The Effect of Electrolyte on the Electrochemical Reduction of CO2 to CO
While a lot of research in the past few decades has focused on the development of new catalysts, support materials, and electrolytes for electrochemical reduction of CO2 to CO, desired performance levels for a viable process i.e., partial current densities for CO (jCO) > 250 mA cm-2 at energetic efficiencies (EE) > 60% are yet to be achieved . Recently, Rosen et al.  demonstrated electrocatalytic conversion of CO2 to CO using ionic liquid EMIM-BF4 as the electrolyte at extremely low cell overpotential of 0.17 V. However, jCO for the reaction was typically of the order of 1-5 mA cm-2. In other work, we showed that using IrO2 as the anode instead of Pt in combination with KOH as the electrolyte lowered the cell overpotential to 0.22 V. Much higher jCO ≈ 250 mA cm-2 was obtained at a cell potential of -3.00 V .
In this work we report the effect of different electrolytes on the electrocatalytic conversion of CO2 to CO using Ag as the cathode and IrO2 as the anode. All experiments were done in an electrochemical flow cell  at ambient conditions. Several electrolytes (KOH, KCl, KHCO3, EMIM-Cl, Choline-Cl, and their combinations) were studied (Figure 1). The concentration of the electrolyte was found to play a major role in the process with jCO increasing almost several folds upon going from 0.5 M to 3.0 M independent of the nature of the anion. jCO as high as 440 mA cm-2 at an EE of ≈ 42% and 230 mA cm-2 at an EE ≈ 54% was observed when using 3.0 M KOH electrolyte. To the best of our knowledge, these are some of the highest jCO levels reported to date in combination with energetic efficiencies exceeding 40%.
The effect of anions on electroreduction of CO2 was also investigated. The onset cathode potential was found to shift in the order OH- < HCO3- < Cl- with the values being -0.13 V, -0.46 V, and -0.60 V vs. RHE, respectively. The Faradaic efficiency for CO (FECO) and jCO was found to change in the reverse order. Furthermore, we also studied whether adding small amounts of EMIM-Cl or Choline-Cl to a KCl electrolyte had any effect on jCO and FECO.
The experimental trends observed in this work can be explained by the interplay of a combination of factors, including pH, effect of conductivity and more importantly greater stabilization or destabilization of rate limiting CO2.- by anions and cations in the double layer. Electrochemical impedance spectroscopy was used to further support these arguments. Such an understanding can be crucial for designing more efficient electrocatalytic systems and can also open up avenues for utilizing low cost catalysts that have traditionally been not very active for CO2 reduction.
We gratefully acknowledge financial support from AF STTR Phase II grant to Dioxide Materials, WPI-I2CNER and a 3M graduate fellowship to SV.
 D. H. Levinson, J. H. Lawrimore, Bull. Am. Met. Soc. 2008, 89.7, S1-S179.
 S. Pacala, R. Socolow, Science 2004, 305, 968-972.
 H. R. M. Jhong, S. Ma, P. J. A. Kenis, Curr. Op. Chem. Eng. 2013, 2.2, 191-199.
 B. A. Rosen, A. Salehi-Khojin, M. R. Thorson, W. Zhu, D. T. Whipple, P. J. A. Kenis, R. I. Masel, Science 2011, 334.6056, 643-644.
 S. Ma, R. Luo, S. Moniri, Y. Lan, P. J. A. Kenis, J. Electrochem. Soc. 2014, 161.10, F1124-F1131.
 D. T. Whipple, E. C. Finke, P. J. A. Kenis, Electrochem. Solid-State Lett. 2010, 13, B109-B111.