Interfacial Complexation Explains Anomalous Diffusion in Nanofluids

A recent report describing dramatic anomalous enhancement in mass transport properties of nanofluids (>1000% increase in tracer dye diffusivity) has excited intense interest, but the findings have yet to be conclusively confirmed or explained. Here we investigate these phenomena using a microfluidic approach to directly probe tracer diffusion so that interactions between the suspension's principle components (nanoparticles, surfactant, and dye) can be clearly identified. Under conditions matching previously reported studies, we unexpectedly observe spontaneous formation of highly focused and intensely fluorescent plumes at the interface between fluid streams, suggesting strong complexation interactions between the dye and nanoparticles. These phenomena, driven by competition between the rates at which free tracer molecules are transported into the interfacial zone subsequently consumed by dye-nanoparticle complexation, have likely been incorrectly interpreted as anomalous diffusion enhancement. These interactions are important to consider when devising tracer-based studies of nanoparticle suspensions and may lay a foundation for new adsorption-based analytical methods.