TY - JOUR
T1 - Observation and Identification of an Atomic Oxygen Structure on Catalytic Gold Nanoparticles
AU - Liu, Kai
AU - Chen, Tao
AU - He, Shuyue
AU - Robbins, Jason P.
AU - Podkolzin, Simon G.
AU - Tian, Fei
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/10/9
Y1 - 2017/10/9
N2 - Interactions between oxygen and gold surfaces are fundamentally important in diverse areas of science and technology. In this work, an oxygen dimer structure was observed and identified on gold nanoparticles in catalytic decomposition of hydrogen peroxide to oxygen and water. This structure, which is different from isolated atomic or molecular oxygen surface structures, was observed with in situ surface-enhanced Raman spectroscopic measurements and identified with density functional theory calculations. The experimental measurements were performed using monodisperse 5, 50 and 400 nm gold particles supported on silica with liquid-phase hydrogen and deuterium peroxides at multiple pH values. The calculations show that on surfaces with coordinatively unsaturated gold atoms, two oxygen atoms preferentially share a gold atom with a bond distance of 0.194–0.196 nm and additionally bind to two other surface gold atoms with a larger bond distance of 0.203–0.213 nm, forming an Au-O-Au-O-Au structure. The formation of this structure depends on reaction rates and conditions.
AB - Interactions between oxygen and gold surfaces are fundamentally important in diverse areas of science and technology. In this work, an oxygen dimer structure was observed and identified on gold nanoparticles in catalytic decomposition of hydrogen peroxide to oxygen and water. This structure, which is different from isolated atomic or molecular oxygen surface structures, was observed with in situ surface-enhanced Raman spectroscopic measurements and identified with density functional theory calculations. The experimental measurements were performed using monodisperse 5, 50 and 400 nm gold particles supported on silica with liquid-phase hydrogen and deuterium peroxides at multiple pH values. The calculations show that on surfaces with coordinatively unsaturated gold atoms, two oxygen atoms preferentially share a gold atom with a bond distance of 0.194–0.196 nm and additionally bind to two other surface gold atoms with a larger bond distance of 0.203–0.213 nm, forming an Au-O-Au-O-Au structure. The formation of this structure depends on reaction rates and conditions.
KW - Au surface
KW - HO decomposition
KW - adsorbed oxygen
KW - kinetic measurements
KW - monodisperse nanoparticles
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U2 - 10.1002/anie.201706647
DO - 10.1002/anie.201706647
M3 - Article
C2 - 28776923
AN - SCOPUS:85028937389
SN - 1433-7851
VL - 56
SP - 12952
EP - 12957
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 42
ER -