Metz, K. M., Sanders, S. E., Pender, J. P., Dix, M. R., Hinds, D. T., Quinn, S. J., et al. (2015). Green Synthesis of Metal Nanoparticles via Natural Extracts: The Biogenic Nanoparticle Corona and Its Effects on Reactivity. ACS Sustainable Chemistry & Engineering.
Abstract: The optical and catalytic properties of metal nanoparticles have attracted significant attention for applications in a wide variety of fields, thus prompting interest in developing sustainable synthetic strategies that leverage the redox properties of natural compounds or extracts. Here, we investigate the surface chemistry of nanoparticles synthesized using coffee as a biogenic reductant. Building on our previously developed synthetic protocols for the preparation of silver and palladium nanoparticle/carbon composite microspheres, a combination of thermogravimetric and spectroscopic methods was used to characterize the carbon microsphere and nanoparticle surfaces. Infrared reflectance spectroscopy and single particle surface enhanced Raman spectroscopy were used to characterize Pd and Ag metal surfaces, respectively, following synthesis. Strongly adsorbed organic layers were found to be present at metal nanoparticle surfaces after synthesis. The catalytic activity of Pd nanoparticles in hydrogenation reactions was leveraged to study the availability of surface sites, and coffee-synthesized nanomaterials were compared to commercial Pd-based hydrogenation catalysts. Our results demonstrate that biogenic adsorbates block catalytic surface sites and affect nanoparticle functionality. These findings highlight the need for careful analysis of surface chemistry as it relates to the specific applications of nanomaterials produced using greener or more sustainable methods.
Metz, K. M., Sanders, S. E., Miller, A. K., & French, K. R. (2014). Uptake and Impact of Silver Nanoparticles on Brassica rapa: An Environmental Nanoscience Laboratory Sequence for a Nonmajors Course. Journal of Chemical Education, 91(2), 264-268.
Abstract: Nanoscience is one of the fast growing fields in science and engineering. Curricular materials ranging from laboratory experiments to entire courses have been developed for undergraduate science majors. However, little material has been developed for the nonmajor students. Here we present a semester-long laboratory sequence developed for a nonmajors course, where students investigate the potential environmental impacts of nanoscience. Students synthesize and characterize silver nanoparticles using green synthetic methods. They then use the suspension of silver nanoparticles to “water” Wisconsin Fast Plants, Brassica rapa, over a three to four week period to simulate environmental exposure. Possible impacts are examined throughout the growth period, and silver uptake by the plants is quantified at the end of the growth period. This lab requires design input from the student, making it an open-ended experiment. Although designed for nonmajors, this lab could easily be adapted for an environmental chemistry or chemical nanoscience course.
Duffy, P., Reynolds, L. A., Sanders, S. E., Metz, K. M., & Colavita, P. E. (2013). Natural reducing agents for electroless nanoparticle deposition: Mild synthesis of metal/carbon nanostructured microspheres. Materials Chemistry and Physics, 140(1), 343-349.
Abstract: Composite materials are of interest because they can potentially combine the properties of their respective components in a manner that is useful for specific applications. Here, we report on the use of coffee as a low-cost, green reductant for the room temperature formation of catalytically active, supported metal nanoparticles. Specifically, we have leveraged the reduction potential of coffee in order to grow Pd and Ag nanoparticles at the surface of porous carbon microspheres synthesized via ultraspray pyrolysis. The metal nanoparticle-on-carbon microsphere composites were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and thermal gravimetric analysis (TGA). To demonstrate the catalytic activity of Pd/C and Ag/C materials, Suzuki coupling reactions and nitroaromatic reduction reactions were employed, respectively.