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Title: Adsorption of small hydrocarbons on rutile TiO2(110)

Abstract

Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1–C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2–C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.

Authors:
 [1];  [1];  [1];  [1]
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1251558
Alternate Identifier(s):
OSTI ID: 1373616
Report Number(s):
PNNL-SA-113158
Journal ID: ISSN 0039-6028; PII: S003960281500374X;
Grant/Contract Number:  
KC0301050-47319; AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Surface Science
Additional Journal Information:
Journal Volume: 1021; Journal Issue: C; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; hydrocarbons; adsorption; desorption; temperature programmed desorption; sticking coefficient

Citation Formats

Chen, Long, Smith, R. Scott, Kay, Bruce D., and Dohnalek, Zdenek. Adsorption of small hydrocarbons on rutile TiO2(110). United States: N. p., 2015. Web. doi:10.1016/j.susc.2015.11.002.
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Chen, Long, Smith, R. Scott, Kay, Bruce D., & Dohnalek, Zdenek. Adsorption of small hydrocarbons on rutile TiO2(110). United States. https://doi.org/10.1016/j.susc.2015.11.002
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Chen, Long, Smith, R. Scott, Kay, Bruce D., and Dohnalek, Zdenek. Sat . "Adsorption of small hydrocarbons on rutile TiO2(110)". United States. https://doi.org/10.1016/j.susc.2015.11.002. https://www.osti.gov/servlets/purl/1251558.
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@article{osti_1251558,
title = {Adsorption of small hydrocarbons on rutile TiO2(110)},
author = {Chen, Long and Smith, R. Scott and Kay, Bruce D. and Dohnalek, Zdenek},
abstractNote = {Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1–C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2–C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.},
doi = {10.1016/j.susc.2015.11.002},
journal = {Surface Science},
number = C,
volume = 1021,
place = {United States},
year = {Sat Nov 21 00:00:00 EST 2015},
month = {Sat Nov 21 00:00:00 EST 2015}
}
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