Surface vibrational spectroscopy. A comparison of the EELS spectra of organic adsorbates at Pt(111) with IR and Raman spectra of the unadsorbed organics

Abstract In this study EELS spectra obtained for the adsorbed species formed from aqueous electrolytes at Pt(111) electrode surfaces are compared with the IR and Raman spectra of the unadsorbed compounds in order to reveal the changes in vibrational spectra resulting from chemisorption of various important functional groups, and to explore the differences in vibrational absorptivities between EELS spectra of adsorbed species and IR and Raman spectra of the corresponding unadsorbed compounds. Of particular interest are the variations in EELS vibrational frequency, bandwidth and absorptivity due to bonding with the surface, intermolecular interactions of adsorbed molecules and changes in adsorbate molecular orientation. The influence of surface bonding on the EELS spectrum of a functional group was explored through studies of phenol (PL), phenol-d6 (PLD6), benzyl alcohol (BZOH), catechol (CT), benzoic acid (BA), 2-picolinic acid (PA), 2,6-pyridine dicarboxylic acid (26PDCA), and propenoic acid (PPEA). The aromatic ring of adsorbed PL, PLD6, BZA, CT, BA, PA and 26PDCA is oriented parallel to the Pt(111) surface. The resulting strong interactions affect the frequencies and relative intensities of the EELS bands: weak CH stretching modes; a large CC stretching band (1600–1650 cm−1), and weak CH bending (700–800 cm−1). The carboxylic acid moieties of BA and PA interact strongly with the Pt surface, while those of 26PDCA do so only when adsorbed at relatively positive electrode potentials. OH stretching and bending are absent from the EELS spectra of adsorbed PL, BZOH and CT, perhaps due to dissociation of the hydroxyl hydrogen during adsorption of the molecule. Adsorption of alkenes at Pt(111) from solution preserves the characteristic CC stretching band near 1650 cm−1; examples are: PPEA; 1-hexene (HXE); propenol (PPEOH); 4-pentenol (PTEOH); and cis-2-butene-1,4-diol (CBED); adsorption of ethene, propene and butene from vacuum at room temperature has been reported to result in loss of double-bond character. Adsorption of propynol (PPYOH) lowers the frequency of the CC triple bond to approximately that of a double bond. EELS spectra of adsorbed pyridine (PY), 2-methylpyridine (2MPY) and 2,6-dimethylpyridine (26DMPY) were examined in order to contrast the vibrational behavior of adsorbates having the aromatic ring perpendicular to the Pt surface (PY and 2MPY), giving rise to strong perturbation of the vibrational spectra or parallel (26DMPY), leading to limited perturbation of the vibrational spectra. Compounds for which the surface interaction is limited primarily to bonding of a single sulfur atom were studied in order to observe the vibrational behavior of a comparatively unperturbed pendant ring or chain: thiophenol (TP); benzylmercaptan (BM); cysteine (CYS); and thiophene (TPE). The expected lack of perturbation was found, making TP, BM and CYS particularly suitable reference compounds for surface vibrational studies of aromatic rings and amino acids. In contrast, L-phenylalanine (PHE) interacts with the Pt(111) surface through the phenyl ring as well as the amino acid functionality. In general, chemisorption and intra-layer intermolecular interaction both lower the surface vibrational frequencies (EELS) and incidentally affect peak amplitudes. Orientation affects peak amplitudes and incidentally affects frequencies insofar as a change in orientation is accompanied by a change in mode of surface bonding. Surface roughness leads to a scrambling of adsorbed states which affects bandwidths, chemical/electrochemical reactivities, and in turn the frequencies and amplitudes of EELS peaks. Specific findings and conclusions are presented for each compound and correlated.