电化学原位表面增强拉曼光谱研究Au@Pd纳米粒子薄膜电极上吸附CO的斯塔克效应

doi:10.1016/S1872-2067(15)61106-8

催化学报 ›› 2016, Vol. 37 ›› Issue (7): 1156-1165.DOI: 10.1016/S1872-2067(15)61106-8

电化学原位表面增强拉曼光谱研究Au@Pd纳米粒子薄膜电极上吸附CO的斯塔克效应

张普^a, 卫怡^a, 蔡俊^a, 陈艳霞^a, 田中群^b

a. 中国科学技术大学化学物理系, 合肥微尺度国家实验室分子原子研究部, 安徽合肥 230026;
b. 厦门大学化学化工学院化学系, 固体表面物理化学国家重点实验室, 福建厦门 361005

收稿日期:2016-03-14 修回日期:2016-04-14 出版日期:2016-06-17 发布日期:2016-06-17
通讯作者: Yan-Xia Chen
基金资助:
国家自然科学基金(21473175);国家重大科学仪器设备开发专项(2011YQ03012416);国家重点基础研究发展计划(973计划,2015CB932301).

Nonlinear Stark effect observed for carbon monoxide chemisorbed on gold core/palladium shell nanoparticle film electrodes, using in situ surface-enhanced Raman spectroscopy

Pu Zhang^a, Yi Wei^a, Jun Cai^a, Yan-Xia Chen^a, Zhong-Qun Tian^b

a. Hefei National Laboratory for Physical Sciences at Microscale Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, Anhui, China;
b. State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, Fujian, China

Received:2016-03-14 Revised:2016-04-14 Online:2016-06-17 Published:2016-06-17
Contact: Yan-Xia Chen
Supported by:
This work was supported by the National Natural Science Foundation of China (21473175), the National Instrumentation Program (2011YQ03012416) and the National Basic Reserarch Program of China (973 Program, 2015CB932301).

摘要/Abstract

摘要：

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CO_ad以及M-CO_ad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CO_ad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0.55Vvs.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CO_ad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-O_M(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-CO_M键的振动频率可以分为三段:dν_C-OM/dE在-1.5~-1.2V范围内是185~207cm^-1/V,在-1.2~-0.15V是83~84cm^-1/V,在-0.2~0.55V是43cm^-1/V;而dν_Pd-COM/dE在-1.5~-1.2V范围内是-10~-8cm^-1/V,在-1.2~-0.15V是-31~-30cm^-1/V,在-0.2~0.55V是-15cm^-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dν_C-OM/dE在-1.2V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CO_ad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.

关键词: 一氧化碳, 表面增强拉曼光谱, 钯, 密度泛函理论, 斯塔克效应

Abstract:

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-O_M and the Pd-CO_M band (here, M denotes the multiply-bonded configuration) displayed three distinct linear regions: dν_C-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, dν_Pd-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 hydrogen evolution reaction (HER) occurred. With the help of periodic density functional theory calculations using two different (2 × 2)-3CO slab models with Pd(111), the unusually high dν_C-OM/dE and the small dν_Pd-COM/dE in the HER region were explained as being due to the conversion of CO_ad from bridge to hollow sites, which was induced by the co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.

Key words: Carbon monoxide, Surface-enhanced Raman spectroscopy, Palladium, Density functional theory, Stark effect

张普, 卫怡, 蔡俊, 陈艳霞, 田中群. 电化学原位表面增强拉曼光谱研究Au@Pd纳米粒子薄膜电极上吸附CO的斯塔克效应[J]. 催化学报, 2016, 37(7): 1156-1165.

Pu Zhang, Yi Wei, Jun Cai,Yan-Xia Chen, Zhong-Qun Tian. Nonlinear Stark effect observed for carbon monoxide chemisorbed on gold core/palladium shell nanoparticle film electrodes, using in situ surface-enhanced Raman spectroscopy[J]. Chinese Journal of Catalysis, 2016, 37(7): 1156-1165.

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电化学原位表面增强拉曼光谱研究Au@Pd纳米粒子薄膜电极上吸附CO的斯塔克效应

Nonlinear Stark effect observed for carbon monoxide chemisorbed on gold core/palladium shell nanoparticle film electrodes, using in situ surface-enhanced Raman spectroscopy

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