Surface Charged Zirconia Nanoparticles prepared by Organophosphorus Surface-Functionalization with Ammonium- or Sulfonate Groups.

Organophosphorus coupling agents bearing permanently charged functional groups (either cationic quaternary ammonium or anionic sulfonates) were synthesized and used for the modification of zirconia nanoparticles with a diameter <10 nm. Surface functionalization was confirmed by FTIR and solid-state NMR spectroscopy. Surface coverages up to 2.3-2.4 molecules/nm(2) were achieved for modification with these charged coupling agents. The pH-dependent charge measurements of homogeneously modified particles showed stable surface charges over a wide range of pH for both ammonium- and sulfonate-functionalized particles. Surface charge measurements of particles co-functionalized with charged coupling molecules and uncharged methyl phosphonic acid revealed a decreasing charge density with increasing amount of uncharged coupling agent. Thus, an adjustment of charges by co-functionalization was obtained on the particle surface. The thus-formed surface-charged colloids were used in a second step for electrostatic-driven aggregation phenomena necessary for layer-by-layer processes. Sulfonate-modified negatively charged SiO2 submicrometer particles of 506 nm in diameter were decorated with ammonium-modified ZrO2 nanoparticles. In addition, a layer-by-layer deposition of alternating charge-modified TiO2 nanoparticles was proven by optical spectroscopy. Due to the broad applicability of organophosphorus coupling agents for surface modification, particularly for transition-metal oxides, the shown route represents a general method for the creation of almost pH-independent charges on the surface of nanoparticles.