Issue 30, 2025

Ptn-Mn(II)Nx and Ptn-Mn(III)Nx are both winning combinations for the durability of these hybrid catalysts in PEM fuel cells: a deep insight into synergism between Pt clusters and MnNx/C sites

Abstract

In this work, we investigated the influence of a carbon substrate (graphene), doped or undoped, on the adsorption energy, and thus the stability, of Pt(n)-clusters/nanoparticles (NPs) grown on it. For substrate doping, we considered N-doping (graphitic or pyridinic), and carbon doping with MnN(2+2)/C or MnN(4+2)/C sites in the immediate vicinity of Pt(n)-clusters/NPs. These non-noble sites, containing Mn(II) or Mn(III), are also capable of oxygen reduction in fuel cells, similar to Pt(n) nanoparticles. The Pt(n)-graphene interaction is initiated by a Pt atom occupying a single carbon vacancy, forming three Pt–C bonds. The entire Pt(n)-cluster/NP is then built upon this atom. A more negative adsorption energy corresponds to stronger adhesion and enhanced cluster stability. This effect is particularly pronounced when the graphene substrate is doped with Mn(II or III)N(4+2)/C or Mn(II or III)N(2+2)/C sites. We further examined whether a Pt(n)-cluster/NP adjacent to a MnNx/C site could stabilize the latter against demetallation in acidic PEM fuel cell environments. Our findings confirm this hypothesis: Pt(n) effectively stabilizes MnNx/C against demetallation. This effect is especially significant for Mn(II)N(4+2)/C and Mn(II)N(2+2)/C sites, previously shown to undergo spontaneous Mn demetallation. In the presence of Pt(n), the formerly spontaneous demetallation becomes a thermodynamic equilibrium (in a closed thermodynamic environment), improving MnNx/C stability. Despite this stabilization, MnNx sites remain less durable than platinum under PEM fuel cell cathode conditions. This led us to examine what happens to Pt(n) adhesion after Mn demetallation. Our calculations show that the Pt–C bonding energy is minimally affected by the demetallated MnNx sites. Thus, Pt(n) clusters should remain stably anchored even after Mn loss. Finally, beyond these stability insights, we reviewed literature regarding the catalytic performance of Pt(n)-MnNx/C hybrid systems, highlighting how they combine the high activity of Pt with the complementary functionalities of non-noble molecular sites. These findings provide theoretical guidance for designing more robust and efficient hybrid electrocatalysts for fuel cell applications.

Graphical abstract: Ptn-Mn(II)Nx and Ptn-Mn(III)Nx are both winning combinations for the durability of these hybrid catalysts in PEM fuel cells: a deep insight into synergism between Pt clusters and MnNx/C sites

Supplementary files

Article information

Article type
Paper
Submitted
14 Nov 2024
Accepted
24 Jun 2025
First published
24 Jun 2025
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. A, 2025,13, 24849-24867

Ptn-Mn(II)Nx and Ptn-Mn(III)Nx are both winning combinations for the durability of these hybrid catalysts in PEM fuel cells: a deep insight into synergism between Pt clusters and MnNx/C sites

V. P. Glibin, J. Dodelet and G. Zhang, J. Mater. Chem. A, 2025, 13, 24849 DOI: 10.1039/D4TA08108K

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements