Electrochemical properties and relaxation times of the hematite/water interface.

Abstract

Electric double layer properties and protonation rates at the surface of a mechanically and chemically polished (001) surface of hematite (α-Fe2O3) contacted with aqueous solutions of NaCl were extracted by electrochemical impedance spectroscopy (EIS). Effects of pH (4-12) and ionic strength (10-1000 mM) on the EIS response of the electrode were predicted using an electrical equivalent circuit model accounting for hematite bulk and interfacial processes. These efforts generated diffuse layer as well as compact layer capacitances and resistance values pertaining to interfacial processes. Diffuse layer capacitance values lie in the 0.5-0.6 μF cm(-2) region and are about 1.5 times smaller than those obtained on a roughened hematite surface. Compact layer capacitances are strongly pH dependent as they pertain to the transfer of ions (charge carriers) from the diffuse layer onto surface (hydr)oxo groups. These values, alongside those of resistance adsorption, pointed a 50% decrease in proton adsorption/desorption resistance under acidic and alkaline conditions relative to that of the point of zero charge (pH 8-9). Increasing ionic strength generally induces larger diffuse layer capacitances, larger adsorption capacitances, and lower resistance values. Such a response is in line with the concept for thinner electric double layers and facilitated proton adsorption reactions by solutions of high ionic strengths. Relaxation times pertaining to the transfer of charge carriers across the compact plane induced by the EIS experiments lie in the 0.7-4.2 s range and become larger under acidic conditions. Decreases in site availability and increases in electrostatic repulsion are two possible contributing factors impeding reaction rates below the point of zero charge. Collectively, these finding are underpinning important relationships between classical views on mineral surface complexation reactions and electrochemical views of semiconductor/water interfaces.