Interplay between element-specific distortions and electrocatalytic oxygen evolution for cobalt-iron hydroxides.

A microscopic understanding of how Fe-doping of Co(OH)2 improves electrocatalytic oxygen evolution remains elusive. We study two Co1-x Fe x (OH)2 series that differ in fabrication protocol and find composition alone poorly correlates to catalyst performance. Structural descriptors extracted using X-ray diffraction, X-ray absorption spectroscopy, and Raman spectroscopy reveal element-specific distortions in Co1-x Fe x (OH)2. These structural descriptors are composition-dependent within individual sample series but inconsistent across fabrication protocols, revealing fabrication-dependence in catalyst microstructure. Correlations between structural parameters from different techniques show that Fe-O resists bond length changes, forcing distortion of Co environments. We find the difference in O-M-O bond angles between Co and Fe sites to correlate with electrocatalytic behavior across both sample series, which we attribute to asymmetric distortion of potential energy surfaces for the Co(iii) to Co(iv) oxidation. A Tafel slope consistent with a rate-limiting step without electron transfer emerges as the O-Co-O angle decreases, implying a distortion-induced transition in the rate-limiting step. The fabrication dependence of electronic and bonding structure in the catalysts should be considered in theoretical and high-throughput analyses of electrocatalyst materials.

Tuning the Oxygen Reduction Reactivity of Layered Perovskites Using the Jahn-Teller Effect.

Compositional tuning of layered perovskite oxides provides a means of systematically studying how local distortions affect fundamental aspects of electrochemical reaction pathways. Structural analysis of a family of samples La1.2Sr0.8Ni1-yCoyO4 shows that Ni-rich compositions have an expanded crystalline c axis, which is anisotropically compressed by systematic Co incorporation. Raman spectra reveal the strong growth of a symmetry forbidden mode, which suggests that Co acts through localized distortions. Crystallographic and spectroscopic parameters describing this structural distortion correlate to the measured Tafel slopes for the oxygen reduction reaction for all Ni-containing samples, which is attributed to the distortion of potential energy surfaces by the Jahn-Teller expansion of d7 Ni(III) cations. Incorporation of Co not only minimizes the distortion but alters the apparent selectivity of the oxygen reduction reaction away from H2O2 and toward H2O. Rotating ring-disk electrochemical measurements, however, indicate that the apparent change in selectivity is due to activation of a first-order chemical disproportionation of H2O2 that is activated by Co in the lattice. These outcomes will support efforts to design electrocatalysts and reactors for the electrochemical synthesis of H2O2.