A General Procedure to Functionalize Agglomerating Nanoparticles Demonstrated on Nanodiamond

Upon reduction of particle size to the nanometer range, one has to deal with the general issue of spontaneous agglomeration, which often obstructs postsynthesis modification of nanoparticle surfaces. A technique to cope with this phenomenon is required to realize a wide variety of applications using nanoparticles in solvents or as refined assemblies. In this article, we report on a new technique to facilitate surface chemistry of nanoparticles in a conventional glassware system. A beads-assisted sonication (BASD) process was examined to break up persistent agglomerates of nanodiamonds in two different reactions for simultaneous surface functionalization. The chosen reactions are the silanization with an acrylate-modified silane and the arylation using diazonium salts. The BASD process can be successfully applied even where the original material is not dispersible in the reaction solvent at all, as the formation of ever smaller, increasingly functionalized agglomerates is improving their solubility. We have confirmed that the presence of ceramic beads enables functionalization of each primary particle, while conventional magnetic stirring or beadless sonication can reach primary particles only when agglomeration is loose, Additionally, mechanical surface modification of nanodiamond was found to take place by BASD with high energy density, leading to sp(2)-hybridized surface patches on nanodiamond. This allowed for the efficient grafting of aryl groups to the surface of primary diamond nanoparticles. Stable, homogeneously functionalized nanodiamond particles in colloidal solution can be obtained by this method.