Understanding the hydroxyl adsorption behavior at Pt electrode surface in high-temperature alkaline solutions

doi:10.1016/j.cjche.2022.04.012

Abstract

Abstract: Since the application in fuel cell, the electrochemical adsorption of hydroxyl has received considerable attention in recent years. While most research mainly focus on the room temperature, in this paper, the electrochemical adsorption of hydroxyl in alkaline solution at high temperature was investigated. An unusual oxidation peak was observed at -0.27 V, suggesting new behavior of hydroxyl adsorption occurred. As is known two kinds of cation hydrated clusters exist in alkaline solution, (H₂O)_x-1M⁺-H₂O-O_adH and (H₂O)_xM⁺-O_adH. For K⁺ and Cs⁺, the cluster shows unstable structure due to the weak interaction between hydrated cation and OH^- especially at high temperature. However, For Li⁺, Na⁺ the cluster structure would be stable, as the interaction force between the hydrated cation and OH^- is so strong. It was revealed that the unusual oxidation peak has some relationship with the (H₂O)_x-1M⁺-H₂O-O_adH cluster (K⁺ and Cs⁺) absorbed at Pt electrode surface. When the temperature was raised, (H₂O)_x-1M⁺-H₂O- and -O_adH was disconnected, then the O_adH absorbed at Pt surface got oxidated. Based on the SEM observation, it was showed the unusual electrochemical oxidation reaction would generate platinum oxides, blocking the reactive sites at Pt electrode surface, thus reducing the electrochemical reactivity of Pt electrode. Accordingly, parameters of alkaline concentration and temperature were systematically studied, it was found that increase temperature or alkaline concentration was in favor of the unusual oxidation reaction. This study provides more understanding of hydroxyl adsorption behavior at Pt electrode surface for the high temperature water solution environment.

Key words: Alkaline solution, Hydroxyl adsorption, Cationic species, High temperature, Cationic hydrated clusters

摘要： Since the application in fuel cell, the electrochemical adsorption of hydroxyl has received considerable attention in recent years. While most research mainly focus on the room temperature, in this paper, the electrochemical adsorption of hydroxyl in alkaline solution at high temperature was investigated. An unusual oxidation peak was observed at -0.27 V, suggesting new behavior of hydroxyl adsorption occurred. As is known two kinds of cation hydrated clusters exist in alkaline solution, (H₂O)_x-1M⁺-H₂O-O_adH and (H₂O)_xM⁺-O_adH. For K⁺ and Cs⁺, the cluster shows unstable structure due to the weak interaction between hydrated cation and OH^- especially at high temperature. However, For Li⁺, Na⁺ the cluster structure would be stable, as the interaction force between the hydrated cation and OH^- is so strong. It was revealed that the unusual oxidation peak has some relationship with the (H₂O)_x-1M⁺-H₂O-O_adH cluster (K⁺ and Cs⁺) absorbed at Pt electrode surface. When the temperature was raised, (H₂O)_x-1M⁺-H₂O- and -O_adH was disconnected, then the O_adH absorbed at Pt surface got oxidated. Based on the SEM observation, it was showed the unusual electrochemical oxidation reaction would generate platinum oxides, blocking the reactive sites at Pt electrode surface, thus reducing the electrochemical reactivity of Pt electrode. Accordingly, parameters of alkaline concentration and temperature were systematically studied, it was found that increase temperature or alkaline concentration was in favor of the unusual oxidation reaction. This study provides more understanding of hydroxyl adsorption behavior at Pt electrode surface for the high temperature water solution environment.

关键词: Alkaline solution, Hydroxyl adsorption, Cationic species, High temperature, Cationic hydrated clusters

Bo Pan, Biao Liu, Shaona Wang, Yeqing Lv, Hao Du, Yi Zhang. Understanding the hydroxyl adsorption behavior at Pt electrode surface in high-temperature alkaline solutions[J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 173-179.

Bo Pan, Biao Liu, Shaona Wang, Yeqing Lv, Hao Du, Yi Zhang. Understanding the hydroxyl adsorption behavior at Pt electrode surface in high-temperature alkaline solutions[J]. 中国化学工程学报, 2023, 54(2): 173-179.

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