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IR and quantum-chemical studies of carboxylic acid and glycine adsorption on rutile TiO2 nanoparticles
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, The Institute of Technology.ORCID iD: 0000-0002-5341-2637
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, The Institute of Technology.ORCID iD: 0000-0002-7171-5383
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, The Institute of Technology.
2006 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 296, no 1, 71-78 p.Article in journal (Refereed) Published
Abstract [en]

  Nanocrystalline TiO2 powders of the rutile polymorph, synthesized by a sol–gel method, were treated with water solutions containing, respectively, formic, acetic, and citric acid and glycine in order to study the adsorption properties of these organic species. The samples were characterized by FTIR, Raman, powder XRD, and TEM. It was found that HCOOH, CH3COOH and HOC(COOH)(CH2COOH)2—but not NH2CH2COOH—adsorbed onto TiO2. The adsorption of HCOOH, CH3COOH and NH2CH2COOH onto the (110) surface of rutile was also studied by quantum-chemical periodic density functional theory (DFT) calculations. The organic molecules were from the computations found to adsorb strongly to the surfaces in a bridge-coordinating mode, where the two oxygens of the deprotonated carboxylic acid bind to two surface titanium ions. Surface relaxation is found to influence adsorption geometries and energies significantly. The results from DFT calculations and ab initio molecular-dynamics simulations of formic acid adsorption onto TiO2 are compared and match well with the experimental IR measurements, supporting the bridge-binding geometry of carboxylic-acid adsorption on the TiO2 nanoparticles.

Place, publisher, year, edition, pages
2006. Vol. 296, no 1, 71-78 p.
Keyword [en]
Titanium oxide; Nanoparticle; Adsorption; Carboxylic acid; Glycine; FTIR; Raman; Quantum-chemical calculations
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-36193DOI: 10.1016/j.jcis.2005.08.037ISI: 000236185600010Local ID: 30468OAI: oai:DiVA.org:liu-36193DiVA: diva2:257041
Available from: 2009-10-10 Created: 2009-10-10 Last updated: 2017-12-13
In thesis
1. Experimental and quantum-chemical studies of the surface interactions between organic molecules and nanocrystals of (a) RE2O3 (RE = Y or Gd); and (b) TiOb2
Open this publication in new window or tab >>Experimental and quantum-chemical studies of the surface interactions between organic molecules and nanocrystals of (a) RE2O3 (RE = Y or Gd); and (b) TiOb2
2005 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The increasing interest for using nanocrystals in bio-medical and optical applications has highlighted the need of molecular functionalisation of nanocrystals. Knowledge of how to attach molecules to the nanocrystal surface is a key factor. This thesis focuses on the surface interactions between nanocrystals of (a) RE2O3 (RE = Y or Gd); and (b) TiO2 and organic molecules, which have been studied experimentally and by quantum-chemical calculations with the intent to elucidate the chemisorption characteristics such as adsorption geometries and energies.

(a) RE2O3 nanocrystal synthesis was performed by a colloidal method based on polyols and by a rapid combustion method. The products were experimentally characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR), Raman, and X-ray photoelectron spectroscopy (XPS). By quantum chemical calculations the chemisorption of formic acid, DEG, water and TMOS at the surface of RE12O18 clusters was studied. From comparison between calculated and experimental vibrational spectra, the binding mode for formic acid on RE2O3 was inferred to be of bridge or bidentate type. XPS and IR showed that DEG chemisorbs on the particle surface and experimental IR spectra of DEG chemisorbed on RE2O3 were consistent with an adsorption mode where the hydroxyl groups are deprotonated according to the quantum-chemical computations.

(b) Synthesis of single-phase rutile TiO2 nanocrystals was done by a sol-gel method and the nanocrystals was subsequently functionalized by organic acids and glycine. Quantum-chemical studies indicate that formic- and acetic acid adsorbs in a bridge or monodentate binding mode, while glycine is suggested to adsorb as a zwitterion with bridge bonded carboxylic group and a hydrogen bonded amino group. However, spectroscopic data showed that the amino acid, unlike the other acids did not adsorb on TiO2 under the given experimental conditions.

Place, publisher, year, edition, pages
Linköping: Linköpings universitet, 2005. 67 p.
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1198
National Category
Inorganic Chemistry Physical Chemistry
Identifiers
urn:nbn:se:liu:diva-29720 (URN)LiU-TEK-LIC-2005:53 (Local ID)91-85457-33-7 (ISBN)LiU-TEK-LIC-2005:53 (Archive number)LiU-TEK-LIC-2005:53 (OAI)
Presentation
(English)
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Available from: 2009-10-09 Created: 2009-10-09 Last updated: 2015-03-11Bibliographically approved

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Ojamäe, LarsPedersen, HenrikKäll, Per-Olov

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