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Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

Author:
  • J. Rosenqvist
  • K. Axe
  • S. Sjoberg
  • Per Persson
Publishing year: 2003
Language: English
Pages: 91-104
Publication/Series: Colloids and Surfaces A: Physicochemical and Engineering Aspects
Volume: 220
Document type: Journal article
Publisher: Elsevier
Additional info: 1-3

Abstract english

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition -O2C-C-n-CO2; n = 0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier. transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with,IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n = 2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n = I and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(111) at the surface. This showed the importance of chelate ring structure for the formation-of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n = 2 only small variations in surface speciation were observed as a function of steric factors; irrespective. of the. relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption model Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles. (C) 2003 Elsevier Science B.V. All. rights reserved.

Keywords

  • Earth and Related Environmental Sciences

Other

Published
  • ISSN: 0927-7757
Per Persson
E-mail: per [dot] persson [at] biol [dot] lu [dot] se

Professor

MEMEG

+46 46 222 17 96

+46 70 266 38 79

E-C350

50

Professor

Centre for Environmental and Climate Research (CEC)

+46 46 222 17 96

+46 70 266 38 79

D350

Ekologihuset, Sölvegatan 37, Lund

50