Infrared spectroelectrochemistry

Ashley, Kevin; Pons, Stanley

doi:10.1021/cr00086a006

Cited by 232 publications

(136 citation statements)

References 46 publications

(55 reference statements)

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“…As can be seen, the SCN -signal was detected on the Ni surface over a wide potential range from severe hydrogen evolution to the surface oxidation region (-2.0 V to +1.0 V). When the potential was kept at -2.0 V, two bands located at 2027 cm -1 and at 2070 cm -1 , assigned to the CN stretch, [28][29][30][31][32][33][34][35][36][37][38] could be observed. At this very negative potential, severe hydrogen evolution may greatly alter the optical system on detecting, which may cause a decrease in the SERS intensity.…”

Section: Scnmentioning

confidence: 99%

“…29 The shifts of these band positions caused by the adsorption and applied potential can be detected, and allow statements to be made about the nature of the adsorption mode and about the surface-adsorbate interaction. 1,30 Although specifically adsorbed SCN -on Au, Ag and Pt surfaces have been studied by IR, 1,28,31-36 SFG 37,38 extensively, and many SERS investigations have been reported on Ag and Au, [39][40][41][42][43][44][45] but not Pt, there is to date no consensus on the potential-dependent behavior of the surface orientation. Both the S-and N-bound thiocyanide exhibit a CN stretching vibration in the 2050 -2165 cm -1 range; 1,[28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] therefore, the use of this band frequency alone as a criterion of the bonding could be somewhat risky.…”

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Analyzing the Adsorption Behavior of Thiocyanide on Pure Pt and Ni Electrode Surfaces by Confocal Microprobe Raman Spectroscopy

et al. 2000

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Surface vibrational spectroscopies, such as infrared (IR), 1,2 Raman 3,4 and sum frequency generation (SFG), 5 are powerful surface analytical tools for in-situ investigating electrochemical interfaces by providing information at the molecular level. Among these techniques, Raman spectroscopy exhibits several advantages over IR spectroscopy and the SFG technique in analyzing solid/liquid interfaces: 3 (i) easy use of near-UV, visible, or near-IR light sources for the excitation of the Raman process, (ii) transparency of the electrolyte for the light beam, (iii) application of standard electrochemical cells without the need of using thin liquid cells, and hence, (iv) easy combination with electrochemical transient measurements in faradaic and non-faradaic regions, (v) easy obtaining vibrational bands related to the adsorbate-surface interaction in the low-frequency region (<500 cm -1 ). However, the lack of detection sensitivity has been a severe obstacle which had impeded the wide application of Raman spectroscopy in surface science and interfacial electrochemistry. In the absence of any resonance Raman or surface-enhancement processes, the typical differential Raman cross section (dσ/dΩ)NRS is less than 10 -29 cm 2 sr -1 compared with 10 -20 cm 2 sr -1 that of IR. 3 Especially in the analysis of adsorbates on the surface, the molecular quantity present is normally on the order of monolayer, or even submonolayer.Accordingly, the corresponding surface Raman intensities expected for a monolayer adsorbates are less than 1 count per second (cps) when standard Raman spectrometer systems are used. The discovery of surface-enhanced Raman scattering (SERS) in the 1970s, 6-8 that the Raman intensities for pyridine adsorbed at electrochemically roughened Ag electrodes were six orders of magnitude larger than those expected from the known differential Raman cross section for pyridine in solution, changed the situation of surface Raman spectroscopy. These findings stimulated worldwide experimental and theoretical research on SERS. Among the various proposed SERS mechanisms, "electromagnetic mechanism" (EM) 9 and "chemical effect" or "charge transfer" (CT) enhancement 10 have been widely accepted as the two main contributions to the giant surface enhancement. In the past two decades, with its high surface sensitivity and ease detecting vibrations in the lowfrequency region, SERS has been extensively applied in surface science, 3,4,9,10 analytical science 11 and life science. 12 Although it has especially provided a wealth of information in understanding solid/liquid and solid/gas interfacial structures, its application was almost restricted to noble metals, i.e., Ag, Au and Cu. 3,4,9,10 Therefore, it is worth finding other SERS substrates which are extensively used in variety of technologically important processes, such as Pt, Ni and Fe metals. Many researchers have been exploring very hard to attain this goal, but successful cases are few. Among them, Fleischmann's group 13 and Weaver's group 14,15 took advantage of the lo...

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Section: Scnmentioning

confidence: 99%

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confidence: 99%

Analyzing the Adsorption Behavior of Thiocyanide on Pure Pt and Ni Electrode Surfaces by Confocal Microprobe Raman Spectroscopy

et al. 2000

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“…Similarly, ratioing a background spectrum to a sample spectrum to produce -what is also commonly known as a difference spcctrum-is a widely used method for obtaining data using Fourier Transform Infrared Spectroscopy. !n general, these difference spectra techniques arc used to eliminate interference from detector response characteristics in combination with optical characteristics of mirrors, sample handling materials (e.g., infrared transparent salts) and other non-sample infrared absorbers in the beam path (e.g., water vapor, C0 2 ). The best sample data will be obtained using a background spectrum where the sample is removed without disturbing anything in the beam path.…”

Section: Distribu-tionz Availability Codesmentioning

confidence: 99%

Interpreting IR Difference Spectra

1991

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From the evaluation of sample difference spectra based on Gaussian “model” peaks with known peak characteristics, it is shown that interpretation of some parameters from difference spectra, resulting from the ratioing or subtraction of a poor background spectra, may be inaccurate or misleading. Difference spectra of this type are commonly observed with the use of techniques such as subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), electrochemically modulated infrared reflectance spectroscopy (EMIRS), or similar infrared spectroelectrochemical techniques, as well as some microsample analyses, studies of biochemical processes, and infrared astronomical observations, to name just a few examples. A mathematical evaluation of the problem is offered to demonstrate what information may realistically be gained from the characteristics of difference spectra. It is shown that in the worst case, where frequency, intensity, and peak width are all changing due to some perturbation of the sample (e.g., from temperature, or surface potential changes between background and sample spectra, etc.), even a qualitative interpretation may not be possible. In many practical cases, however, we show that at least a qualitative interpretation of the data can be obtained from difference spectra. Spectroelectrochemical applications for the calculations shown here are presented as examples, although these results impact a wider range of applications.

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“…IR spectroelectrochemical detection systems have been applied widely to solve different electrochemical problems as described in several review articles [1,2]. Basically, IR detection modes of transmittance, external reflection, and internal reflection are adaptable to the IR spectroelectrochemical detection systems.…”

Section: Introductionmentioning

confidence: 99%

A New Infrared Spectroelectrochemical Cell for the Detection of Species Generated by Platinum and Screen‐Printed Carbon Electrodes

Shih

Yang

2006

Electroanalysis

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In this paper, we describe a simple and effective infrared (IR) spectroelectrochemical cell for detecting species generated from an electrochemical system featuring low-IR-reflectivity electrodes. The IR detection mode of attenuated total reflection (ATR) was employed to construct the spectroelectrochemical cell. Two kinds of electrodes, platinum (Pt) and screen-printed carbon (SPC), were used to examine the performance of this new cell in detection of electroactive species generated by cyclic voltammetry. Because data generated from highly reflective electrodes are available in the literature, Pt electrode was used to characterize the performances of the developed spectroelectrochemical cell. Results indicated that species generated electrochemically can be observed readily and their responses were comparable to those described in the literature. The cell volume could be lower than 300 mL, which suggests that this approach may be very useful to obtain chemical information during electrochemistry for biological fluids with limited sample volumes. By examining the electrochemical behavior of several amino acids using both Pt and SPC electrodes, the redox behaviors can be readily observed indicating a new spectroelectrochemical cell was successfully developed for the purpose of using of SPC electrode.

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Infrared spectroelectrochemistry

Cited by 232 publications

References 46 publications

Analyzing the Adsorption Behavior of Thiocyanide on Pure Pt and Ni Electrode Surfaces by Confocal Microprobe Raman Spectroscopy

Analyzing the Adsorption Behavior of Thiocyanide on Pure Pt and Ni Electrode Surfaces by Confocal Microprobe Raman Spectroscopy

Interpreting IR Difference Spectra

A New Infrared Spectroelectrochemical Cell for the Detection of Species Generated by Platinum and Screen‐Printed Carbon Electrodes

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