Scanning tunneling microscopy study of formate species synthesized from CO{sub 2} hydrogenation and prepared by adsorption of formic acid over Cu(111)

Journal Article · Thu Feb 17 04:00:00 EST 2000 · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical

DOI:https://doi.org/10.1021/jp9920242· OSTI ID:20017541

Fujitani, T; Choi, Y; Sano, M; Kushida, Y; Nakamura, J

The adsorption structure of formate species on Cu(111), prepared by two different methods, was studied using ultrahigh vacuum scanning tunneling microscopy (UHV-STM), that is, the synthesis by the hydrogenation of CO{sub 2} at atmospheric pressure and the adsorption of formic acid on an oxygen-precovered Cu(111). Linear chains of formate molecules were imaged by the hydrogenation of CO{sub 2} by STM at low formate coverage with the distance to the nearest neighbor of the formate species estimated to be 5.0 {+-} 0.2{angstrom}, twice that of the nearest Cu--Cu neighbor. The adsorption phase of formate thus grows linearly at the initial stage by an anisotropic attractive interaction between the formate species. The ordered structure of the formate species changed in the order of p(2 x 4), c(2 x 8), (7 x 7), p(2 x 3), (5 x 5), and c(2 x 4) with increasing formate coverage, indicating that various ordered structures appeared corresponding to the small change in the formate coverage. All the formate structures, except for (7 x 7) and (5 x 5), consisted of the same chain as observed at low coverage, with the distance between the formate chains, resulting in a lowering of the adsorption energy of the formate species as reported in the literature. On the other hand, (4 x 4) and (3 x 7/2) structures were observed upon exposing the Cu(111) surface to formic acid at 2 and 15 L, respectively, showing no chain structure of the formate species. At low formate coverage, no molecular image was observed, indicating that the formate species diffuses more rapidly than the scanning of the STM tip. Thus, the adsorption structure of formate on Cu(111) was found to be different depending on the preparation method. It is suggested that the difference in the adsorption structure strongly influences the rate constant of the previously reported formate decomposition.

• Research Organization: National Inst. for Resources and Environment, Tsukuba, Ibaraki (JP)
• OSTI ID: 20017541
• Journal Information: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 6 Vol. 104; ISSN 1089-5647; ISSN JPCBFK
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
10 SYNTHETIC FUELS
CARBON DIOXIDE
CATALYTIC EFFECTS
COPPER
FORMATES
FORMIC ACID
HYDROGENATION
METHANATION
METHANOL
SYNTHESIS