In situ infrared study of water-sulfate coadsorption on gold(111) in sulfuric acid solutions

被引:282
作者
Ataka, K [1 ]
Osawa, M [1 ]
机构
[1] Hokkaido Univ, Catalysis Res Ctr, Sapporo, Hokkaido 060, Japan
关键词
D O I
10.1021/la971110v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Potential-dependent reorientation of a water molecule, adsorption of sulfate, and interactions between water and sulfate on a highly ordered Au(111) electrode surface in sulfuric acid solutions have been investigated in situ as a function of applied potential by means of surface-enhanced infrared absorption spectroscopy. The spectrum of the water layer at the interface changes in both intensity and frequency as the applied potential changes due to the reorientation of water molecules. The orientations deduced from infrared spectra are in good agreement with the predictions made by molecular dynamics simulations at potentials below and around the potential of zero charge (pzc) of the electrode where sulfate adsorption is negligible. At potentials above the pzc, sulfate anion is adsorbed at S-fold hollow sites on the (111) surface via three oxygen atoms. When the potential is increased and the fractional coverage of sulfate reaches to about one-half of full coverage, adsorbed sulfate anions start to form short-ranged domains and greatly change the water layer structure. Water molecules stabilize the sulfate domains by bridging neighboring sulfate anions via hydrogen bonding. The weak tunneling spots observed in the reported scanning tunneling microscopy images of the well-ordered (root 3 x root 7) sulfate adlayers on (111) metal surfaces are attributed to water molecules that bridge adjacent adsorbed sulfate anions.
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页码:951 / 959
页数:9
相关论文
共 37 条
[1]   ELEMENTARY STEPS OF ELECTROCHEMICAL OXIDATION OF SINGLE-CRYSTAL PLANES OF AU .1. CHEMICAL BASIS OF PROCESSES INVOLVING GEOMETRY OF ANIONS AND THE ELECTRODE SURFACES [J].
ANGERSTEINKOZLOWSKA, H ;
CONWAY, BE ;
HAMELIN, A ;
STOICOVICIU, L .
ELECTROCHIMICA ACTA, 1986, 31 (08) :1051-1061
[2]   ELEMENTARY STEPS OF ELECTROCHEMICAL OXIDATION OF SINGLE-CRYSTAL PLANES OF AU .2. A CHEMICAL AND STRUCTURAL BASIS OF OXIDATION OF THE (111) PLANE [J].
ANGERSTEINKOZLOWSKA, H ;
CONWAY, BE ;
HAMELIN, A ;
STOICOVICIU, L .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1987, 228 (1-2) :429-453
[3]   Potential-dependent reorientation of water molecules at an electrode/electrolyte interface studied by surface-enhanced infrared absorption spectroscopy [J].
Ataka, K ;
Yotsuyanagi, T ;
Osawa, M .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (25) :10664-10672
[4]  
BANGE K, 1984, SURF SCI, V136, P38
[5]   DINUCLEAR, METAL METAL-BONDED PLATINUM(III) COMPOUNDS .1. PREPARATION AND STRUCTURE OF K2[PT2(SO4)4(OSME2)2].4H2O [J].
COTTON, FA ;
FALVELLO, LR ;
HAN, S .
INORGANIC CHEMISTRY, 1982, 21 (07) :2889-2891
[6]  
Delahay P., 1965, Double layer and electrode kinetics.
[7]   The kinetics of structural changes in anionic adlayers on stepped Au(111)(s) electrodes from sulfuric acid solutions [J].
Dretschkow, T ;
Wandlowski, T .
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1997, 101 (04) :749-757
[8]   THE ADSORPTION OF SULFATE ON GOLD(111) IN ACIDIC AQUEOUS-MEDIA - ADLAYER STRUCTURAL INFERENCES FROM INFRARED-SPECTROSCOPY AND SCANNING-TUNNELING-MICROSCOPY [J].
EDENS, GJ ;
GAO, XP ;
WEAVER, MJ .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1994, 375 (1-2) :357-366
[9]   A STUDY OF BISULFATE ADSORPTION ON PT(111) SINGLE-CRYSTAL ELECTRODES USING INSITU FOURIER-TRANSFORM INFRARED-SPECTROSCOPY [J].
FAGUY, PW ;
MARKOVIC, N ;
ADZIC, RR ;
FIERRO, CA ;
YEAGER, EB .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1990, 289 (1-2) :245-262
[10]   Anion adsorption from sulfuric acid solutions on Pt(111) single crystal electrodes [J].
Funtikov, AM ;
Stimming, U ;
Vogel, R .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1997, 428 (1-2) :147-153