CO在贵金属电极表面吸附及氧化的电化学原位表面增强拉曼光谱研究
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摘要
一氧化碳(CO)分子对阳极电催化剂的毒化是低温质子交换膜燃料电池及直接甲醇燃料电池研究中迫切需要解决的问题,提高燃料电池阳极电催化剂的活性及抗CO中毒能力是质子交换膜燃料电池实现商业化的关键所在。从分子水平上深入理解CO在贵金属上的吸附行为及氧化机理有助于解决CO的毒化问题,这也是燃料电池电催化领域重要的研究课题。
本博士论文利用原位表面增强拉曼光谱(SERS)技术对一氧化碳分子在Pt、Pd、Ru、Rh贵金属核壳结构纳米粒子薄膜电极表面的吸附行为及电化学氧化机理进行了系统的研究。主要结果总结如下：
1.系统地研究了CO表面覆盖度、溶液pH值以及CO分压对CO在Au@Pt核壳结构纳米粒子薄膜电极表面的吸附行为的影响。研究发现随着COad覆盖度的增加,Pt—COL(顶位吸附CO)振动频率红移,C---OL振动频率蓝移,而Pt—COL及C—OL的谱带强度则均增大。从CO饱和的H2SO4溶液切换到N2饱和的H2SO4溶液后,Pt—COL和C----OL的峰强度分别增加了6%和30%，Pt—COL的伸缩振动频率及C—OL的伸缩振动频率分别蓝移到红移了4 cm-1。根据拉曼光谱的强度、振动频率和CO分子间偶极耦合作用的定量分析得知Pt—COL带强度增加主要来源于CO分子取向的变化,Pt—COL频率变化来源于化学作用；另一方面C---OL带强度增加来源于吸附CO分子的偶极耦合作用和取向变化,C—OL带频率变化来源于偶极耦合作用及化学作用。另外在相同电势下在酸性(H2SO4)和中性(Na2SO4)溶液间切换的时间分辨SERS研究中,H2SO4溶液中的Pt—COL及C---OL频率分别比Na2SO4溶液低2 cm-1及高7 cm-1,此频率变化主要来源于H2SO4溶液中的共吸附氢原子导致的CO分子从“准线式位”向线式位的偏移。当溶液从H2SO4或NaOH溶液切换到Na2SO4溶液后,Pt—COL及C----OL带强度急剧降低约50%,此强度降低主要来自于SERS化学增强因子的变化。
2.通过研究不同pH溶液中CO在Au@Pt纳米粒子薄膜电极上吸附的电位效果而探讨了电化学Stark效应。结果表明在所研究的电势区间Stark斜率dvC—OL,B/dE(C—OL,B表示线式及桥式吸附的CO)为正值而dvPt—COL,B/dE为负值。dvPt—CoL,B/dE在整个电势区间基本不变,dvC—OL,B/dE随电势负移明显增加。上述受电势影响的光谱行为可以用d(Pt)→2π*(CO)反馈及5σ(CO)→sp(Pt)成键的化学作用和CO分子之间的偶极耦合作用来解释。由于Pt—CO振动模的偶极耦合作用比较弱,测量的dvPt—COL,B/dE能够直接作为电势导致Pt—CO键长及键强变化的依据。根据理论推导的关联Pt—CO键长、吸附能与振动频率的解析公式及实验测量的Pt—CO振动频率,我们估算出当电极电势发生变化时,COL(COB)的吸附能变化为0.20(0.37) eV/V,而COL(COB)键长变化为0.005 (0.01) A/V。COB比COL的△Eb／△E更大说明COB的化学键对界面电场的变化比COL更为敏感。另外,我们进行了基于周期性slab模型的DFT理论计算,得到了COad表面覆盖度为0.25及0.75 ML时不同电场下的Pt—CO及C--O的振动频率及Stark斜率。DFT理论计算得到的dvPt—COL,B/dE and dvC—OL,B/dE比电化学实验观测值要小得多,另外基于slab模型的DFT理论计算结果表明|dvPt—COL/dE|>|dvPt—COB/dE|,这与实验结果矛盾,说明DFT计算所使用模型或计算方法仍旧需要进一步改进。
3.研究了酸性溶液中CO在Au@Pt核壳纳米粒子薄膜电极上氧化前峰机理。另外利用表面增强拉曼光谱研究了不同pH溶液中CH3OH在Au@Pt纳米粒子薄膜电极上的氧化机理。在氢原子欠电位沉积(H-upd)电势区间吸附的CO在CO饱和的酸性溶液中进行电位扫描时在0.4～0.8 V出现氧化前峰,而在双电层电势区间吸附时则无氧化前峰出现。通过定量比较0.06和0.35V下饱和吸附CO后的拉曼光谱,发现其拉曼光谱没有明显的区别。因此推断在氧化前峰区CO氧化的难易程度很可能不是由表面CO的吸附构型决定,而是来源于不同吸附电势下的Pt基底的晶格结构变化。原位SERS实验发现Au@Pt内米粒子薄膜电极上甲醇在酸性、中性和碱性溶液中的氧化机理是类似的。甲醇在Au@Pt纳米粒子薄膜电极表面脱氢生成的CO以顶位和桥位吸附,三种溶液中COL和COB的比例有很大差别,这可能是三种溶液中界面电场以及电极表面共吸附物种不同导致的。
4.利用表面增强拉曼光谱研究了不同pH值溶液中CO在Au@Pd纳米粒子薄膜电极上的吸附行为,并利用DFT理论计算了不同吸附位、电极电势及覆盖度下CO在Pd(111)表面吸附的键长、吸附能、振动频率。计算结果表明CO在Pd(111)上最稳定的吸附位为穴位,CO在Pd上的吸附能随着电势负移而降低。在-1～0.5 V／A的电场范围内,Pd—COL,M及C—OL,M的振动频率与电极电势成线性关系,说明CO在Pd上吸附时,单纯的电场作用会导致线性的Stark效应。中性和碱性溶液中的原位SERS实验发现Pd—COM及C---OM振动的Stark斜率存在明显的非线性行为。原位电化学SERS实验结果表明Pd—COM及C—OM振动的Stark斜率可以分为三部分：i)从-1.5至-1.2 V,分别为-8～-10和185～207 cm-1/V; ii)从-1.2到-0.15 V,分别为-30-～-31和83～84 cm-1/V; iii)从-0.2到0.55 V, Pd—COM及C—OM振动的Stark斜率分别为-15及43 cm-1／V。根据同步记录的循环伏安曲线,中性和碱性溶液中Stark斜率发生突变的电位恰好对应于析氢起始电位。结合周期性密度泛函理论计算的结果,中性和碱性溶液中的非线性Stark效应来源于析氢电位区间在Pd电极上的共吸附氢原子所导致的CO从桥位向穴位的转化。
5.初步研究了CO在Au@Ru及Au@Rh壳纳米薄膜粒子电极上的吸附及氧化行为。在酸性溶液中,55 nm Au@2 nm Ru纳米粒子不稳定,易出现针孔。在中性溶液中55 nm Au@2 nm Ru纳米粒子比较稳定,在较负电位区间(-1.2～-0.6 V vs.NHE)仅观察到吸附在Ru上吸附的CO的Ru—CO振动和C—-O振动峰；在较正电位区间(大于-0.6Vvs.NHE)Ru发生氧化,可以同时观察到吸附在Ru和RuOx上的Ru—CO及C—--O谱带。RuOx上吸附CO的C—O谱带强度比Ru上吸附CO的C—O谱带强度要大得多,这主要是由于RuOx上吸附CO的C—O振动的拉曼散射截面较大的缘故。在酸性和中性溶液中CO在Au@Rh上吸附的原位SERS实验表明Au@Rh纳米粒子不稳定,易形成“针孔”。在碱性溶液中Au@Rh纳米粒子比较稳定。通过原位SERS实验验证了CO饱和的NaOH溶液中,CO在Au@Rh核壳纳米粒子薄膜电极上的氧化机理为Langmuir-Hinshelwood类型反应。
综上所述,通过表面增强拉曼光谱及密度泛函理论的研究结果,从分子水平上理解了CO在几种贵金属纳米粒子表面的吸附及氧化机理,为研究开发具有抗CO中毒并具有高催化活性的低温质子交换膜燃料电池阳极催化剂提供了理论指导。
Fuel cells are expected to play important roles for the sustainable society. However, most of the fuel cells working at low temperature, such as proton exchange membrance fuel cell (PEMFC) and direct methanol fuel cell (DMFC), meet the same serious problem, i.e, deactivation of anode catalyst induced by adsorption of carbon monoxide (CO) from the fuel. Hence, a fundamental understanding of the adsorption and oxidation of CO at noble metal electrodes such as platinum (Pt) and palladinum (Pd), which is one of the most important components in the anode electrocatalysts, will be of great help to alleviate the CO poisoning problem.
In this Ph.D. thesis, the adsorption and oxidation of CO molecules at core-shell nanoparticle electrodes of Au@M are investigated systematically [where Au and M (M=Pt, Pd, Rh, Ru) represent core and shell materials, respectively] by in-situ surface-enhanced Raman spectroscopy (SERS) measurements. These results are briefly summarized below.
1. The effects of CO coverage, CO partial pressure, and solution pH on the vibrational properties of Pt—CO and C—O stretching modes of CO adlayer at Au@Pt core-shell nanoparticle electrodes. With the increase in COad coverage a decrease (increase) in the Pt—COL (COL) peak frequency together with the increase of all the band intensities are observed. The chemical effects are considered to be responsible for the frequency change of Pt—COL stretching band, and both the chemical and the dipole-dipole coupling effects within adsorbed CO molecules are the main causes for frequency change of C—OL.With the solution switch from CO-saturated 0.5 M H2SO4 solution to CO-free 0.5 M H2SO4 solution at 0.06 V, the peak intensities of Pt—COL and C—OLincrease ca.6% and ca.30%, respectively, together with a slight change in the peak frequency. The intensity change of Pt—COL is mainly attributed to the CO orientation change, while the dipole coupling effects, chemical effects and the CO orientation change are responsible for the intensity and frequency changes of the C—OL stretching vibration. The SERS spectra recorded upon changes in the electrolyte between H2SO4, Na2SO4 and NaOH at constant potentials reveal that a substantial change (up to 50%) in the band intensities of Pt—CO and CO stretching vibrations. In addition, the C—OL (Pt—COL) peak frequency is ca.7 cm-1 higher (2 cm-1 lower) in H2SO4 than that in Na2SO4, while no differences in the peak frequencies have been discerned when switching between in Na2SO4 and NaOH. Small lateral shift of COad from atop edges to exactly atop positions upon the the co-adsorption of H atoms in H2SO4 has been proposed to explain such frequency change, while the band intensity changes are identified to be due to the changes in the chemical enhancement factor upon the electrolyte switch.
2. Potential dependence of CO adsorption at Au@Pt nanoparticle electrodes in a wide potential window. Throughout the potential regime examined, the Stark slopes of dvC—O/dE are always positive while that of dvPt—CO/dE are negative. The Stark slopes of dvPt—CO/dE are almost constant while that of dvC—O/dE increase toward negative potentials. Qualitatively, all the potential-dependent spectral behavior can be rationalized by the delicate changes in the counterweighing effects of the chemical bonding (d(Pt)→2π*(CO) back-donation and 5σ(CO)→sp(Pt) donation) and the dipole—dipole coupling interaction, the latter originates from potential induced changes in the fractional surface coverage of COL and COB species. Based on the fact that the influence of the dipole—dipole coupling interaction on the Pt—CO vibration is'negligible, the measured dvpt-co/dE can serve as indicator to evaluate the potential-induced changes in bonding strength and bond length of Pt-CO. From which we estimate the potential induced changes in the binding energies and bonding lengths of COL (COB) of ca. 0.20 (0.37) eV/V and 0.005 (0.01) A/V, respectively. The larger△Eb/△E of COB than COL reveals that the chemical bonding of COB is more sensitive to the changes in the interfacial electric field than that of COL. Peoridic DFT calculations have been performed to estimate the field-depdendent vibrational frequencies and Stark slopes for the saturated CO adlayer. The DFT calculations demonstrate that the Stark slopes of dvpt-co/dE and dvC—O/dE are much smaller than the present observation. The predicted order of the Stark slope of metal-adsorbate stretching vibrations, i.e.,|dvPt—COL/dE|>|dvPt-COB/dE| as predicted by peoridic DFT calculations, contradicts our experimental observation as well as that from DFT calculations using the cluster model.
3. The origin of pre-peak in bulk CO oxidation at Au@Pt electrode and the mechanism elucidation of methanol electro-oxidation in electrolyte solutions with different pH. A pre-peak has been reported between 0.4～0.8 V for the oxidation of CO pre-adsorbed in the hydrogen adsorption potential region in a CO saturated 0.5 M H2SO4 solution; The pre-peak disappear if CO pre-adsorbed in the double layer region. However, the essential nature for the pre-peak is still in controversy. The in-situ SERS spectra of CO pre-adsorbed at 0.06 and 0.35 V have been determined and no distinguished differences are observed in spectra between the two potentials. It is proposed that the pre-peak is not caused by the CO adsorption structure, but due to the adlayer structure change on the Pt electrode surface. The mechanisms of methanol oxidation in acid, neutral, and basic solutions are found to be similar from the in-situ SERS measurements. CO from methanol dehydrogenation can adsorb at atop and bridge site on Pt surface. The ratios of COL and COB significantly change with solution pH, which may be related with the electric field and co-adsorbed species.
4. SERS characterization and DFT calculation of CO adsorption at Au@Pd electrodes in the solutions with different pH. DFT calculations reveal that hollow site is the most stable adsorption site for COad on Pd(111) surface and CO binding energy for CO adsorption on Pd(111) surface increase with the negative shift of electrode potential. In the electric field region of -1～0.5 V/A, the vibrational frequencies of Pd—COL,M and C—OL,M are linear with the external electric field. EC-SERS studies reveal that the Stark slopes of both Pd—CO and C—O stretching vibrations can be divided into three distinct region:dvC-OM/dE decreases from 185～207 cm-1/V (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, dvPd-COM/dE changes from-8～-10 cm-1/V (from -1.5 to -1.2 V) to-31～-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 voltammetry reveals that at E<-1.2 V hydrogen evolution reaction (HER) occurs. Based on the results of cyclic voltammetry and periodic DFT calculations, the unusual high dvC—OM/dE and the small dvPd—COM/dE in HER region are explained by the conversion of COad from bridge-to hollow-sites induced by co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.
5. The adsorption and electrochemical oxidation of CO at Au@Ru and Au@Rh nanoparticle electrodes. It is found that the Au@Ru core-shell nanoparticles are unstable and contain pinhole on the surface in acidic solution. The Au@Ru core-shell nanoparticles are relatively stable in neutral solution and have been evaluated. It is found that the bands of Ru—CO and C—O vibration modes are observed in the potential region (-1.2～-0.6 V vs. NHE). These band intensities greatly changes with potential. The bands of Ru—CO and C—O vibrations for CO bound to reduced and oxidized Ru surface sites are obtained in the more positive potential region (>-0.6 V vs. NHE). The C—O band intensity of COad on oxidized surface sites is much larger than that on reduced Ru surface sites, which probably originates from the larger Raman scattering cross-section of C—O vibration of COad on oxidized surface sites than that on reduced Ru surface sites. In-situ SERS experiments of CO adsorption on Au@Rh core-shell nanoparticle electrode reveal that Au@Rh nanoparticle electrode is only stable in basic solution. The mechanism of CO oxidation on Au@Rh nanoparticle electrode in CO saturated basic solution was found to be of the Langmuir-Hinshelwood type.
Based on the present in-situ SERS and DFT calcualtions, we have a more comprehensive understanding of adsorption and electrochemical oxidation of CO on Pt, Pd, Rh, and Ru electrode surfaces, which could provide the general guidance for the research and development of high active anode catalysts with good CO-tolerant ability for the fuel cells working at the low temperatures.
本博士论文利用原位表面增强拉曼光谱(SERS)技术对一氧化碳分子在Pt、Pd、Ru、Rh贵金属核壳结构纳米粒子薄膜电极表面的吸附行为及电化学氧化机理进行了系统的研究。主要结果总结如下：
1.系统地研究了CO表面覆盖度、溶液pH值以及CO分压对CO在Au@Pt核壳结构纳米粒子薄膜电极表面的吸附行为的影响。研究发现随着COad覆盖度的增加,Pt—COL(顶位吸附CO)振动频率红移,C---OL振动频率蓝移,而Pt—COL及C—OL的谱带强度则均增大。从CO饱和的H2SO4溶液切换到N2饱和的H2SO4溶液后,Pt—COL和C----OL的峰强度分别增加了6%和30%，Pt—COL的伸缩振动频率及C—OL的伸缩振动频率分别蓝移到红移了4 cm-1。根据拉曼光谱的强度、振动频率和CO分子间偶极耦合作用的定量分析得知Pt—COL带强度增加主要来源于CO分子取向的变化,Pt—COL频率变化来源于化学作用；另一方面C---OL带强度增加来源于吸附CO分子的偶极耦合作用和取向变化,C—OL带频率变化来源于偶极耦合作用及化学作用。另外在相同电势下在酸性(H2SO4)和中性(Na2SO4)溶液间切换的时间分辨SERS研究中,H2SO4溶液中的Pt—COL及C---OL频率分别比Na2SO4溶液低2 cm-1及高7 cm-1,此频率变化主要来源于H2SO4溶液中的共吸附氢原子导致的CO分子从“准线式位”向线式位的偏移。当溶液从H2SO4或NaOH溶液切换到Na2SO4溶液后,Pt—COL及C----OL带强度急剧降低约50%,此强度降低主要来自于SERS化学增强因子的变化。
2.通过研究不同pH溶液中CO在Au@Pt纳米粒子薄膜电极上吸附的电位效果而探讨了电化学Stark效应。结果表明在所研究的电势区间Stark斜率dvC—OL,B/dE(C—OL,B表示线式及桥式吸附的CO)为正值而dvPt—COL,B/dE为负值。dvPt—CoL,B/dE在整个电势区间基本不变,dvC—OL,B/dE随电势负移明显增加。上述受电势影响的光谱行为可以用d(Pt)→2π*(CO)反馈及5σ(CO)→sp(Pt)成键的化学作用和CO分子之间的偶极耦合作用来解释。由于Pt—CO振动模的偶极耦合作用比较弱,测量的dvPt—COL,B/dE能够直接作为电势导致Pt—CO键长及键强变化的依据。根据理论推导的关联Pt—CO键长、吸附能与振动频率的解析公式及实验测量的Pt—CO振动频率,我们估算出当电极电势发生变化时,COL(COB)的吸附能变化为0.20(0.37) eV/V,而COL(COB)键长变化为0.005 (0.01) A/V。COB比COL的△Eb／△E更大说明COB的化学键对界面电场的变化比COL更为敏感。另外,我们进行了基于周期性slab模型的DFT理论计算,得到了COad表面覆盖度为0.25及0.75 ML时不同电场下的Pt—CO及C--O的振动频率及Stark斜率。DFT理论计算得到的dvPt—COL,B/dE and dvC—OL,B/dE比电化学实验观测值要小得多,另外基于slab模型的DFT理论计算结果表明|dvPt—COL/dE|>|dvPt—COB/dE|,这与实验结果矛盾,说明DFT计算所使用模型或计算方法仍旧需要进一步改进。
3.研究了酸性溶液中CO在Au@Pt核壳纳米粒子薄膜电极上氧化前峰机理。另外利用表面增强拉曼光谱研究了不同pH溶液中CH3OH在Au@Pt纳米粒子薄膜电极上的氧化机理。在氢原子欠电位沉积(H-upd)电势区间吸附的CO在CO饱和的酸性溶液中进行电位扫描时在0.4～0.8 V出现氧化前峰,而在双电层电势区间吸附时则无氧化前峰出现。通过定量比较0.06和0.35V下饱和吸附CO后的拉曼光谱,发现其拉曼光谱没有明显的区别。因此推断在氧化前峰区CO氧化的难易程度很可能不是由表面CO的吸附构型决定,而是来源于不同吸附电势下的Pt基底的晶格结构变化。原位SERS实验发现Au@Pt内米粒子薄膜电极上甲醇在酸性、中性和碱性溶液中的氧化机理是类似的。甲醇在Au@Pt纳米粒子薄膜电极表面脱氢生成的CO以顶位和桥位吸附,三种溶液中COL和COB的比例有很大差别,这可能是三种溶液中界面电场以及电极表面共吸附物种不同导致的。
4.利用表面增强拉曼光谱研究了不同pH值溶液中CO在Au@Pd纳米粒子薄膜电极上的吸附行为,并利用DFT理论计算了不同吸附位、电极电势及覆盖度下CO在Pd(111)表面吸附的键长、吸附能、振动频率。计算结果表明CO在Pd(111)上最稳定的吸附位为穴位,CO在Pd上的吸附能随着电势负移而降低。在-1～0.5 V／A的电场范围内,Pd—COL,M及C—OL,M的振动频率与电极电势成线性关系,说明CO在Pd上吸附时,单纯的电场作用会导致线性的Stark效应。中性和碱性溶液中的原位SERS实验发现Pd—COM及C---OM振动的Stark斜率存在明显的非线性行为。原位电化学SERS实验结果表明Pd—COM及C—OM振动的Stark斜率可以分为三部分：i)从-1.5至-1.2 V,分别为-8～-10和185～207 cm-1/V; ii)从-1.2到-0.15 V,分别为-30-～-31和83～84 cm-1/V; iii)从-0.2到0.55 V, Pd—COM及C—OM振动的Stark斜率分别为-15及43 cm-1／V。根据同步记录的循环伏安曲线,中性和碱性溶液中Stark斜率发生突变的电位恰好对应于析氢起始电位。结合周期性密度泛函理论计算的结果,中性和碱性溶液中的非线性Stark效应来源于析氢电位区间在Pd电极上的共吸附氢原子所导致的CO从桥位向穴位的转化。
5.初步研究了CO在Au@Ru及Au@Rh壳纳米薄膜粒子电极上的吸附及氧化行为。在酸性溶液中,55 nm Au@2 nm Ru纳米粒子不稳定,易出现针孔。在中性溶液中55 nm Au@2 nm Ru纳米粒子比较稳定,在较负电位区间(-1.2～-0.6 V vs.NHE)仅观察到吸附在Ru上吸附的CO的Ru—CO振动和C—-O振动峰；在较正电位区间(大于-0.6Vvs.NHE)Ru发生氧化,可以同时观察到吸附在Ru和RuOx上的Ru—CO及C—--O谱带。RuOx上吸附CO的C—O谱带强度比Ru上吸附CO的C—O谱带强度要大得多,这主要是由于RuOx上吸附CO的C—O振动的拉曼散射截面较大的缘故。在酸性和中性溶液中CO在Au@Rh上吸附的原位SERS实验表明Au@Rh纳米粒子不稳定,易形成“针孔”。在碱性溶液中Au@Rh纳米粒子比较稳定。通过原位SERS实验验证了CO饱和的NaOH溶液中,CO在Au@Rh核壳纳米粒子薄膜电极上的氧化机理为Langmuir-Hinshelwood类型反应。
综上所述,通过表面增强拉曼光谱及密度泛函理论的研究结果,从分子水平上理解了CO在几种贵金属纳米粒子表面的吸附及氧化机理,为研究开发具有抗CO中毒并具有高催化活性的低温质子交换膜燃料电池阳极催化剂提供了理论指导。
Fuel cells are expected to play important roles for the sustainable society. However, most of the fuel cells working at low temperature, such as proton exchange membrance fuel cell (PEMFC) and direct methanol fuel cell (DMFC), meet the same serious problem, i.e, deactivation of anode catalyst induced by adsorption of carbon monoxide (CO) from the fuel. Hence, a fundamental understanding of the adsorption and oxidation of CO at noble metal electrodes such as platinum (Pt) and palladinum (Pd), which is one of the most important components in the anode electrocatalysts, will be of great help to alleviate the CO poisoning problem.
In this Ph.D. thesis, the adsorption and oxidation of CO molecules at core-shell nanoparticle electrodes of Au@M are investigated systematically [where Au and M (M=Pt, Pd, Rh, Ru) represent core and shell materials, respectively] by in-situ surface-enhanced Raman spectroscopy (SERS) measurements. These results are briefly summarized below.
1. The effects of CO coverage, CO partial pressure, and solution pH on the vibrational properties of Pt—CO and C—O stretching modes of CO adlayer at Au@Pt core-shell nanoparticle electrodes. With the increase in COad coverage a decrease (increase) in the Pt—COL (COL) peak frequency together with the increase of all the band intensities are observed. The chemical effects are considered to be responsible for the frequency change of Pt—COL stretching band, and both the chemical and the dipole-dipole coupling effects within adsorbed CO molecules are the main causes for frequency change of C—OL.With the solution switch from CO-saturated 0.5 M H2SO4 solution to CO-free 0.5 M H2SO4 solution at 0.06 V, the peak intensities of Pt—COL and C—OLincrease ca.6% and ca.30%, respectively, together with a slight change in the peak frequency. The intensity change of Pt—COL is mainly attributed to the CO orientation change, while the dipole coupling effects, chemical effects and the CO orientation change are responsible for the intensity and frequency changes of the C—OL stretching vibration. The SERS spectra recorded upon changes in the electrolyte between H2SO4, Na2SO4 and NaOH at constant potentials reveal that a substantial change (up to 50%) in the band intensities of Pt—CO and CO stretching vibrations. In addition, the C—OL (Pt—COL) peak frequency is ca.7 cm-1 higher (2 cm-1 lower) in H2SO4 than that in Na2SO4, while no differences in the peak frequencies have been discerned when switching between in Na2SO4 and NaOH. Small lateral shift of COad from atop edges to exactly atop positions upon the the co-adsorption of H atoms in H2SO4 has been proposed to explain such frequency change, while the band intensity changes are identified to be due to the changes in the chemical enhancement factor upon the electrolyte switch.
2. Potential dependence of CO adsorption at Au@Pt nanoparticle electrodes in a wide potential window. Throughout the potential regime examined, the Stark slopes of dvC—O/dE are always positive while that of dvPt—CO/dE are negative. The Stark slopes of dvPt—CO/dE are almost constant while that of dvC—O/dE increase toward negative potentials. Qualitatively, all the potential-dependent spectral behavior can be rationalized by the delicate changes in the counterweighing effects of the chemical bonding (d(Pt)→2π*(CO) back-donation and 5σ(CO)→sp(Pt) donation) and the dipole—dipole coupling interaction, the latter originates from potential induced changes in the fractional surface coverage of COL and COB species. Based on the fact that the influence of the dipole—dipole coupling interaction on the Pt—CO vibration is'negligible, the measured dvpt-co/dE can serve as indicator to evaluate the potential-induced changes in bonding strength and bond length of Pt-CO. From which we estimate the potential induced changes in the binding energies and bonding lengths of COL (COB) of ca. 0.20 (0.37) eV/V and 0.005 (0.01) A/V, respectively. The larger△Eb/△E of COB than COL reveals that the chemical bonding of COB is more sensitive to the changes in the interfacial electric field than that of COL. Peoridic DFT calculations have been performed to estimate the field-depdendent vibrational frequencies and Stark slopes for the saturated CO adlayer. The DFT calculations demonstrate that the Stark slopes of dvpt-co/dE and dvC—O/dE are much smaller than the present observation. The predicted order of the Stark slope of metal-adsorbate stretching vibrations, i.e.,|dvPt—COL/dE|>|dvPt-COB/dE| as predicted by peoridic DFT calculations, contradicts our experimental observation as well as that from DFT calculations using the cluster model.
3. The origin of pre-peak in bulk CO oxidation at Au@Pt electrode and the mechanism elucidation of methanol electro-oxidation in electrolyte solutions with different pH. A pre-peak has been reported between 0.4～0.8 V for the oxidation of CO pre-adsorbed in the hydrogen adsorption potential region in a CO saturated 0.5 M H2SO4 solution; The pre-peak disappear if CO pre-adsorbed in the double layer region. However, the essential nature for the pre-peak is still in controversy. The in-situ SERS spectra of CO pre-adsorbed at 0.06 and 0.35 V have been determined and no distinguished differences are observed in spectra between the two potentials. It is proposed that the pre-peak is not caused by the CO adsorption structure, but due to the adlayer structure change on the Pt electrode surface. The mechanisms of methanol oxidation in acid, neutral, and basic solutions are found to be similar from the in-situ SERS measurements. CO from methanol dehydrogenation can adsorb at atop and bridge site on Pt surface. The ratios of COL and COB significantly change with solution pH, which may be related with the electric field and co-adsorbed species.
4. SERS characterization and DFT calculation of CO adsorption at Au@Pd electrodes in the solutions with different pH. DFT calculations reveal that hollow site is the most stable adsorption site for COad on Pd(111) surface and CO binding energy for CO adsorption on Pd(111) surface increase with the negative shift of electrode potential. In the electric field region of -1～0.5 V/A, the vibrational frequencies of Pd—COL,M and C—OL,M are linear with the external electric field. EC-SERS studies reveal that the Stark slopes of both Pd—CO and C—O stretching vibrations can be divided into three distinct region:dvC-OM/dE decreases from 185～207 cm-1/V (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, dvPd-COM/dE changes from-8～-10 cm-1/V (from -1.5 to -1.2 V) to-31～-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 voltammetry reveals that at E<-1.2 V hydrogen evolution reaction (HER) occurs. Based on the results of cyclic voltammetry and periodic DFT calculations, the unusual high dvC—OM/dE and the small dvPd—COM/dE in HER region are explained by the conversion of COad from bridge-to hollow-sites induced by co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.
5. The adsorption and electrochemical oxidation of CO at Au@Ru and Au@Rh nanoparticle electrodes. It is found that the Au@Ru core-shell nanoparticles are unstable and contain pinhole on the surface in acidic solution. The Au@Ru core-shell nanoparticles are relatively stable in neutral solution and have been evaluated. It is found that the bands of Ru—CO and C—O vibration modes are observed in the potential region (-1.2～-0.6 V vs. NHE). These band intensities greatly changes with potential. The bands of Ru—CO and C—O vibrations for CO bound to reduced and oxidized Ru surface sites are obtained in the more positive potential region (>-0.6 V vs. NHE). The C—O band intensity of COad on oxidized surface sites is much larger than that on reduced Ru surface sites, which probably originates from the larger Raman scattering cross-section of C—O vibration of COad on oxidized surface sites than that on reduced Ru surface sites. In-situ SERS experiments of CO adsorption on Au@Rh core-shell nanoparticle electrode reveal that Au@Rh nanoparticle electrode is only stable in basic solution. The mechanism of CO oxidation on Au@Rh nanoparticle electrode in CO saturated basic solution was found to be of the Langmuir-Hinshelwood type.
Based on the present in-situ SERS and DFT calcualtions, we have a more comprehensive understanding of adsorption and electrochemical oxidation of CO on Pt, Pd, Rh, and Ru electrode surfaces, which could provide the general guidance for the research and development of high active anode catalysts with good CO-tolerant ability for the fuel cells working at the low temperatures.
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