Electrocatalytic reduction of nitrate on activated rhodium electrode surfaces

Electrodeposited rhodium films on titanium substrates have been electrochemically activated to produce a high area surface with a specific activity for nitrate electroreduction directly to N-2. The activation process involves oxidation/reduction cycles in an alkaline, KCl electrolyte containing nitrate ions. Surfaces of up to 230 times the geometric area are achieved, together with a surface morphological modi. cation. While the active surface, once formed, is intrinsically unstable during long-term nitrate reduction, its activity can be maintained in situ by an electrochemical cycling procedure. The high area rhodium has the form of a nano-structured 'sponge', with a surface area of ca. 19 m(2) g(-1). The morphological modi. cation is evidenced by a change in the hydrogen UPD structure, changes in the surface redox behaviour associated with OH adsorption, and a reduction in the activation energy for nitrate reduction from ca. 47 to 20 kJ mol(-1). The reduction in activation energy, however, is accompanied by a decrease in the pre-exponential factor, and this apparent compensation effect results in similar rate constants on the activated and unactivated surfaces. The enhancement in the catalyst's activity for nitrate reduction results from an increase in the relative activity of nitrate reduction over water reduction. The activated catalyst sustains steady state nitrate reduction at an increased over-potential before the reaction to N-2 decays, and hydrogen evolution and reduction to ammonia take place. The presence of nitrate ions is essential for the formation of the active surface, and specifically adsorbed nitrate ions and reductive intermediates are present at the surface when it is reformed. A mechanism for the elementary surface reaction steps involved in nitrate reduction, and the apparent 'habit' growth of the active surface phase in the nitrate containing solution is discussed.