On the Mechanism of the Oxygen Reduction Reaction on Au(poly) in Aqueous Alkaline Electrolytes: A Critical Reassessment
On the Mechanism of the Oxygen Reduction Reaction on Au(poly) in Aqueous Alkaline Electrolytes: A Critical Reassessment
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DOI：
10.1021/acs.jpcc.1c02683
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发表时间：
2021-06-17
影响因子：
3.7
通讯作者：
Scherson, Daniel
中科院分区：
文献类型：
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作者：
Strobl, Jonathan R.;Scherson, Daniel
本文提出了在0.1M NaOH+0.9M NaClO_4水溶液中多晶金上氧还原的机理，该机理与Ignaczaket等人最近提出的理论论证相一致。[Nano Energy 2016 26 558-564]，形成溶液相超氧化物，O-2(-)是最初的速度决定步骤，随后是可逆的(Nernstian)单电子还原生成溶液相过氧化氢，HO2-(AQ)，而不是像其他作者假设的那样，通过吸附的O-2-的二级置换。该模型还考虑了HO2-(AQ)和O-2(AQ)直接还原生成OH-(AQ)。对旋转环盘电极在O2饱和和Ar吹扫的HO2-(AQ)溶液中收集的数据进行了详细的数学分析，从而有可能在较宽的电势范围内确定所提机理中各个步骤的唯一一组动力学速率常数。
A mechanism is herein proposed for the reduction of oxygen on polycrystalline Au in 0.1 M NaOH + 0.9 M NaClO4 aqueous electrolytes, that assumes, in agreement with theoretical arguments put forward rather recently by Ignaczaket al.. [Nano Energy 2016 26 558-564], formation of solution-phase superoxide, O-2(-), as the initial, rate-determining step, followed by a reversible (Nernstian) one-electron reduction to yield solution-phase peroxide, HO2-(aq), and not by a second-order dismutation of adsorbed O-2-, as has been postulated by other authors. Also considered in this model is the direct reduction of HO2-(aq) and O-2(aq) to generate OH-(aq). A detailed mathematical analysis of data collected with a rotating ring-disk electrode in O-2-saturated and Ar-purged HO2-(aq)-containing solutions made it possible to determine a unique set of kinetic rate constants for the various steps in the proposed mechanism over a wide potential range.