Electrochemical Synthesis of Urea from Carbon Dioxide and Nitrite at Cobalt Phthalocyanine-Ion Liquid Electrodes

Abstract

Electrochemical coreduction of carbon dioxide and nitrogen oxyanion/oxide pollutants are attractive processes for simultaneous environmental remediation and sustainable production of urea. The development of suitable technology requires catalysts and electrodes that provide higher efficiencies by decreasing the overpotential required and increasing the faradaic efficiency. Electrode design is a key element in this process through which the environment of the catalyst can be manipulated to optimize activity and selectivity. Here, ionic liquids have been used to control the coreduction of carbon dioxide and nitrite at a cobalt phthalocyanine catalyst. Increasing the hydrophobicity of the catalyst layer with a mixture of 1-butylpyridinium hexafluorophosphate and trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide was found to increase the faradaic efficiency for urea formation to 27% at the lowest overpotential (−0.064 V vs RHE), from 3% for a Nafion binder. Modulation of the electronic structure, arrangement (aggregation vs adsorption on the carbon support) and/or mobility (via solubilization) of the CoPc catalyst appear to play a role in determining the rate and faradaic efficiency of urea production. Combining the CoPc catalyst with a carbon supported Cu cocatalyst increased the rate of urea production by 195% at –0.064 V.