Ragassi Gianluca, Sitta Elton, Pan Changwei, Gao Qingyu, Varela Hamilton
São Carlos Institute of Chemistry (IQSC), University of São Paulo (USP), PO Box 780, 13560-970, São Carlos, SP, Brazil.
Department of Chemistry, Federal University of Sao Carlos (UFSCar), Sao Carlos, Brazil.
Chemphyschem. 2024 Aug 19;25(16):e202400359. doi: 10.1002/cphc.202400359. Epub 2024 Jun 20.
The interaction between organic molecules and oxidized catalyst surfaces has frequently been used to study the fuel crossover from the anode to the cathode in direct liquid fuel cells. In such experiments, the oxidized surface is put in contact with the fuel under open circuit conditions, and the evolution of the potential is registered. The open circuit potential (OCP) vs. time features can then inform on the reactivity of the fuel with the oxidized surface and provide valuable information not only to applications in fuel cells but also to the electrochemical reform of those molecules to produce clean hydrogen. In this paper, we present an experimental investigation of the open circuit interaction between ethanol or 2-propanol with oxidized platinum surfaces. Besides the OCP time traces, we have also employed cyclic voltammetry and fast oxide reduction sweep in the presence of the alcohols. Comparable reaction currents are obtained in the cyclic voltammogram, but the electro-oxidation of 2-propanol sets in at considerably lower overpotentials than that of ethanol. At the high potential region, both the magnitude and the potential of the current peak are nearly identical in both cases. In contrast, under open circuit conditions, the interaction of ethanol with the oxidized platinum surface is more pronounced than that found for 2-propanol, and these results are corroborated by the facile reduction of the platinum oxides along the fast backward sweep for the case of the latter.
有机分子与氧化催化剂表面之间的相互作用经常被用于研究直接液体燃料电池中燃料从阳极到阴极的交叉渗透。在这类实验中,将氧化表面在开路条件下与燃料接触,并记录电位的变化。开路电位(OCP)随时间的变化特征可以反映燃料与氧化表面的反应活性,不仅能为燃料电池的应用提供有价值的信息,还能为这些分子的电化学重整以生产清洁氢气提供有价值的信息。在本文中,我们对乙醇或2-丙醇与氧化铂表面之间的开路相互作用进行了实验研究。除了OCP时间曲线外,我们还在醇类存在的情况下采用了循环伏安法和快速氧化物还原扫描。在循环伏安图中获得了相当的反应电流,但2-丙醇的电氧化在比乙醇低得多的过电位下开始。在高电位区域,两种情况下电流峰的大小和电位几乎相同。相比之下,在开路条件下,乙醇与氧化铂表面的相互作用比2-丙醇更为明显,并且对于后者,铂氧化物沿快速反向扫描的容易还原证实了这些结果。