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Title: High Pressure Scanning Tunneling Microscopy and High PressureX-ray Photoemission Spectroscopy Studies of Adsorbate Structure,Composition and Mobility during Catalytic Reactions on A Model SingleCrystal

Abstract

Our research focuses on taking advantage of the ability of scanning tunneling microscopy (STM) to operate at high-temperatures and high-pressures while still providing real-time atomic resolution images. We also utilize high-pressure x-ray photoelectron spectroscopy (HPXPS) to monitor systems under identical conditions thus giving us chemical information to compare and contrast with the structural and dynamic data provided by STM.

Authors:
 [1]
  1. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Science and Engineering Division
OSTI Identifier:
883801
Report Number(s):
LBNL-60167
R&D Project: 517101; BnR: KC0203010; TRN: US200615%%256
DOE Contract Number:
AC02-05CH11231
Resource Type:
Thesis/Dissertation
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MONITORS; MONOCRYSTALS; PHOTOEMISSION; RESOLUTION; SCANNING TUNNELING MICROSCOPY; SPECTROSCOPY; X-RAY PHOTOELECTRON SPECTROSCOPY

Citation Formats

Montano, Max O. High Pressure Scanning Tunneling Microscopy and High PressureX-ray Photoemission Spectroscopy Studies of Adsorbate Structure,Composition and Mobility during Catalytic Reactions on A Model SingleCrystal. United States: N. p., 2006. Web. doi:10.2172/883801.
Montano, Max O. High Pressure Scanning Tunneling Microscopy and High PressureX-ray Photoemission Spectroscopy Studies of Adsorbate Structure,Composition and Mobility during Catalytic Reactions on A Model SingleCrystal. United States. doi:10.2172/883801.
Montano, Max O. Sun . "High Pressure Scanning Tunneling Microscopy and High PressureX-ray Photoemission Spectroscopy Studies of Adsorbate Structure,Composition and Mobility during Catalytic Reactions on A Model SingleCrystal". United States. doi:10.2172/883801. https://www.osti.gov/servlets/purl/883801.
@article{osti_883801,
title = {High Pressure Scanning Tunneling Microscopy and High PressureX-ray Photoemission Spectroscopy Studies of Adsorbate Structure,Composition and Mobility during Catalytic Reactions on A Model SingleCrystal},
author = {Montano, Max O.},
abstractNote = {Our research focuses on taking advantage of the ability of scanning tunneling microscopy (STM) to operate at high-temperatures and high-pressures while still providing real-time atomic resolution images. We also utilize high-pressure x-ray photoelectron spectroscopy (HPXPS) to monitor systems under identical conditions thus giving us chemical information to compare and contrast with the structural and dynamic data provided by STM.},
doi = {10.2172/883801},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}

Thesis/Dissertation:
Other availability
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  • Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.
  • The aim of the work presented therein is to take advantage of scanning tunneling microscope’s (STM) capability for operation under a variety of environments under real time and at atomic resolution to monitor adsorbate structures and mobility under high pressures, as well as to design a new generation of STM systems that allow imaging in situ at both higher pressures (35 atm) and temperatures (350 °C).
  • High-pressure, high-temperature scanning tunneling microscopy (HPHTSTM) was used to study adsorbate structures and reactions on single crystal model catalytic systems. Studies of the automobile catalytic converter reaction [CO + NO → 1/2 N 2 + CO 2] on Rh(111) and ethylene hydrogenation [C 2H 4 + H 2 → C 2H 6] on Rh(111) and Pt(111) elucidated information on adsorbate structures in equilibrium with high-pressure gas and the relationship of atomic and molecular mobility to chemistry. STM studies of NO on Rh(111) showed that adsorbed NO forms two high-pressure structures, with the phase transformation from the (2 x 2) structuremore » to the (3 x 3) structure occurring at 0.03 Torr. The (3 x 3) structure only exists when the surface is in equilibrium with the gas phase. The heat of adsorption of this new structure was determined by measuring the pressures and temperatures at which both (2 x 2) and (3 x 3) structures coexisted. The energy barrier between the two structures was calculated by observing the time necessary for the phase transformation to take place. High-pressure STM studies of the coadsorption of CO and NO on Rh(111) showed that CO and NO form a mixed (2 x 2) structure at low NO partial pressures. By comparing surface and gas compositions, the adsorption energy difference between topsite CO and NO was calculated. Occasionally there is exchange between top-site CO and NO, for which we have described a mechanism for. At high NO partial pressures, NO segregates into islands, where the phase transformation to the (3 x 3) structure occurs. The reaction of CO and NO on Rh(111) was monitored by mass spectrometry (MS) and HPHTSTM. From MS studies the apparent activation energy of the catalytic converter reaction was calculated and compared to theory. STM showed that under high-temperature reaction conditions, surface metal atoms become mobile. Ethylene hydrogenation and its poisoning by CO was also studied by STM on Rh(111) and Pt(111). Poisoning was found to coincide with decreased adsorbate mobility. Under ethylene hydrogenation conditions, no order is detected by STM at 300 K, as hydrogen and ethylidyne, the surface species formed by gas-phase ethylene, are too mobile. When CO is introduced, the reaction stops, and ordered structures appear on the surface. For Rh(111), the structure is predominantly a mixed c(4 x 2), though there are some areas of (2 x 2). For Pt(111), the structure is hexagonal and resembles the Moire pattern seen when Pt(111) is exposed to pure CO. From these studies it is concluded that CO poisons by stopping adsorbate mobility. This lack of adsorbate mobility prevents the adsorption of ethylene from the gas phase by hindering the creation of adsorption sites.« less
  • Results of this thesis show that STM measurements can provide information about the surfaces and their adsorbates. Stability of Pt(110) under high pressures of H 2, O 2, and CO was studied (Chap. 4). In situ UHV and high vacuum experiments were carried out for sulfur on Pt(111) (Chap.5). STM studies of CO/S/Pt(111) in high CO pressures showed that the Pt substrate undergoes a stacking-fault-domain reconstruction involving periodic transitions from fcc to hcp stacking of top-layer atoms (Chap.6). In Chap.7, the stability of propylene on Pt(111) and the decomposition products were studied in situ with the HPSTM. Finally, in Chap.8,more » results are presented which show how the Pt tip of the HPSTM was used to locally rehydrogenate and oxidize carbonaceous clusters deposited on the Pt(111) surface; the Pt tip acted as a catalyst after activation by short voltage pulses.« less