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Title: Autocatalytic water dissociation on Cu(110) at near ambient conditions

Abstract

Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated based on X-ray photoelectron spectroscopy studies carried out in-situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H{sub 2}O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Broensted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Materials Sciences Division
OSTI Identifier:
926164
Report Number(s):
LBNL-99E
Journal ID: ISSN 0002-7863; JACSAT; TRN: US200807%%502
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 130; Journal Issue: 9; Related Information: Journal Publication Date: 2008
Country of Publication:
United States
Language:
English
Subject:
36; BONDING; DISSOCIATION; WATER; WATER VAPOR; X-RAY PHOTOELECTRON SPECTROSCOPY; Autocatalytic water dissociation WGS

Citation Formats

Mulleregan, Alice, Andersson, Klas, Ketteler, Guido, Bluhm, Hendrik, Yamamoto, Susumu, Ogasawara, Hirohito, Pettersson, Lars G.M., Salmeron, Miquel, and Nilsson, Anders. Autocatalytic water dissociation on Cu(110) at near ambient conditions. United States: N. p., 2007. Web.
Mulleregan, Alice, Andersson, Klas, Ketteler, Guido, Bluhm, Hendrik, Yamamoto, Susumu, Ogasawara, Hirohito, Pettersson, Lars G.M., Salmeron, Miquel, & Nilsson, Anders. Autocatalytic water dissociation on Cu(110) at near ambient conditions. United States.
Mulleregan, Alice, Andersson, Klas, Ketteler, Guido, Bluhm, Hendrik, Yamamoto, Susumu, Ogasawara, Hirohito, Pettersson, Lars G.M., Salmeron, Miquel, and Nilsson, Anders. Wed . "Autocatalytic water dissociation on Cu(110) at near ambient conditions". United States. doi:. https://www.osti.gov/servlets/purl/926164.
@article{osti_926164,
title = {Autocatalytic water dissociation on Cu(110) at near ambient conditions},
author = {Mulleregan, Alice and Andersson, Klas and Ketteler, Guido and Bluhm, Hendrik and Yamamoto, Susumu and Ogasawara, Hirohito and Pettersson, Lars G.M. and Salmeron, Miquel and Nilsson, Anders},
abstractNote = {Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated based on X-ray photoelectron spectroscopy studies carried out in-situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H{sub 2}O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Broensted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.},
doi = {},
journal = {Journal of the American Chemical Society},
number = 9,
volume = 130,
place = {United States},
year = {Wed May 16 00:00:00 EDT 2007},
month = {Wed May 16 00:00:00 EDT 2007}
}
  • Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated on the basis of X-ray photoelectron spectroscopy studies carried out in situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H{sub 2}O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Broensted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.
  • We have investigated the reaction of water vapor with the MgO(100) surface using ambient pressure X-ray photoelectron spectroscopy (AP-XPS), which permits the study of the chemical composition of the MgO/water vapor interface at p(H{sub 2}O) in the Torr range. Water dissociation on thin MgO(100) films of 4-5.5 monolayers (ML) grown on Ag(100) was studied under isobaric conditions at p(H{sub 2}O) ranging from 0.005 to 0.5 Torr and temperatures from 380 to -10 C, up to a maximum relative humidity (RH) of 20%. At RH < 0.01% dissociative adsorption occurs only at defect sites (0.08 ML), while terrace sites remain unreactivemore » toward water dissociation. In the range 0.01 < RH < 0.1% there is an abrupt onset of dissociative adsorption at terrace sites which saturates at 1 ML at 0.1% RH, and is accompanied by an increase in molecular water adsorption. At 20% RH there is 1 ML of molecularly adsorbed water interacting with a fully hydroxylated interface on MgO(100). The observed onset of hydroxylation near 0.01% RH is suggested to be due to water molecules aggregating at the surface, leading to an autocatalytic dissociation of water at MgO(100) terrace sites.« less
  • The interaction of water with clean Ni(110) at temperatures between 425 and 770 K has been studied by work function ([Delta][phi]), desorption mass analysis, and low-energy electron diffraction (LEED). Water is observed to dissociate on clean Ni(110), forming adsorbed oxygen and H[sub 2](g) in a process which is itself catalyzed (and hence termed autocatalytic) by the adsorbed oxygen product. Initial dissociation of water is believed to originate on defects where adsorbed oxygen then promotes growth of O (2 [times] 1) islands in a process which becomes self-poisoning in the limit of saturation of the (2 [times] 1) phase (0.5 MLmore » (ML = monolayer)). The growth kinetics indicate the autocatalysis process is most active when the oxygen coverage is 0.1 ML. A statistical theory supported by computer simulation is developed which models the autocatalytic growth kinetics in terms of nucleation of islands along step edges. The temperature dependence of autocatalysis exhibits a maximum at approx. 600 K. This complex temperature dependence is explained in terms of transition-state theory. 25 refs., 10 figs.« less
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  • No abstract prepared.