利用操作全反射 X 射线吸收光谱探测电极-液体界面

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL
A. Grespi , A. Larsson , G. Abbondanza , J. Eidhagen , D. Gajdek , J. Manidi , A. Tayal , J. Pan , L.R. Merte , E. Lundgren
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引用次数: 0

摘要

研究电化学(EC)过程的传统方法虽然很成功,但都是基于电流/电压测量,只能提供有关性能的信息,而不能直接观察电极表面发生的化学和结构变化。这些过程都发生在电极-电解质界面,其结构是决定其行为的主要因素,但由于需要超高真空环境,大多数表面敏感实验技术都仅限于原位条件。在这篇论文中,我们报告了在 P64 光束线(汉堡 DESY)使用简单、多功能的 EC 流动池,利用硬 X 射线散射和光谱技术进行多模态表面敏感研究的全外反射几何(Refle-XAFS)操作 X 射线吸收光谱。我们的研究表明,Refle-XAFS 方法可用于研究工业合金和模型电极在恶劣电化学环境下的化学表面变化,而不局限于薄膜样品。我们研究了耐腐蚀镍铬钼合金表面被动膜的发展和破坏,以及多晶金(poly-Au)的电氧化过程,这与水电解的基础研究息息相关。尽管电解质和电解槽的 PEEK 壁对光束有很强的衰减,但使用低至 8 keV 的光束能量仍能检测到纳米级的表面氧化膜。确定了镍合金 59 在 pH 值为 7 和 12 的 1 M NaCl 溶液中的钝性击穿区,显示了阳极极化过程中表面氧化物成分的差异。在 0.05 M H2SO4 中观察了聚金的电氧化过程,显示了在 OER 过程中从二维 Au1+/3+ 到三维厚 Au3+ 表面氧化物/氢氧化物的发展过程。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Probing the electrode-liquid interface using operando total-reflection X-ray absorption spectroscopy

Probing the electrode-liquid interface using operando total-reflection X-ray absorption spectroscopy

Traditional methods to study electrochemical (EC) processes, although successful, are based on current/voltage measurements, providing information about performances rather than offering a direct observation of chemical and structural changes occurring at the electrode surface. These processes are localized at the electrode-electrolyte interface, the structure of which is the main determinant of their behavior, but most surface sensitive experimental techniques are limited to ex situ conditions, owing to the need for an ultra-high vacuum environment. In this contribution, we report operando X-ray absorption spectroscopy in total external reflection geometry (Refle-XAFS) at P64 beamline (DESY, Hamburg), using a simple and versatile EC flow cell designed for multimodal surface sensitive studies with hard X-ray scattering and spectroscopy techniques. We show that the Refle-XAFS method can be used to study chemical surface changes of industrial alloys and model electrodes in harsh electrochemical environments, without being limited to thin film samples. The surface passive film development and breakdown of a corrosion-resistant Ni-Cr-Mo alloy and the electro-oxidation of polycrystalline gold (poly-Au), relevant for fundamental studies on water electrolysis, were investigated. Despite the strong attenuation of the beam by the electrolyte and the PEEK walls of the EC cell, nanoscale surface oxide films were detected using beam energies down to 8 keV. The passivity breakdown region of Ni alloy 59 in 1 M NaCl at pH 7 and pH 12 was identified, showing differences in the composition of the surface oxides during anodic polarization. The electro-oxidation of poly-Au in 0.05 M H2SO4 was observed, showing a progression from two-dimensional Au1+/3+ to three-dimensional thick Au3+ surface oxide/hydroxide during OER.

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来源期刊
Surface Science
Surface Science 化学-物理:凝聚态物理
CiteScore
3.30
自引率
5.30%
发文量
137
审稿时长
25 days
期刊介绍: Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to: • model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions • nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena • reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization • phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization • surface reactivity for environmental protection and pollution remediation • interactions at surfaces of soft matter, including polymers and biomaterials. Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.
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