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Chemisorption Geometry, Vibrational Spectra, and Thermal Desorption of Formic Acid on TiO2 (110)

Journal Article · · Surface Review and Letters
 [1];  [2];  [3];  [2]
  1. unknown
  2. BATTELLE (PACIFIC NW LAB)
  3. ASSOC WESTERN UNIVERSITY
+ Show Author Affiliations

We have used high-energy X-ray photoelectron spectroscopy and diffraction (XPS/XPD), low-energy electron diffraction (LEED), high-resolution electron energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD) to determine the molecular orientation, long-range order, vibrational freequencies, and desorption temperatures for formic acid and its decomposition products on TiO2(110). Molecular adsorption occurs at coverages approaching one monolayer, producing a weakly ordered (2x1) surface structure. High-energy XPD reveals that the formate binds rigidly in a bidentate fashion through the oxygens to Ti cation rows along the [001] direction with an O-C-O bond angle of 126 +- 4 degrees. During TPD some surface protons and formate anions recombine and desorb as formic acid above 250 k. However, most of the decomposition products follow reaction pathways leading to H2O, CO and H2CO desorption. Water is formed in TPD below 500 K via the abstraction of lattice oxygen by deposited acid protons.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1511006
Report Number(s):
PNNL-SA-27794
Journal Information:
Surface Review and Letters, Journal Name: Surface Review and Letters Journal Issue: 1 Vol. 5
Country of Publication:
United States
Language:
English

References (9)

TPD and HREELS investigation of the reaction of formic acid on zirconium dioxide(100) journal December 1993
An HREELS and TPD study of water on TiO2(110): the extent of molecular versus dissociative adsorption journal June 1996
Final-state effects in photoelectron diffraction journal January 1990
STM-imaging of formate intermediates adsorbed on a TiO2(110) surface journal August 1994
Switchover of Reaction Paths in the Catalytic Decomposition of Formic Acid on TiO2(110) Surface journal April 1994
Formic Acid Decomposition on the {110}-Microfaceted Surface of TiO2(100): Insights Derived from 18O-Labeling Studies journal October 1995
Structural dependence of the selectivity of formic acid decomposition on faceted titania (001) surfaces journal September 1990
Surface carboxylate species on Cu(100) studied by angle-scanned photoelectron diffraction and LCAO-LDF calculations journal August 1994
Elastic scattering and interference of backscattered primary, Auger and X-ray photoelectrons at high kinetic energy: principles and applications journal October 1992

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Related Subjects

oxide
titanium oxide
formic acid
titanium oxide
XPS
LEED