Differential reactivity of Cu(111) and Cu(100) during nitrate reduction in acid electrolyte

The interactions of nitrate with Cu(100) and Cu(111) in acidic solution are studied by cyclic voltammetry (CV) and in situ electrochemical scanning tunneling microscopy (EC-STM). CV results show that reduction of nitrate on Cu(111) commences at 0.0 V vs. Ag/AgCl while the corresponding potential is -0.3 V on Cu(100). EC-STM images show that the terrace of both Cu(111) and Cu(100) are atomically flat at potentials more negative than -0.7 V. The Cu(100) surface exhibits flat terraces throughout the entire cathodic potential range. Close to OCP, step edges start to corrode. In contrast to Cu(100), the first layer of Cu(111) is converted to an atomically rough and defected surface - associated with nascent surface oxidation at potentials positive of -0.7 V. This surface oxidation is correlated with nitrate reduction.