Complementary to this, IR experiments showed new bands in the N-H region in addition to those from *NH2 when both CO2 and NH3 were present, particularly when pulsed potentials were applied (Fig. ). These bands roughly match the N-H vibrations of the C-N products produced and thus are indicative of enhanced C-N bond formation through pulsing. In the absence of CO2, bands relating to NO3 -(1389 cm -1 ) and NO2 -(1232 cm -1 ) are seen, stemming from the oxidation of NH3. Similarly, once CO2 was introduced, pulsed conditions gave rise to new bands at 1051, 1278, 1450 and 1616 cm -1 arising from the possible emergence of C-N products (4f). In particular, the C-N vibrational modes of the C-N reduction products fall near the 1616 cm -1 band observed in our experiment though we cannot yet unambiguously make this assignment as HCO3 - also features a band in this region. Bands below 900 cm -1 may stem from Cu-C/N/O modes and several new bands in this region upon pulsing would be consistent with the existance of partially oxidized surface intermediates in combination with partially reduced CO2R products. In order to (i) determine whether NH2 or NH3 is the key species that reacts with a CO2 reduction reaction intermediate to create the C-N bond, (ii) identify the role of the anodic oxidizing potential which, as seen in experiments above, helped with the overall formation of C-N bond products, and (iii) discover the most favourable coupling step to form a stable C-N intermediate, we have performed density functional theory (DFT) calculations.