Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films

Lixin Cao, Franz Josef Spiess, Aimin Huang, Steven L. Suib, Timothy N. Obee, Steven O. Hay, James Freihaut

Research output: Contribution to journalArticle

80 Citations (Scopus)

Abstract

Three types of films were prepared by a dip-coating process for the photocatalyzed decomposition of 1-butene in a gas-solid reaction. Under UV illumination (λ > 300 nm, 352 nm peak intensity), ultrasmall SnO2 with a diameter of 5 nm exhibited initial photoactivity as high as 3 times that of P-25 TiO2 (30 nm) in the absence of water vapor whereas SnO2-1 (22 nm) did not show photoactivity. Quantum size effects were mainly responsible for the high photoactivity achieved by SnO2. Inactivity of SnO2-1 film was due to the absence of active hydroxyl groups on the catalyst surface and low surface areas. By investigation of the effects of humidity, water has two different functions: maintaining constant oxidation rates at low water levels by replenishing hydroxyl groups and decreasing the photoactivity at high water levels by competitive adsorption with butene on active sites. Compared with TiO2, SnO2 cannot withstand high humidity since it is very sensitive to water concentration. Hydroxyl groups on catalyst surfaces are the active centers for the reaction. The occurrence of obvious deactivation on SnO2 films was due to the depletion of hydroxyl groups and the accumulation of carbonate species on particle surfaces, i.e., M-OCOOR species in place of M-OH. The kinetic data correlate with a Langmuir-Hinshelwood single-site model. XRD, UV-vis spectroscopy, and FTIR techniques were employed to characterize the particle size, band gaps, and surface properties of the catalysts.

Original languageEnglish (US)
Pages (from-to)2912-2917
Number of pages6
JournalJournal of Physical Chemistry B
Volume103
Issue number15
StatePublished - Apr 15 1999

Fingerprint

butenes
Butenes
Hydroxyl Radical
Oxidation
oxidation
Water levels
catalysts
water
Catalysts
humidity
Atmospheric humidity
Water
Carbonates
Steam
Ultraviolet spectroscopy
deactivation
Water vapor
surface properties
Surface properties
coating

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Cao, L., Spiess, F. J., Huang, A., Suib, S. L., Obee, T. N., Hay, S. O., & Freihaut, J. (1999). Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films. Journal of Physical Chemistry B, 103(15), 2912-2917.
Cao, Lixin ; Spiess, Franz Josef ; Huang, Aimin ; Suib, Steven L. ; Obee, Timothy N. ; Hay, Steven O. ; Freihaut, James. / Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films. In: Journal of Physical Chemistry B. 1999 ; Vol. 103, No. 15. pp. 2912-2917.
@article{868ddd379aff4dfab6224f0cafec4ab7,
title = "Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films",
abstract = "Three types of films were prepared by a dip-coating process for the photocatalyzed decomposition of 1-butene in a gas-solid reaction. Under UV illumination (λ > 300 nm, 352 nm peak intensity), ultrasmall SnO2 with a diameter of 5 nm exhibited initial photoactivity as high as 3 times that of P-25 TiO2 (30 nm) in the absence of water vapor whereas SnO2-1 (22 nm) did not show photoactivity. Quantum size effects were mainly responsible for the high photoactivity achieved by SnO2. Inactivity of SnO2-1 film was due to the absence of active hydroxyl groups on the catalyst surface and low surface areas. By investigation of the effects of humidity, water has two different functions: maintaining constant oxidation rates at low water levels by replenishing hydroxyl groups and decreasing the photoactivity at high water levels by competitive adsorption with butene on active sites. Compared with TiO2, SnO2 cannot withstand high humidity since it is very sensitive to water concentration. Hydroxyl groups on catalyst surfaces are the active centers for the reaction. The occurrence of obvious deactivation on SnO2 films was due to the depletion of hydroxyl groups and the accumulation of carbonate species on particle surfaces, i.e., M-OCOOR species in place of M-OH. The kinetic data correlate with a Langmuir-Hinshelwood single-site model. XRD, UV-vis spectroscopy, and FTIR techniques were employed to characterize the particle size, band gaps, and surface properties of the catalysts.",
author = "Lixin Cao and Spiess, {Franz Josef} and Aimin Huang and Suib, {Steven L.} and Obee, {Timothy N.} and Hay, {Steven O.} and James Freihaut",
year = "1999",
month = "4",
day = "15",
language = "English (US)",
volume = "103",
pages = "2912--2917",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "15",

}

Cao, L, Spiess, FJ, Huang, A, Suib, SL, Obee, TN, Hay, SO & Freihaut, J 1999, 'Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films', Journal of Physical Chemistry B, vol. 103, no. 15, pp. 2912-2917.

Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films. / Cao, Lixin; Spiess, Franz Josef; Huang, Aimin; Suib, Steven L.; Obee, Timothy N.; Hay, Steven O.; Freihaut, James.

In: Journal of Physical Chemistry B, Vol. 103, No. 15, 15.04.1999, p. 2912-2917.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films

AU - Cao, Lixin

AU - Spiess, Franz Josef

AU - Huang, Aimin

AU - Suib, Steven L.

AU - Obee, Timothy N.

AU - Hay, Steven O.

AU - Freihaut, James

PY - 1999/4/15

Y1 - 1999/4/15

N2 - Three types of films were prepared by a dip-coating process for the photocatalyzed decomposition of 1-butene in a gas-solid reaction. Under UV illumination (λ > 300 nm, 352 nm peak intensity), ultrasmall SnO2 with a diameter of 5 nm exhibited initial photoactivity as high as 3 times that of P-25 TiO2 (30 nm) in the absence of water vapor whereas SnO2-1 (22 nm) did not show photoactivity. Quantum size effects were mainly responsible for the high photoactivity achieved by SnO2. Inactivity of SnO2-1 film was due to the absence of active hydroxyl groups on the catalyst surface and low surface areas. By investigation of the effects of humidity, water has two different functions: maintaining constant oxidation rates at low water levels by replenishing hydroxyl groups and decreasing the photoactivity at high water levels by competitive adsorption with butene on active sites. Compared with TiO2, SnO2 cannot withstand high humidity since it is very sensitive to water concentration. Hydroxyl groups on catalyst surfaces are the active centers for the reaction. The occurrence of obvious deactivation on SnO2 films was due to the depletion of hydroxyl groups and the accumulation of carbonate species on particle surfaces, i.e., M-OCOOR species in place of M-OH. The kinetic data correlate with a Langmuir-Hinshelwood single-site model. XRD, UV-vis spectroscopy, and FTIR techniques were employed to characterize the particle size, band gaps, and surface properties of the catalysts.

AB - Three types of films were prepared by a dip-coating process for the photocatalyzed decomposition of 1-butene in a gas-solid reaction. Under UV illumination (λ > 300 nm, 352 nm peak intensity), ultrasmall SnO2 with a diameter of 5 nm exhibited initial photoactivity as high as 3 times that of P-25 TiO2 (30 nm) in the absence of water vapor whereas SnO2-1 (22 nm) did not show photoactivity. Quantum size effects were mainly responsible for the high photoactivity achieved by SnO2. Inactivity of SnO2-1 film was due to the absence of active hydroxyl groups on the catalyst surface and low surface areas. By investigation of the effects of humidity, water has two different functions: maintaining constant oxidation rates at low water levels by replenishing hydroxyl groups and decreasing the photoactivity at high water levels by competitive adsorption with butene on active sites. Compared with TiO2, SnO2 cannot withstand high humidity since it is very sensitive to water concentration. Hydroxyl groups on catalyst surfaces are the active centers for the reaction. The occurrence of obvious deactivation on SnO2 films was due to the depletion of hydroxyl groups and the accumulation of carbonate species on particle surfaces, i.e., M-OCOOR species in place of M-OH. The kinetic data correlate with a Langmuir-Hinshelwood single-site model. XRD, UV-vis spectroscopy, and FTIR techniques were employed to characterize the particle size, band gaps, and surface properties of the catalysts.

UR - http://www.scopus.com/inward/record.url?scp=0000281196&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000281196&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000281196

VL - 103

SP - 2912

EP - 2917

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 15

ER -

Cao L, Spiess FJ, Huang A, Suib SL, Obee TN, Hay SO et al. Heterogeneous Photocatalytic Oxidation of 1-Butene on SnO2 and TiO2 Films. Journal of Physical Chemistry B. 1999 Apr 15;103(15):2912-2917.