59th Annual Report on Research 2014

The grant was awarded to the University of Washington for Professor James Mayer.

Current address and contact information:

Professor James Mayer, Department of Chemistry, Yale University

225 Prospect St., PO Box 208107, New Haven CT 06520-8107

203-436-9456; james.mayer@yale.edu

Our ACS-PRF New Direction grant has enabled us to start and pursue a number of projects exploring how protons modulate the interfacial reaction chemistry of metal oxide nanoparticles (NPs) and related materials. This award was our first outside funding for this direction, and the work supported by ACS-PRF has been the basis for subsequently funded proposals from NSF and DARPA, and an internal proposal within the Center for Enabling New Technologies Through Catalysis (CENTC), an NSF Phase II Center for Chemical Innovation.

A no-cost extension was granted in September 2013 and the residual funds were used to provide partial support for four graduate students: Miles Braten, Jennifer Peper, Tom Porter, and Carolyn Valdez. In addition, Hayli Larson did undergraduate research with Carolyn for the first half of 2014 and was supported (on another award) during a portion of summer 2014.

Miles Braten has developed techniques to measure the kinetics of proton-coupled electron transfer from reduced ZnO nanocrystals to TEMPO, and the results are proving to be very interesting. He and I both presented his work in talks at the ACS National Meeting this past August (2014) in San Francisco. Jennifer Peper and Tom Porter have been working on the chemistry of reduced aqueous TiO₂ nanoparticles. Tom discovered some new reactions of these interesting reagents, and reported that work in a chapter of his PhD thesis. Jennifer has discovered a range of interesting properties of these materials, including their changes in absorbance and reactivity with pH; a couple of publications are in the planning stages. Carolyn Valdez has published two papers in 2013 and 2014, one in J. Am. Chem. Soc. on the chemical charging of ZnO nanocrystals and the effects of protons, the other in ACS Nanoon the surface coverage by dodecylamine ligands on these nanoparticles. One other paper is in preparation.

All of these experiments are building toward an understanding of how protons and electrons modulate and participate in the reactivity of the metal-oxide surface. This fundamental understanding will be valuable in a number of areas of science and technology. We are excited that our new approach is providing interesting and valuable new insights.