Doping Induced Enhancement of Activity and Stability for Oxygen Evolution Reaction with Isomaterially Heterostructured MnO2
Authors: Sadiq Mohammad Mazhar , Jha Anurag , Pala Raj 
Published: August 2024

A “Non-Native” phase (NNP) differs from the thermodynamically most stable bulk Native in its discrete translational symmetry. The relative difference in surface and bulk energy with respect to the native phase (NP)determines the stability of NNP. The isomaterial hetero-structured NP-NNP composite provides a pathway to assemble structures that have optimal properties of NNP and NP. The surface and sub-surface energies can also be modulated by doping as the dopants may segregate and stabilize grain boundaries. This study demonstrates that the isomaterial heterostructure of the NP, β-N MnO2, and Ramsdellite, r-NN1 MnO2, known as γ-N-NN1-MnO2 intergrowth, enhances the OER activity and stability.

The hydrothermal route was used to synthesize isomaterial heterostructured γ/N-NN1-MnO2 with varying concentrations of dopants (10%, 15%, and 20% Ni and Co). X-ray diffraction was used to characterize the material, and after Rietveld refinement, phase quantification revealed that as the dopant concentration increased, the amount of the thermodynamically stable β-N MnO2 phase increased. Planes identified in XRD were also confirmed using high-resolution transmission electron microscopy (HRTEM) and the analysis of selective area electron diffraction (SAED) patterns. It appears that doping was successful based on the shifting of peaks in XRD and differences in unit cell volume and crystallite size calculated using the Debye-Scherrer equation before and after doping. With an increase in dopant concentration and thus improved OER activity, the average oxidation state as determined by X-ray photoelectron spectroscopy followed a downward trend, which is known to improve OER activity. The peaks shifted to lower frequency values as seen by Raman spectroscopy, which implies a weakening of Mn—O bond strength, indicating that dopants Ni and Co may have replaced part of the Mn atoms in the MnO2 intergrowth structure. Scanning electron microscopy (SEM) revealed spherical-shaped nanoparticles with spike-like overgrowths, which were further confirmed by HRTEM. The uniform dispersion of dopants was demonstrated by SEM and energy dispersive spectroscopy (EDS). Elemental quantification of the samples was done using EDS and scanning transmission electron microscopy (STEM). Using HRTEM, the presence of grain boundaries was confirmed.

The study of dopants segregating to the grain boundary is conducted through DFT simulations. In many instances, the dopants actively contribute to the OER activity, except for the case of Ni in the NN1 sub-phase of the γ-N-NN1-MnO2 intergrowth, which is apparent by the slightly lower activity of Ni-doped samples compared to Co. This is because Ni remains in the bulk while Co segregates to the surface. A three-electrode setup (Ag/AgCl as the reference electrode, Pt mesh as the counter electrode, and catalyst as the working electrode) was used in 1M KOH to conduct electrochemical experiments. To achieve 10 mA/cm2, the 15% Co-doped electrocatalyst used the least amount of overpotential, 320 mV. According to electrochemical measurements and analysis, the doped samples show low Tafel slope, high specific activity, roughness factor, and charge transfer resistance from electrochemical impedance spectroscopy, all of which suggest improved overall activity for the oxygen evolution process (OER) for the doped over undoped samples. DFT simulations rationalize the enhancement of OER using the Bader charge analysis, the associated Gibbs free energy of the Sabatier principle plotted as the volcano plot.