Combined ATR-FTIR and DFT study of cyclohexanone adsorption on hydrated TiO2 anatase surfaces

A.R. Almeida, Ana Rita Almeida, Monica Calatayud, Frederik Tielens, Jacob A. Moulijn, Guido Mul

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

The adsorption of cyclohexanone on different planes ((100), (101), and (001)) of anatase TiO2, with variable level of hydration, was evaluated by density functional theory (DFT) calculations. Surface hydration was found to affect the cyclohexanone adsorption enthalpy and the calculated infrared absorption frequencies of the preferred adsorbed configurations considerably. A good correlation was found between two experimentally observed absorption frequencies at 1694 and at 1681 cm–1 of cyclohexanone adsorbed on TiO2, determined by attenuated total reflection Fourier transform infrared (ATR-FTIR), and frequencies calculated for conformations of cyclohexanone interacting with the (101) surface with low and intermediate levels of hydration, respectively. The corresponding adsorption enthalpies of these adsorbed conformations amount to −23.5 and −37.0 kJ/mol, respectively. In addition, DFT calculations show that cyclohexanone physisorption on hydrated (100) yields an adsorption enthalpy of −89.4 kJ/mol. This might be a conformation contributing to irreversible adsorption of cyclohexanone known to occur experimentally after photocatalytic activation of TiO2. Other phenomena of relevance to irreversible adsorption are also briefly discussed
Original languageEnglish
Pages (from-to)14164-14172
Number of pages9
JournalJournal of physical chemistry C
Volume115
Issue number29
DOIs
Publication statusPublished - 2011

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anatase
Titanium dioxide
Density functional theory
Fourier transforms
density functional theory
Infrared radiation
Adsorption
adsorption
Hydration
hydration
Conformations
Enthalpy
enthalpy
Physisorption
Infrared absorption
infrared absorption
titanium dioxide
cyclohexanone
Chemical activation
activation

Keywords

  • METIS-280310
  • IR-95289

Cite this

Almeida, A.R. ; Almeida, Ana Rita ; Calatayud, Monica ; Tielens, Frederik ; Moulijn, Jacob A. ; Mul, Guido. / Combined ATR-FTIR and DFT study of cyclohexanone adsorption on hydrated TiO2 anatase surfaces. In: Journal of physical chemistry C. 2011 ; Vol. 115, No. 29. pp. 14164-14172.
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title = "Combined ATR-FTIR and DFT study of cyclohexanone adsorption on hydrated TiO2 anatase surfaces",
abstract = "The adsorption of cyclohexanone on different planes ((100), (101), and (001)) of anatase TiO2, with variable level of hydration, was evaluated by density functional theory (DFT) calculations. Surface hydration was found to affect the cyclohexanone adsorption enthalpy and the calculated infrared absorption frequencies of the preferred adsorbed configurations considerably. A good correlation was found between two experimentally observed absorption frequencies at 1694 and at 1681 cm–1 of cyclohexanone adsorbed on TiO2, determined by attenuated total reflection Fourier transform infrared (ATR-FTIR), and frequencies calculated for conformations of cyclohexanone interacting with the (101) surface with low and intermediate levels of hydration, respectively. The corresponding adsorption enthalpies of these adsorbed conformations amount to −23.5 and −37.0 kJ/mol, respectively. In addition, DFT calculations show that cyclohexanone physisorption on hydrated (100) yields an adsorption enthalpy of −89.4 kJ/mol. This might be a conformation contributing to irreversible adsorption of cyclohexanone known to occur experimentally after photocatalytic activation of TiO2. Other phenomena of relevance to irreversible adsorption are also briefly discussed",
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Combined ATR-FTIR and DFT study of cyclohexanone adsorption on hydrated TiO2 anatase surfaces. / Almeida, A.R.; Almeida, Ana Rita; Calatayud, Monica; Tielens, Frederik; Moulijn, Jacob A.; Mul, Guido.

In: Journal of physical chemistry C, Vol. 115, No. 29, 2011, p. 14164-14172.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Combined ATR-FTIR and DFT study of cyclohexanone adsorption on hydrated TiO2 anatase surfaces

AU - Almeida, A.R.

AU - Almeida, Ana Rita

AU - Calatayud, Monica

AU - Tielens, Frederik

AU - Moulijn, Jacob A.

AU - Mul, Guido

PY - 2011

Y1 - 2011

N2 - The adsorption of cyclohexanone on different planes ((100), (101), and (001)) of anatase TiO2, with variable level of hydration, was evaluated by density functional theory (DFT) calculations. Surface hydration was found to affect the cyclohexanone adsorption enthalpy and the calculated infrared absorption frequencies of the preferred adsorbed configurations considerably. A good correlation was found between two experimentally observed absorption frequencies at 1694 and at 1681 cm–1 of cyclohexanone adsorbed on TiO2, determined by attenuated total reflection Fourier transform infrared (ATR-FTIR), and frequencies calculated for conformations of cyclohexanone interacting with the (101) surface with low and intermediate levels of hydration, respectively. The corresponding adsorption enthalpies of these adsorbed conformations amount to −23.5 and −37.0 kJ/mol, respectively. In addition, DFT calculations show that cyclohexanone physisorption on hydrated (100) yields an adsorption enthalpy of −89.4 kJ/mol. This might be a conformation contributing to irreversible adsorption of cyclohexanone known to occur experimentally after photocatalytic activation of TiO2. Other phenomena of relevance to irreversible adsorption are also briefly discussed

AB - The adsorption of cyclohexanone on different planes ((100), (101), and (001)) of anatase TiO2, with variable level of hydration, was evaluated by density functional theory (DFT) calculations. Surface hydration was found to affect the cyclohexanone adsorption enthalpy and the calculated infrared absorption frequencies of the preferred adsorbed configurations considerably. A good correlation was found between two experimentally observed absorption frequencies at 1694 and at 1681 cm–1 of cyclohexanone adsorbed on TiO2, determined by attenuated total reflection Fourier transform infrared (ATR-FTIR), and frequencies calculated for conformations of cyclohexanone interacting with the (101) surface with low and intermediate levels of hydration, respectively. The corresponding adsorption enthalpies of these adsorbed conformations amount to −23.5 and −37.0 kJ/mol, respectively. In addition, DFT calculations show that cyclohexanone physisorption on hydrated (100) yields an adsorption enthalpy of −89.4 kJ/mol. This might be a conformation contributing to irreversible adsorption of cyclohexanone known to occur experimentally after photocatalytic activation of TiO2. Other phenomena of relevance to irreversible adsorption are also briefly discussed

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