Rational design to increase the activity of the Bocarsly catalyst for reduction of carbon dioxide to reduced forms of carbon

In 1994 and again in 2008 Bocarsly announced the discovery of a new stunningly efficient catalyst for the electrochemical reduction of carbon dioxide to formic acid, formaldehyde, and ultimately methanol. In 2010 Bocarsly presented experimental and theoretical mechanistic studies identifying the rate-limiting step as formation of a pyridyl N-C bond bond with CO₂ to give a carbamic acid intermediate. We will discuss a general strategy for improving the activity of the catalyst system by rational design of a catalyst for which the activation barrier of this step should be reduced. The synthesis of a series of catalysts, which should have a systematic variation of catalytic activity, will be presented along with preliminary results for assessment of their activity relative to Bocarsly 's original catalyst.