Design and Synthesis of Ir/Ru Pyrochlore Catalysts for the Oxygen Evolution Reaction Based on Their Bulk Thermodynamic Properties

Density functional theory (DFT) has proven to be an invaluable and effective tool for identifying highly active electrocatalysts for the oxygen evolution reaction (OER). Herein, we take a computational approach to first identify a series of rare-earth pyrochlore oxides based on Ir and Ru as potential OER catalysts. The DFT-based phase diagrams, Pourbaix diagrams (E vs pH), projected density of states, and band energy diagrams were used to identify prospective OER catalysts based on rare-earth Ir and Ru pyrochlores. The predicted materials were synthesized using the spray-freeze freeze-drying approach to afford nanoparticulate oxides conforming to the pyrochlore structural type A 2 B 2 O 7 where A = Nd, Gd, or Yb and B = Ir or Ru. In agreement with the computed Pourbaix diagrams, the materials were found to be moderately stable under OER conditions. All prepared materials show higher stability as compared to the benchmark IrO 2 catalyst, and the OER mass activity of Yb 2 Ir 2 O 7 and the ruthenate pyrochlores (Nd 2 Ru 2 O 7, Gd 2 Ru 2 O 7, and Yb 2 Ru 2 O 7 ) were also found to exceed those of the benchmark IrO 2 catalyst. We find that the OER activity of each pyrochlore series (i.e., iridate or ruthenate) generally improves as the size of the A-site cation decreases, indicating that maintaining control over the structure can be used to influence the electrocatalytic properties.