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Thiol adsorption on metal oxide nanoparticles.

Owen C Grimm1, R M Dulanga S Somaratne, Yiwen Wang

  • 1Department of Chemistry, The University of Massachusetts Lowell, Lowell, MA 01854, USA. James_Whitten@uml.edu.

Physical Chemistry Chemical Physics : PCCP
|April 20, 2021
PubMed
Summary

Thiol adsorption on metal oxide nanoparticles was studied. Adsorption of 2-naphthalenethiol and methanethiol occurred only on ZnO, TiO2, and In2O3 nanoparticles, confirmed by fluorescence and XPS. DFT calculations supported these findings.

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Area of Science:

  • Materials Science
  • Surface Chemistry
  • Nanotechnology

Background:

  • Metal oxide nanoparticles are widely used in various applications.
  • Understanding surface interactions is crucial for nanoparticle functionalization.
  • Thiol compounds are important in surface modification and sensing.

Purpose of the Study:

  • To investigate the adsorption behavior of thiols on diverse metal oxide nanoparticles.
  • To identify specific metal oxides that effectively adsorb thiols.
  • To elucidate the mechanism of thiol adsorption on metal oxide surfaces.

Main Methods:

  • Screening adsorption using fluorescence spectroscopy with 2-naphthalenethiol.
  • X-ray photoelectron spectroscopy (XPS) for in situ analysis of methanethiol adsorption.
  • Density Functional Theory (DFT) calculations on metal oxide clusters.

Main Results:

  • Adsorption of both 2-naphthalenethiol and methanethiol was observed exclusively on ZnO, TiO2, and In2O3 nanoparticles.
  • No significant adsorption was detected on Al2O3, CeO2, Fe2O3, Gd2O3, Ho2O3, NiO, SiOx, WO3, Y2O3, and ZrO2.
  • DFT calculations indicated that dissociative adsorption occurs via hydroxyl group replacement, forming water.

Conclusions:

  • The adsorption of thiols on metal oxide nanoparticles is highly dependent on the specific metal oxide material.
  • The relative strengths of metal-sulfur and metal-hydroxyl bonds govern thiol adsorption.
  • Nanoparticle size and geometry play a minor role in the adsorption process.