Electrochemical production of H₂O₂ on palladium-based clusters driven by metal–support interaction

Journal Article · Wed Oct 08 00:00:00 UTC 2025 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/d5ta05763a · OSTI ID:2999807

Bharathan, Prabhu  ^[1]; Li, Can  ^[1]; Zhao, Bo ^[2]; Dennett, Anna ^[1]; Zhang, Lihua  ^[3]; Fang, Jiye  ^[1]

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1. State Univ. of New York (SUNY), Binghamton, NY (United States)
2. Texas Tech Univ., Lubbock, TX (United States)
3. Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Utilizing palladium (Pd) clusters as active sites offers a promising route to minimize noble metal consumption in electrochemical hydrogen peroxide (H₂O₂) production. In this work, we present a synthesis approach for anchoring Pd-based clusters onto carbon-supported CeO₂ nanosubstrates to enable efficient H₂O₂ generation via the two-electron oxygen reduction reaction (ORR) pathway. By systematically adjusting Pd loading, we evaluated its impact on H₂O₂ yield and production rate. The catalyst with the lowest Pd content (0.027 wt%) exhibited outstanding performance, achieving 97% H₂O₂ selectivity, 94.2 faradaic efficiency at 0.7 V vs. RHE, and a peak production rate of 195.8 mol g_Pd⁻¹ h⁻¹. A formulation containing 0.35 wt% Pd delivered a peak ORR mass activity nearly three times as high as that of commercial 10 wt% Pd/C, while retaining comparable electrochemical stability. These enhancements are attributed to synergistic effects among isolated PdO clusters, CeO₂ nanocrystals, and the conductive carbon support, which together facilitate oxygen adsorption and promote the two-electron ORR pathway. Analysis after accelerated durability testing further revealed a tendency toward cluster agglomeration and mass transfer from smaller to larger nanocrystals, indicative of a coarsening mechanism. Overall, this study underscores the promise of low-Pd PdO–CeO₂–carbon hybrid catalysts for scalable and efficient H₂O₂ electrosynthesis, while highlighting stability as a critical area for future improvement.

• Research Organization: Brookhaven National Laboratory (BNL), Upton, NY (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
• Grant/Contract Number: SC0012704
• OSTI ID: 2999807
• Report Number(s): BNL--229078-2025-JAAM
• Journal Information: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 44 Vol. 13; ISSN 2050-7488; ISSN 2050-7496
• Publisher: Royal Society of ChemistryCopyright Statement
• Country of Publication: United States
• Language: English