Arsenic species interactions with a porous carbon electrode as determined with an electrochemical quartz crystal...

The interactions of arsenic species with platinum and porous carbon electrodes were investigated with an electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry in alkaline solutions. It is shown that the redox reactions in arsenic-containing solutions, due to arsenic reduction/deposition, oxidation/desorption, and electrocatalyzed oxidation by Pt can be readily distinguished with the EQCM. This approach was used to show that the arsenic redox reactions on the carbon electrode are mechanistically similar to that on the bare Pt electrode. This could not be concluded with just classical cyclic voltammetry alone due to the obfuscation of the faradaic features by the large capacitative effects of the carbon double layer.For the porous carbon electrode, a continual mass loss was always observed during potential cycling, with or without arsenic in the solution. This was attributed to electrogasification of the carbon. The apparent mass loss per cycle was observed to decrease with increasing arsenic concentration due to a net mass increase in adsorbed arsenic per cycle that increased with arsenic concentration, offsetting the carbon mass loss. Additional carbon adsorption sites involved in arsenic species interactions are created during electrogasification, thereby augmenting the net uptake of arsenic per cycle.It is demonstrated that EQCM, and in particular the information given by the behavior of the time derivative of the mass vs. potential, or massogram, is very useful for distinguishing arsenic species interactions with carbon electrodes. It may also prove to be effective for investigating redox/adsorption/desorption behavior of other species in solution with carbon materials as well.