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Title: Formic Acid Adsorption on Anatase TiO2(001)-(1 × 4) Thin Films Studied by NC-AFM and STM

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
DOI:https://doi.org/10.1021/jp020617y· OSTI ID:1423427

Atomic resolution scanning tunneling microscopy (STM), non-contact atomic force microscopy (NC-AFM), X-ray photoemission spectroscopy (XPS), low-energy electron diffraction (LEED) and formic acid adsorption experiments were used to characterize the (001) surface of anatase TiO2. A combination of NC-AFM and STM imaging was used to distinguish features due to geometrical and electronic effects. The contrast in images of the bare (1 × 4) surface and the formate-covered surface is dominated by the surface topography in both NC-AFM and STM, although electronic effects in the troughs contribute features to the STM images that are absent from NC-AFM images. High resolution imaging by STM and NC-AFM revealed that the highest point of the ridge of the (1 × 4) structure consists of a single row of atoms. Formate adsorbs at under-coordinated Ti sites in the added rows with a minimum separation of 2a0, and never adsorbs in the trenches even though the trenches also likely expose under-coordinated Ti atoms. The sticking probability of formate on the anatase TiO2(001)-(1 × 4) surface is near unity initially, and falls dramatically once the saturation coverage of 1/8 ML is reached. We show that of the current models for the (1 × 4) reconstruction, an added row plus surface oxygen vacancy model and the recently proposed ad-molecule model are in best agreement with all of the data.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1423427
Report Number(s):
PNNL-SA-36055; KP1704020
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 106, Issue 33; ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

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