Transmission Electron Microscopy and Synchrotron Radiation. Nano Letters (2024).
2. Au-Nanorods Supporting Pd and Pt Nanocatalysts for the Hydrogen Evolution Reaction: Pd Is Revealed to Be a Better Catalyst than Pt. Nanomaterials (2023).
3. Electrochemical Stability and Degradation of Commercial Pd/C Catalyst in Acidic Media. The Journal of Physical Chemistry C (2021).
4. Direct PtSn Alloy Formation by Pt Electrodeposition on Sn Surface. Scientific Reports (2020).