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- W2503131567 abstract "Reviewed here are surface electrochemical studies of organic molecules adsorbed at well-defined Pt(111) electrode surfaces from aqueous solution. Emphasis is placed upon studies of nicotinic acid (NA), pyridine (PYR), and nine related pyridine carboxylic acids. Packing densities (moles per unit area) adsorbed from solution at controlled pH and electrode potential, and measured by means of Auger spectroscopy are discussed. Vibrational spectra of each adsorbed obtained by use of electron energy-loss spectroscopy (EELS) are compared with the IR spectra of the parent compounds. Electrochemical reactivity is studied by use of cyclic voltammetry. Monolayer structures observed by means of low-energy electron diffraction (LEED) are described. Substances studied are as follows: 3-pyridine carboxylic acid (nicotinic acid, NA, niacin); pyridine (PYR); 3-pyridylhydroquinone (3PHQ), synthesized here for the first time; 4-pyridine carboxylic acid (isonicotinic acid, INA); 2-pyridine carboxylic acid (picolinic acid, PA); 3,4-pyridine dicarboxylic acid (3,4PDA); and the analogous other pyridine dicarboxylic acids 3,5PDA, 2,3PDA, 2,4PDA and 2,6PDA. Each of the pyridine derivatives is adsorbed at Pt(111) in a tilted vertical orientation; an angle of 70-75° between the pyridyl plane and the Pt(111) surface is typical. Pt-N bonding is evidently the predominant mode of surface attachment of these compounds, although coordination of carboxylate is an important mode of additional surface attachment at positive potentials. EELS spectra display strong O-H stretching vibrations near 3550-1 cm due to carboxylic acids in the meta and para-positions, and weak-to-moderate signals near 3350 cm-1 due to ortho-carboxylates. Nicotinic acid and related meta-carboxylic acids display the remarkable characteristic that coordination of the pendant carboxylic acid moieties to the Pt surface is controlled by electrode potential. Oxidative coordination of the carboxylate pendant occurs at positive electrode potentials, resulting in disappearance of the O-H vibration and loss of surface acidity as judged by absence of reactivity towards KOH. Carboxylate in the 4-position of pyridine (as in INA) is virtually independent of electrode potential, whereas strong coordination of ortho-carboxylates to the Pt surface is present at most electrode potentials. Adsorbed pyridine carboxylic acids are stable in vacuum; when returned to solution the adsorbed material displays the same chemical and electrochemical properties as prior to evacuation." @default.
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- W2503131567 date "1988-11-11" @default.
- W2503131567 modified "2023-09-23" @default.
- W2503131567 title "Molecular Adsorption at Well-Defined Platinum Surfaces" @default.
- W2503131567 doi "https://doi.org/10.1021/bk-1988-0378.ch002" @default.
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