title: Ligand functionality as a versatile tool to control the assembly behavior of preformed titania nanocrystals.
abstract: Nanoparticle powders composed of surface-functionalized anatase crystals with diameters of about 3 nm self-organize into different structures upon redispersion in water. The assembly is directed by a small amount of a low-molecular-weight functional ligand (the "assembler") adsorbed on the surface of the nanoparticles. The ligand functionality determines the anisotropy of the resulting structures. Multidentate ligands, such as trizma ((HOCH(2))(3)CNH(2)) and serinol ((HOCH(2))(2)CNH(2)), with a chargeable terminal group preferentially induce the formation of anisotropic nanostructures several hundreds of nanometers in total length, whereas all the other investigated ligands (ethanolamine H(2)N(CH(2))(2)OH, glycine hydroxamate H(2)NCH(2)CONHOH, dopamine (OH)(2)C(6)H(3)(CH(2))(2)NH(3)Cl, tris (HOCH(2))(3)CCH(3)) mainly lead to uncontrolled agglomeration. Experimental data suggests that the anisotropic assembly is a consequence of the water-promoted desorption of the organic ligands from the {001} faces of the crystalline building blocks together with the dissociative adsorption of water on these crystal faces. Both processes induce the preferred attachment of the titania nanoparticles along the [001] direction. The use of polydentate and charged ligands to functionalize the surface of nanoparticles thus provides a versatile tool to control their arrangement on the nanoscale.
authors.affiliation: Max-Planck-Institute of Colloids and Interfaces, Colloid Chemistry, Research Campus Golm, Germany.
authors.forename: Julien
authors.initials: J
authors.lastname: Polleux
authors.forename: Nicola
authors.initials: N
authors.lastname: Pinna
authors.forename: Markus
authors.initials: M
authors.lastname: Antonietti
authors.forename: Christian
authors.initials: C
authors.lastname: Hess
authors.forename: Ute
authors.initials: U
authors.lastname: Wild
authors.forename: Robert
authors.initials: R
authors.lastname: Schlögl
authors.forename: Markus
authors.initials: M
authors.lastname: Niederberger
mesh_terms: D000327:Adsorption; D003460:Crystallization; D008024:Ligands; D008970:Molecular Weight; D049329:Nanostructures / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010316:Particle Size; D014025:Titanium / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; C009495:titanium dioxide; D014025:Titanium