Faradaic efficiency MeOH/ %

Photoelectrochemical and Electrochemical Conversion of Carbon Dioxide to Methanol and Higher Order Products Mediated by Pyridinium Based Electrocatalysts Emily E. Barton and Andrew B. Bocarsly* Princeton University, Department of Chemistry Frick Laboratory, Washington Road, Princeton, NJ 08544 *corresponding author email: bocarsly@princeton.edu With rising CO2 emissions there has been increasing interest in possible artificial schemes for converting the green-house gas into valuable fuels and small organics which are currently derived from oil and natural gas. The chemical sequestration of CO2 by synthesis of simple alcohols is an extremely advantageous design as it would lead to the production of commodities both useful as chemical materials precursors as well as valuable fuels. We have previously reported on a stable system containing a soluble pyridinium component at hydrogenated Pd and Pt metal electrodes for the reduction of CO2 to methanol.1 Metal electrodes are notoriously inefficient for CO2 reduction because of the extremely high overpotentials needed to drive the reaction, coupled with the competition of H2 evolution when aqueous electrolyte is employed. Our system operated, however, very close to the thermodynamically reversible potential (~100-200 mV overpotential) and lead to faradaic efficiencies for methanol production near 30%. We have also found that we can export this chemistry to a p-GaP semiconductor to reduce CO2 to methanol with near 100% faradaic efficiency at underpotentials greater than 300 mV below the thermodynamic potential of -0.52V vs SCE at our system pH.2 Thus, our process offers the prospect of a pure solar energy conversion system requiring no input of electrical power. Recent studies have now been focused on elucidating the complex mechanism of CO2 reduction by pyridinium. Through such studies, we have found that by simply changing certain substituent groups on the pyridine ring we can drastically change the electrochemistry of our system to produce higher order products such as ethanol, isopropanol, and acetone as well as increased methanol yields. In this paper we will discuss our recent results on increased methanol yield and higher order products from the electroreduction of CO2 as well as the elucidation of possible electroactive carbamate intermediates that play a key role in product formation. In addition we will discuss our current work on systems for reducing carbon dioxide to value added products using light energy at semiconductor electrodes.

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3.3

Increasing pKa
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9.7

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Concentration protonated/ mM
Figure 1. Dependence of methanol production at hydrogenated Pd electrodes on the concentration of pyridinium. The pH of the solutions stayed constant between 5.2 5.6. At pH below 5, hydrogen evolution greatly competes with carbon dioxide reduction thus various substituted pyridines with different pKas were employed to change the concentration of pyridinium ion, which is the active catalyst. A linear correlation between pyridinium concentration and methanol formation was observed. Interestingly two outliers were seen, with 4dimethylaminopyridine showing 30% faradaic efficiency for formaldehyde. References 1. G. Seshadri, C. Lin, A. B. Bocarsly, J. Electroanal. Chem. 372, 145 (1994). 2. E. E. Barton, D. M. Rampulla, A. B Bocarsly, J. Am. Chem. Soc. 130, 6342 (2008).