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2017 ; 114
(13
): E2556-E2562
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Electron transfer between anatase TiO(2) and an O(2) molecule directly observed
by atomic force microscopy
#MMPMID28289217
Setvin M
; Hulva J
; Parkinson GS
; Schmid M
; Diebold U
Proc Natl Acad Sci U S A
2017[Mar]; 114
(13
): E2556-E2562
PMID28289217
show ga
Activation of molecular oxygen is a key step in converting fuels into energy, but
there is precious little experimental insight into how the process proceeds at
the atomic scale. Here, we show that a combined atomic force microscopy/scanning
tunneling microscopy (AFM/STM) experiment can both distinguish neutral O(2)
molecules in the triplet state from negatively charged (O(2))(-) radicals and
charge and discharge the molecules at will. By measuring the chemical forces
above the different species adsorbed on an anatase TiO(2) surface, we show that
the tip-generated (O(2))(-) radicals are identical to those created when (i) an
O(2) molecule accepts an electron from a near-surface dopant or (ii) when a
photo-generated electron is transferred following irradiation of the anatase
sample with UV light. Kelvin probe spectroscopy measurements indicate that
electron transfer between the TiO(2) and the adsorbed molecules is governed by
competition between electron affinity of the physisorbed (triplet) O(2) and band
bending induced by the (O(2))(-) radicals. Temperature-programmed desorption and
X-ray photoelectron spectroscopy data provide information about thermal stability
of the species, and confirm the chemical identification inferred from AFM/STM.