Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms Jo¨ rgen Rosenqvist 1 , Kristina Axe, Staffan Sjo¨ berg, Per Persson * Department of Chemistry, Inorganic Chemistry, Umea˚ University, SE-901 87 Umea, Sweden Received 22 October 2002; accepted 11 February 2003 Abstract The adsorption of the dicarboxylates o -phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition  O 2 C /C n /CO 2  ; 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 /1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) 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 mode. 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. # 2003 Elsevier Science B.V. All rights reserved. Keywords: Gibbsite; Carboxylates; Adsorption; FTIR spectroscopy; Bonding mechanisms 1. Introduction There are numerous studies devoted to the chemistry of aluminum (hydr)oxides. This interest is, to a large extent, generated by their ubiquitous presence in soils and natural aquatic environ- ments, and by their use and presence in technolo- gical applications and processes (e.g. the Bayer * Corresponding author. Tel.: /46-90-786-55-73; fax: /46- 90-786-91-95. E-mail address: per.persson@chem.umu.se (P. Persson). 1 Present address: Department of Land, Air and Water Resources, University of California, Davis, CA 95616, USA. Colloids and Surfaces A: Physicochem. Eng. Aspects 220 (2003) 91 /104 www.elsevier.com/locate/colsurfa 0927-7757/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0927-7757(03)00063-3