Sustainable Science: Undergraduate Thesis Research on CO2-Reduction Catalysis Published in ACS Journal

Solar reduction of carbon dioxide to regenerate fuels or other useful materials is an area of intense international research toward therhenium-hydride bond goal of sustainability. Photochemical processes based on catalysis by rhenium and other transition metals are well developed, but mechanistic details of some catalytic cycles have remained poorly understood. Professor Gonghu Li and his UNH collaborators, undergraduate Jay Agarwal and Professor Richard Johnson, have provided a key to this puzzle through the recent publication of a research article in the Journal of Physical Chemistry A. The UNH team utilized density functional theory and many hundreds of hours of supercomputer time to model a catalytic cycle for formate production via CO2 reduction mediated by a rhenium(I) tricarbonyl complex. Based on prior studies in the literature, the researchers examined the role of triethylamine as both the hydrogen atom and electron donor for reducing CO2 into formate.  Structures of key intermediate stages were identified, including the transition state for CO2 insertion into a rhenium-hydride bond (shown above).  These findings provide a molecular-level understanding of catalytic formate production via CO2 reduction by description of a complete catalytic cycle.  The article is accessible through the following website. 

http://pubs.acs.org/doi/abs/10.1021/jp111342r                                                            

This research formed the basis for Jay Agarwal’s Senior Thesis in the Chemistry Department. After graduating from UNH in May 2010, Jay continues his scientific adventures in Professor Henry Schaefer’s group in the Chemistry Department at the University of Georgia.