Improved Rate for the Oxygen Reduction Reaction in a Sulfuric Acid Electrolyte using a Pt(111) Surface Modified with Melamine

Zorko, Milena; Farinazzo Bergamo Dias Martins, Pedro; Connell, Justin G.; Lopes, Pietro Papa; Markovic, Nenad M.; Stamenkovic, Vojislav R.; Strmcnik, Dusan

doi:10.1021/acsami.0c18167

Improved Rate for the Oxygen Reduction Reaction in a Sulfuric Acid Electrolyte using a Pt(111) Surface Modified with Melamine

Journal Article · Wed Jan 06 00:00:00 EST 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c18167· OSTI ID:1774142

^[1]; ^[2]; ^[2]; ^[2]; Markovic, Nenad M. ^[2]; ^[2]; ^[2]

Argonne National Lab. (ANL), Lemont, IL (United States); Centre of Excellence for Low-Carbon Technologies (CoE LCT), Ljubljana (Slovenia)
Argonne National Lab. (ANL), Lemont, IL (United States)

The feasible commercialization of alkaline, phosphoric acid and polymer electrolyte membrane fuel cells depends on the development of oxygen reduction reaction (ORR) electrocatalysts with improved activity, stability, and selectivity. The rational design of surfaces to ensure these improved ORR catalytic requirements relies on the so-called "descriptors" (e.g., the role of covalent and noncovalent interactions on platinum surface active sites for ORR). Here, we demonstrate that through the molecular adsorption of melamine onto the Pt(111) surface [Pt(111)-M_ad], the activity can be improved by a factor of 20 compared to bare Pt(111) for the ORR in a strongly adsorbing sulfuric acid solution. Additionally, the M_ad moieties act as "surface-blocking bodies," selectively hindering the adsorption of (bi)sulfate anions (well-known poisoning spectator of the Pt(111) active sites) while the ORR is unhindered. This modified surface is further demonstrated to exhibit improved chemical stability relative to Pt(111) patterned with cyanide species (CN_ad), previously shown by our group to have a similar ORR activity increase compared to bare Pt(111) in a sulfuric acid electrolyte, with Pt(111)-M_ad retaining a greater than ninefold higher ORR activity relative to bare Pt(111) after extensive potential cycling as compared to a greater than threefold higher activity retained on a CN_ad-covered Pt(111) surface. We suggest that the higher stability of the Pt(111)-M_ad interface stems from melamine's ability to form intermolecular hydrogen bonds, which effectively turns the melamine molecules into larger macromolecular entities with multiple anchoring sites and thus more difficult to remove.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1774142

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 2 Vol. 13; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Improved Rate for the Oxygen Reduction Reaction in a Sulfuric Acid Electrolyte using a Pt(111) Surface Modified with Melamine

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