In situ FTIR studies of coadsorption of CN− and CO on Pt(110) electrode surface

Tian, Li; Li, Jun‐Tao; Ye, Jinyu; Zhang, Chunhua; Sun, Shi‐Gang

doi:10.1016/j.jelechem.2011.04.028

Cited by 13 publications

(23 citation statements)

References 30 publications

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“…Linearly bound CO on Pt-NPs exhibits a strong IR absorption band, which sensitively responds to electrochemical potentials of the electrode. 26,27 By changing the potential, the CO stretch frequency can be varied in a potential range of -0.5 to about +0.4V. In this potential range CO is stable on small Pt-NPs, but complete CO desorption is observed for potentials larger than +0.4 V. 26,27 Fig.…”

Section: Introductionmentioning

confidence: 97%

Surface-Sensitive Spectro-electrochemistry Using Ultrafast 2D ATR IR Spectroscopy

2016

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A new method is presented for the combination of spectro-electrochemistry and femtosecond 2D IR spectroscopy. The key concept is based on ultrathin (similar to nm) conductive layers of noble metals and indium-tin oxide (ITO) as working electrodes on a single-reflection attenuated total reflectance (ATR) element in conjunction with ultrafast, multidimensional ATR spectroscopy. The ATR geometry offers prominent benefits in ultrafast spectro-electrochemistry, that is, surface sensitivity for studying electrochemical processes directly at the solvent-electrode interface as well as the application of strongly IR-absorbing solvents such as water due to a very short effective path length of the evanescent wave at the interface. We present a balanced comparison between usable electrode materials regarding their performance in the ultrafast ATR setup. The electrochemical performance is demonstrated by vibrational Stark-shift spectroscopy of carbon monoxide (CO) adsorbed to platinum-coated, ultrathin ITO electrodes. We furthermore measure vibrational relaxation and spectral diffusion of the stretching mode from surfacebound CO dependent on the applied potential to the working electrode and find a negligible impact of the electrode potential on ultrafast CO dynamics.

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Section: Introductionmentioning

confidence: 97%

Surface-Sensitive Spectro-electrochemistry Using Ultrafast 2D ATR IR Spectroscopy

2016

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“…In addition to organic MLs equipped with different IR labels, strong interest also exists in the characterization of the vibrational properties of small molecules with only few atoms, such as carbon monoxide (CO) 89,135,172,304 , adsorbed hydrogen 89,[305][306][307] , pseudo-halides (e.g. CN -) 90,[308][309][310] , or water 50,52,[311][312][313][314] . These adsorbates are important in heterogeneous catalysis and also allow one to address fundamental questions of substrate-adsorbate coupling and energy transfer.…”

Section: Monolayers Of Small Moleculesmentioning

confidence: 99%

“…In a potential range of -1 V to +0.4 V, the frequency of the stretching mode of linearly-bound CO changes due to a vibrational Stark-shift with a tuning rate of 24 cm -1 V -1 (Figure 30 (d)), in good agreement with earlier reports obtained by other methods. 271,310,334 The Stark-effect is commonly explained by two combined effects, i.e. (i) potential-dependent changes in electron densities in the molecular orbitals of the adsorbate 332,335,336 , and (ii) potential-dependent changes in energetic positions of vibrational states relative to each other due to slightly different dipole moments in these levels 337,338 .…”

Section: D Atr Ir At Electrode Surfacesmentioning

confidence: 99%

Surface-Sensitive and Surface-Specific Ultrafast Two-Dimensional Vibrational Spectroscopy

2016

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Ultrafast two-dimensional infrared spectroscopy (2D IR) has been advanced in recent years toward measuring signals from only a monolayer of sample molecules at solid-liquid and solid-gas interfaces. A series of experimental methods has been introduced, which in the chronological order of development are 2D sum-frequency-generation (2D SFG), transmission 2D IR, and reflection 2D IR, the latter in either internal, attenuated total reflection (ATR), or external reflection configuration. The different variants of 2D vibrational spectroscopy are based on either the even-order or the odd-order nonlinear susceptibility, and all allow resolving similar molecular temporal and spectral information. In this review, we introduce the basic principles of the different methods of 2D vibrational spectroscopy at surfaces along with a balanced overview on the technological aspects as well as benefits and shortcomings. We furthermore discuss the current scope of applications for 2D vibrational surface spectroscopy, which spans an impressively broad range of samples from biological molecules to heterogeneous catalysts. The emphasis is on the ultrafast structural dynamics of molecules at interfaces, environmental interactions, and intermolecular interactions. We furthermore consider important recent technological developments of 2D vibrational surface spectroscopy, which employ (i) surface enhancement, (ii) methods for studying electrochemical interfaces, and (iii) extensions for resolving nonequilibrium processes (transient 2D IR). A detailed outlook is finally given regarding important future applications and technological developments of 2D vibrational surface spectroscopy.

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“…With the increase of potential, the background changes apparently caused from water simultaneously consumed and produced. The bipolar nature of the CO L band is indicative of the fact that this adsorbate was present at both the reference and the sample potentials, with the characteristic frequency showing a potential dependent shift [33]. For CO L , the bipolar bands are difficult to quantitate, so we use the intensity variation of CO 2 to monitor the process of methanol oxidation.…”

Section: In-situ Ftir Spectroscopy Studiesmentioning

confidence: 99%

CeO2 nanorods with high energy surfaces as electrocatalytical supports for methanol electrooxidation

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et al. 2015

Electrochimica Acta

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In situ FTIR studies of coadsorption of CN− and CO on Pt(110) electrode surface

Cited by 13 publications

References 30 publications

Surface-Sensitive Spectro-electrochemistry Using Ultrafast 2D ATR IR Spectroscopy

Surface-Sensitive Spectro-electrochemistry Using Ultrafast 2D ATR IR Spectroscopy

Surface-Sensitive and Surface-Specific Ultrafast Two-Dimensional Vibrational Spectroscopy

CeO2 nanorods with high energy surfaces as electrocatalytical supports for methanol electrooxidation

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