Peroxide electroreduction on Bi-modified Au surfaces: Vibrational spectroscopy and density functional calculations

被引:72
作者
Li, X
Gewirth, AA
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
[2] Univ Illinois, Fredrick Seitz Mat Res Lab, Urbana, IL 61801 USA
关键词
D O I
10.1021/ja034125q
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The mechanism of the electroreduction of peroxide on Bi-submonolayer-modified Au(111) surfaces is examined using surface-enhanced Raman scattering (SERS) measurements along with detailed density functional theory (DFT) calculations. The spectroscopy shows the presence of Bi-OH and Bi-O species at potentials just positive of that where peroxide is reduced. These species are not present in solutions absent either peroxide or Bi. DFT calculations show that peroxide is unstable relative to Bi-OH when Bi is present in the (2 x 2) configuration on Au(111) known from previous work to be catalytically active. The spacing between Bi adatoms is such that peroxide association with two Bi cannot occur without O-O bond cleavage. The full Bi monolayer is catalytically inactive and exhibits none of the Bi-OH or Bi-O signals seen for the active surface. The calculations show that as the Bi coverage becomes greater and the Bi adatom spacing becomes smaller, peroxide can adsorb on Bi without O-O bond rupture. These results indicate an important role for M-OH species in peroxide electroreduction.
引用
收藏
页码:7086 / 7099
页数:14
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