Carbon monoxide oxidation on a Pt(111) electrode studied by in-situ IRAS and STM: coadsorption of CO with water on Pt(111)

Yoshimi, Koichiro; Song, Moon‐Bong; Ito, M.

doi:10.1016/s0039-6028(96)01081-3

Cited by 84 publications

(83 citation statements)

References 11 publications

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“…The inhomogeneous distribution could be caused by the crystallinity of Pt or water hydrogen bonding to the CO or both. Previously, features in the OH stretch region have been attributed to H 2 O molecules coadsorbed with the CO monolayer (37). Moreover, recent DFT calculations have shown that there are strong/weak hydrogen-bonding interactions between the coadsorbed H 2 O and the bridge/atop-adsorbed CO molecules (38).…”

Section: Formalism Of Hd 2d Sfg Spectroscopymentioning

confidence: 99%

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy

Xiong

Laaser

Mehlenbacher

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

166

232

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In the last ten years, two-dimensional infrared spectroscopy has become an important technique for studying molecular structures and dynamics. We report the implementation of heterodyne detected two-dimensional sum-frequency generation (HD 2D SFG) spectroscopy, which is the analog of 2D infrared (2D IR) spectroscopy, but is selective to noncentrosymmetric systems such as interfaces. We implement the technique using mid-IR pulse shaping, which enables rapid scanning, phase cycling, and automatic phasing. Absorptive spectra are obtained, that have the highest frequency resolution possible, from which we extract the rephasing and nonrephasing signals that are sometimes preferred. Using this technique, we measure the vibrational mode of CO adsorbed on a polycrystalline Pt surface. The 2D spectrum reveals a significant inhomogenous contribution to the spectral line shape, which is quantified by simulations. This observation indicates that the surface conformation and environment of CO molecules is more complicated than the simple "atop" configuration assumed in previous work. Our method can be straightforwardly incorporated into many existing SFG spectrometers. The technique enables one to quantify inhomogeneity, vibrational couplings, spectral diffusion, chemical exchange, and many other properties analogous to 2D IR spectroscopy, but specifically for interfaces. multidimensional spectroscopy | vibrational spectroscopy | surface-sensitive | Pt catalysis | CO monolayer M olecular spectroscopies are some of the best tools for studying structures and dynamics. Two particularly useful variants are sum-frequency generation (SFG) and two-dimensional infrared (2D IR) spectroscopy. SFG spectroscopy provides a vibrational spectrum of molecular systems that lack an inversion center (1), and so has become a valuable tool for probing interfaces because no signal arises from the bulk. SFG spectroscopy has helped reveal the surface structure of liquids, characterize the surfaces of materials, and probe membrane proteins, to name only a few applications (2-5). 2D IR spectroscopy is also a vibrational spectroscopy, although not interface specific. 2D IR spectroscopy spreads the infrared spectrum into a second coordinate so that coupled vibrational modes are correlated by cross peaks, vibrational dynamics quantified by 2D line shapes, and energy transfer or chemical exchange revealed from peak intensities (6-8), in addition to many other capabilities not possible with linear one-dimensional (1D) vibrational spectroscopies like SFG spectroscopy. 2D IR spectroscopy is now being used to study protein structure and dynamics, solvent dynamics, charge transfer in semiconductors, and many other processes (9-12). These two techniques might be considered the core technologies of modern infrared spectroscopy.In this article, we combine the surface sensitivity of SFG spectroscopy with the multidimensional capabilities of 2D IR spectroscopy in a technique that we call heterodyne detected (HD) 2D SFG spectroscopy. With this technique, one obtain...

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Section: Formalism Of Hd 2d Sfg Spectroscopymentioning

confidence: 99%

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy

Xiong

Laaser

Mehlenbacher

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

166

232

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“…Presence of such non-hydrogen bonded water molecules was concluded on Au [69] at 3612 cm −1 above 0.77 V in 0.5 M HClO 4 in the absence of adsorbed CO. On Pt(1 1 1) in UHV, co-adsorption of CO and water has been investigated by IRAS at low temperatures by studying effect of water (D 2 O) on ν(CO) bands of adsorbed CO and of CO on ν(OD) bands of adsorbed water. Formation of intermingled islands comprised of CO and D 2 O molecules present in the adjacent sites was concluded by analyzing the C-O and O-D stretching spectra [10,76,77]. Effect of 3 ML of H 2 O on the pre-adsorbed c(4 × 2) − 2CO (θ CO = 0.5) layer was also examined on Pt(1 1 1) at 110 K. A new band observed at 3612 cm −1 was interpreted as the ν(OH) of H 2 O interacting with co-adsorbed CO [10].…”

Section: Change In Surface Water Ad-layer Accompanied With Co Adsorptionmentioning

confidence: 99%

“…The in situ infrared reflection absorption spectroscopy (IRAS) has played an important role in characterizing adsorbed CO on polycrystalline [1][2][3] as well as single crystal [4][5][6][7][8][9][10][11][12][13][14] platinum electrodes. These studies have met the practical needs to anomalies [15][16][17][23][24][25][26][27][28][29] which makes it difficult to conduct quantitative analysis of band intensity as well as band position of CO adsorbed on the catalyst.…”

Section: Introductionmentioning

confidence: 99%

Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods

Sato

Kunimatsu

Uchida

et al. 2007

Electrochimica Acta

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“…The presence of water molecules and electrolyte ions were suggested to be in the CO adlayers [32]. Water species have also been detected at potentials as low as 0.05 V, which increases the effective surface coverage by (CO) ad compared with those obtained in UHV conditions [33][34][35]. Other experiments performed with Pt single crystals in 1 M sulphuric acid have shown that the O-H bond is weakened as a consequence of the strengthening of the Pt-O bond at potentials ca.…”

Section: Discussionmentioning

confidence: 89%

Heterogeneously assisted oxidation of adsorbates from carbonmonoxide, methanol and ethanol by hydrogen peroxide solutions on platinum electrodes in sulphuric acid

et al. 2006

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The influence of hydrogen peroxide on the adsorption and oxidation of carbon monoxide, methanol and ethanol adlayers on porous Pt electrodes were studied in 2 M sulphuric acid solution by means of cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). The oxidation of adsorbed species is observed at electrode potentials far less negative than those required for electrochemical adsorbate oxidation. The oxidation by H 2 O 2 is dependent on its concentration in solution, as well as on the adsorbates and their coverages. In all cases the isolated adlayers are oxidised by dissolved H 2 O 2 . However, the presence of H 2 O 2 during adsorption partially inhibits adlayer formation from CH 3 OH and C 2 H 5 OH, but avoids almost completely the adsorption of carbon monoxide. The removal of the residues from the surface by dissolved hydrogen peroxide probably occurs through O ad species formed during the heterogeneous decomposition reaction of H 2 O 2 on Pt.

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Carbon monoxide oxidation on a Pt(111) electrode studied by in-situ IRAS and STM: coadsorption of CO with water on Pt(111)

Cited by 84 publications

References 11 publications

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy

Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods

Heterogeneously assisted oxidation of adsorbates from carbonmonoxide, methanol and ethanol by hydrogen peroxide solutions on platinum electrodes in sulphuric acid

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