Probing the active sites of oxide encapsulated electrocatalysts with controllable oxygen evolution selectivity†

EES catalysis Pub Date : 2024-04-17 DOI:10.1039/D4EY00074A
William D. H. Stinson, Robert S. Stinson, Jingjing Jin, Zejie Chen, Mingjie Xu, Fikret Aydin, Yinxian Wang, Marcos F. Calegari Andrade, Xiaoqing Pan, Tuan Anh Pham, Katherine E. Hurst, Tadashi Ogitsu, Shane Ardo and Daniel V. Esposito
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Abstract

Electrocatalysts encapsulated by nanoscopic overlayers can control the rate of redox reactions at the outer surface of the overlayer or at the buried interface between the overlayer and the active catalyst, leading to complex behavior in the presence of two competing electrochemical reactions. This study investigated oxide encapsulated electrocatalysts (OECs) comprised of iridium (Ir) thin films coated with an ultrathin (2–10 nm thick) silicon oxide (SiOx) or titanium oxide (TiOx) overlayer. The performance of SiOx|Ir and TiOx|Ir thin film electrodes towards the oxygen evolution reaction (OER) and Fe(II)/Fe(III) redox reactions were evaluated. An improvement in selectivity towards the OER was observed for all OECs. Overlayer properties, namely ionic and electronic conductivity, were assessed using a combination of electroanalytical methods and molecular dynamics simulations. SiOx and TiOx overlayers were found to be permeable to H2O and O2 such that the OER can occur at the MOx|Ir (M = Ti, Si) buried interface, which was further supported with molecular dynamics simulations of model SiO2 coatings. In contrast, Fe(II)/Fe(III) redox reactions occur to the same degree with TiOx overlayers having thicknesses less than 4 nm as bare electrocatalyst, while SiOx overlayers inhibit redox reactions at all thicknesses. This observation is attributed to differences in electronic transport between the buried interface and outer overlayer surface, as measured with through-plane conductivity measurements of wetted overlayer materials. These findings reveal the influence of oxide overlayer properties on the activity and selectivity of OECs and suggest opportunities to tune these properties for a wide range of electrochemical reactions.

Abstract Image

探究具有可控氧进化选择性的氧化物封装电催化剂的活性位点
由纳米覆盖层封装的电催化剂可以控制覆盖层外表面或覆盖层与活性催化剂之间埋藏界面的氧化还原反应速率,从而在存在两个相互竞争的电化学反应时产生复杂的行为。本研究调查了氧化物封装电催化剂(OECs),它由涂有超薄(2-10 nm 厚)氧化硅(SiOx)或氧化钛(TiOx)覆盖层的铱(Ir)薄膜组成。对 SiOx|Ir 和 TiOx|Ir 薄膜电极在氧进化反应(OER)和铁(II)/铁(III)氧化还原反应中的性能进行了评估。结果表明,所有 OEC 都提高了对 OER 的选择性。采用电分析方法和分子动力学模拟相结合的方法评估了包覆层的特性,即离子导电性和电子导电性。研究发现,SiOx 和 TiO¬x 覆盖层可渗透 H2O 和 O2,因此 OER 可发生在 MOx|Ir (M = Ti,Si)埋藏界面上,这一点通过对模型 SiO2 涂层进行分子动力学模拟得到了进一步证实。相比之下,厚度小于 4 纳米的 TiOx 覆盖层与裸电催化剂发生的 Fe(II)/Fe(III) 氧化还原反应程度相同,而所有厚度的 SiOx 覆盖层都会抑制氧化还原反应。这一观察结果归因于埋藏界面和外覆盖层表面之间电子传输的差异,这是用浸湿覆盖层材料的通面电导率测量法测得的。这些发现揭示了氧化物覆盖层特性对 OEC 活性和选择性的影响,并为调整这些特性以适应各种电化学反应提供了机会。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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