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Dynamics of Volatile Products in the Electro-oxidation of Ethanol on Pt/C and PtSn/C Catalysts

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Author(s):
Vilas-Boas, N. ; Tessaro, G. N. ; Hostert, L. ; de Oliveira-Filho, A. G. S. ; Perez, J. ; Varela, H.
Total Authors: 6
Document type: Journal article
Source: Journal of Physical Chemistry C; v. 129, n. 42, p. 10-pg., 2025-10-09.
Abstract

Ethanol electro-oxidation reaction (EEOR) is a strategically important reaction for the development of fuel cells and low-temperature electrolysis technologies, although its application is hindered by slow kinetics and poor selectivity toward the C1 pathway (CO2 formation) on platinum-based catalysts. In this study, the dynamic formation of volatile products (acetaldehyde, acetic acid, and CO2) was investigated during the EEOR on Pt/C and PtSn/C electrodes in acidic media, with particular emphasis on oscillatory conditions using online electrochemical mass spectrometry (OLEMS). PtSn/C catalysts were synthesized via chemical reduction and characterized by XRD, TEM, and XPS, revealing smaller particle sizes, a higher proportion of oxidized Pt species, and the presence of Sn4+ as SnO2. OLEMS experiments showed earlier onset for acetaldehyde, CO2, and acetic acid products for PtSn/C. Despite the low volatility of acetic acid, its production was confirmed and quantified by high-performance liquid chromatography (HPLC), reaching up to 965.2 ppm at 0.5 V, which is 97 times higher than that of Pt/C. Multivariate linear regression (MLR) analysis revealed a greater contribution of acetic acid and CO2 to the faradaic current for PtSn/C, indicating a substantial shift in the reaction pathway. Under oscillatory conditions, PtSn/C exhibited greater robustness, lower potential amplitude, and reduced susceptibility to surface poisoning. These results highlight the role of Sn in enhancing surface regeneration and promoting deeper oxidation pathways, demonstrating the importance of catalyst design in tuning the selectivity and efficiency of the EEOR. (AU)

FAPESP's process: 21/00675-4 - Tying up materials for electrochemical energy storage and catalysis
Grantee:Roberto Manuel Torresi
Support Opportunities: Research Projects - Thematic Grants
FAPESP's process: 24/12749-0 - Electro-oxidation of ethanol towards the production of energy and clean hydrogen
Grantee:Leandro Hostert
Support Opportunities: Scholarships in Brazil - Post-Doctoral
FAPESP's process: 20/15230-5 - Research Centre for Greenhouse Gas Innovation - RCG2I
Grantee:Julio Romano Meneghini
Support Opportunities: Research Grants - Applied Research Centers Program
FAPESP's process: 20/01177-5 - From Fundamental to Application: New Frontiers in Fuel Cell Technologies
Grantee:Nigel Peter Brandon
Support Opportunities: Research Projects - SPEC Program
FAPESP's process: 19/22183-6 - Electrocatalysis VI: Fundamental and Applied Aspects of Emerging and Classical Problems in Electrochemical Energy Conversion
Grantee:Edson Antonio Ticianelli
Support Opportunities: Research Projects - Thematic Grants