The potential (E)‐dependent vibrational behavior of a saturated CO adlayer on Au‐core Pd‐shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, using in situ surface‐enhanced Raman spectroscopy (SERS). Over the whole of the examined potential region (–1.5 to 0.55 V vs. NHE), the peak frequencies of both the C–OM and the Pd–COM band (here, M denotes the multiply‐bonded configuration) displayed three distinct linear regions:dνC–OM/dE decreased from~185–207 (from–1.5 to–1.2 V) to~83–84 cm–1/V (–1.2 to–0.15 V), and then to 43 cm–1/V (–0.2 to 0.55 V);on the other hand, dνPd–COM/dE changed from~–10 to–8 cm–1/V (from–1.5 to–1.2 V) to~–31 to–30 cm–1/V (–1.2 to–0.15 V), and then to–15 cm–1/V (–0.2 to 0.55 V). The simultaneously recorded cyclic voltammograms revealed that at E<–1.2 V, a hydro‐gen evolution reaction (HER) occurred. With the help of periodic density functional theory calcula‐tions using two different (2 × 2)‐3CO slab models with Pd(111), the unusually high dνC–OM/dE and the small dνPd–COM/dE in the HER region were explained as being due to the conversion of COad from bridge to hollow sites, which was induced by the co‐adsorbed hydrogen atoms formed from disso‐ciated water at negative potentials.%电化学 Stark效应是指电极溶液界面的吸附物或金属-吸附物之间的化学键的振动频率随电极电势而发生变化的现象.研究该效应,可以更好地理解吸附物与基底的相互作用(如吸附构型、吸附取向和覆盖度等随电位的变化),也可反过来推断电极基底的电子构型及其随电势的变化规律,对理解电化学双电层的结构以及电催化反应的构效关系都很有帮助.多年以来,电极表面吸附 CO的电化学 Stark效应广受关注,是由于 CO为很多小分子氧化的中间产物,研究 CO的谱学行为,可加深对 CO以及其它能产生 CO中间物有机小分子的电催化氧化机理和动力学的理解；另一方面, CO与过渡金属之间普遍存在s给电子以及p反馈电子作用,因此 CO也可作为探针分子,通过考察 COad以及 M–COad的振动频率的变化,可推断相应条件下基底的电子与几何结构等信息. 本文使用电化学原位表面增强拉曼技术,在一个大的电势范围内考察了 Au@Pd纳米粒子薄膜电极上饱和吸附 CO的振动光谱行为,以期更好地理解 COad与基底的成键作用与电极电势之间的关系.由于纯 Pd电极表面的拉曼信号太弱,实验使用具有核壳结构的 Au@Pd纳米粒子薄膜作为模型电极,并利用 Au核的拉曼增强特性.宽广的电势范围约–1.5到0.55V vs. NHE,通过使用酸性、中性以及碱性电解质得以实现.实验考察的电势上限由 COad氧化起始电位决定,而下限由强烈氢析干扰测量所限制.结果表明,在检测的电势范围内, C–OM(M指在电极表面的桥式吸附CO和穴位吸附 CO所形成的谱带重叠)和 Pd–COM键的振动频率可以分为三段： dνC–OM/dE在–1.5~–1.2 V范围内是185~207 cm–1/V,在–1.2~–0.15 V是83~84 cm–1/V,在–0.2~0.55 V是43 cm–1/V；而 dνPd–COM/dE在–1.5~–1.2 V范围内是–10~–8 cm–1/V,在–1.2~–0.15 V是–31~–30 cm–1/V,在–0.2~0.55 V是–15 cm–1/V.与同时记录的极化曲线对比,认为在中性和碱性介质中所观察到 dνC–OM/dE在–1.2 V附近的急剧变化与电极表面发生了强烈的析氢反应有关.另外，结合密度泛函理论模型计算,认为共吸附的 H减少了 COad从桥式构型到穴位构型的转变,在酸性介质中这种变化不明显,可能是由于对应的电势较高,桥式吸附的 CO比例越大,桥式向穴位的转变本身相对较少.
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