Abstract Ambient pressure X-ray photoelectron spectroscopy (APXPS) has evolved into an effective tool to analyze the chemical states of interfaces relevant to realistic environments and operating conditions. Herein we employ a graphene-capped microvolume arrays sample platform for scanning photoelectron spectro-microscopy (SPEM) of electrified liquid-solid electrochemical interfaces. By using highly electron and X-ray transparent graphene membrane as a working electrode, we probed the electronic structure of a model electrochemical system under operando conditions within the first few nanometers of the electrode/liquid electrolyte interface. We report the conditions when highly focused X-ray irradiation affects the chemistry at the liquid–solid interface due to solvent radiolysis by primary radiation, photoelectrons as well as secondary electrons. We recorded radiolytic products by photoemission spectroscopy and characterized their impact on the chemical speciation at the electrified solid-liquid interface. Three different exposure regimes were tested to elucidate the onset and dependence of XPS radiolytic signatures of the dose rate. The observed effects highlight the need for careful consideration of radiolytic processes for artifact-free liquid phase XPS measurements and data interpretation.

中文翻译：

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聚焦X射线束光电子能谱中液体电解质的辐射损伤

摘要 环境压力 X 射线光电子能谱 (APXPS) 已发展成为分析与现实环境和操作条件相关的界面化学状态的有效工具。在此，我们采用石墨烯封端的微体积阵列样品平台来扫描带电液固电化学界面的光电子能谱显微镜 (SPEM)。通过使用高度电子和 X 射线透明的石墨烯膜作为工作电极，我们在电极/液体电解质界面的前几纳米内在操作条件下探测了模型电化学系统的电子结构。我们报告了由于初级辐射、光电子和次级电子的溶剂辐射分解，当高度聚焦的 X 射线辐射影响液-固界面的化学反应时的条件。我们通过光电发射光谱记录了辐射分解产物，并表征了它们对带电固液界面化学形态的影响。测试了三种不同的暴露方案以阐明剂量率的 XPS 辐射分解特征的发生和依赖性。观察到的影响强调需要仔细考虑无伪影液相 XPS 测量和数据解释的辐射分解过程。