Nonaqueous synthesis of metal oxide nanoparticles: Review and indium oxide as case study for the dependence of particle morphology on precursors and solvents

Nonaqueous solution routes to metal oxide nanoparticles are a valuable alternative to the well-known aqueous sol-gel processes, offering advantages such as high crystallinity at low temperatures, robust synthesis parameters and ability to control the crystal growth without the use of surfactants. In the first part of the review, we give an overview of the various nonaqueous routes to metal oxides, their surface functionalization and their assembly into well-defined nanostructures. However, we will strongly focus on surfactant-free processes developed in our group. Within the various reaction systems such as metal halides-benzyl alcohol, metal alkoxides-benzyl alcohol, metal alkoxides-ketones, metal acetylacetonates-benzyl alcohol and metal acetylacetonates-benzylamine we will discuss representative examples in order to show the versatility of this approach. The careful characterization of the organic species in the final reaction mixtures provides information about possible condensation mechanisms. Depending on the system several reaction pathways have been postulated: (i) elimination of organic ethers as result of condensation between two metal alkoxide precursors; (ii) C-C bond formation between the alkoxy ligand of the metal alkoxide precursor and the solvent benzyl alcohol under formation of a metal hydroxyl species, which can undergo further condensation; (iii) ketimine and aldol-like condensation steps, which in the metal acetylacetonate systems are preceded by a solvolysis of the precursor, involving C-C bond cleavage. In the second part of the paper we will focus on the synthesis of indium oxide nanoparticles using different precursors and solvents. Indium oxide represents an instructive example how the oxide precursors and the solvents influence the particle morphology. These findings make it possible to tailor particle size and shape of a particular metal oxide by the appropriate choice of the reaction system.