Self-Supported Ag/Pt/Pd Alloy Aerogels as High-Performance Bifunctional and Durable Electrocatalysts for Methanol and Ethanol Oxidation Reactions

Rajib Sarkar; Lisa S Graves; Jessie R Taylor; Indika U Arachchige

doi:10.1021/acsami.3c07740

Self-Supported Ag/Pt/Pd Alloy Aerogels as High-Performance Bifunctional and Durable Electrocatalysts for Methanol and Ethanol Oxidation Reactions

ACS Appl Mater Interfaces. 2023 Oct 30. doi: 10.1021/acsami.3c07740. Online ahead of print.

Authors

Rajib Sarkar¹, Lisa S Graves¹, Jessie R Taylor¹, Indika U Arachchige¹

Affiliation

¹ Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006, United States.

PMID: 37903332
DOI: 10.1021/acsami.3c07740

Abstract

Assembly of nanoparticles (NPs) into functional macrostructures is imperative for the development of NP-based devices. However, existing methods employ insulating organic ligands, polymers, and biomolecules as mediators for the NP assembly, which are detrimental for charge transport and interparticle coupling that impede the efficient integration of low-dimensional properties. Herein, we report a methodology for the direct self-supported assembly of Ag/Pt/Pd alloy NPs into high surface area (119.1 ± 3.9 to 140.1 ± 5.7 m²/g), mesoporous (19.7 ± 6.2 to 23.0 ± 1.6 nm), and conducting nanostructures (aerogels) that show superior electrocatalytic activity and stability in methanol (MOR) and ethanol (EOR) oxidation reactions. Ultrasmall (3.9 ± 1.3 nm) and quasi-spherical Ag/Pt/Pd alloy NPs were synthesized via stepwise galvanic replacement reaction (GRR) of glutathione (GSH)-coated Ag NPs. As-synthesized NPs were transformed into free-standing alloy hydrogels via chemical oxidation of the GSH ligands. The composition of alloy aerogels was tuned by varying the oxidant/thiolate molar ratio of the precursor NP sol that prompts Ag dealloying with in situ generated HNO₃, selectively enriching the Pt and Pd catalytic sites on the aerogel surface. The highest-performing alloy aerogel (Ag_0.449Pt_0.480Pd_0.071) demonstrates excellent mass activity for methanol (3179.5 mA/mg) and ethanol (2444.5 mA/mg) electro-oxidation reactions, which are ∼4-5 times higher than those of commercial Pt/C and Pd/C electrocatalysts. The aerogel also maintained high alcohol oxidation activity for 17 h at a constant potential of -0.3 V in an alkaline medium. The synergistic effects of noble metal alloying, high surface area and mesoporosity, and the pristine active surface of aerogels provide efficient interaction of analytes with the nanostructure surface, facilitating both MOR and EOR activity and improving tolerance for poisonous byproducts, enabling the Ag/Pt/Pd alloy aerogel a promising (electro)catalyst for a number of new technologies.

Keywords: Ag dealloying; Ag/Pt/Pd alloy NPs; alcohol electro-oxidation reactions; metal aerogels; oxidation-induced NP self-assembly.