Tuning the Electronic Structure of a Ni-Vacancy-Enriched AuNi Spherical Nanoalloy via Electrochemical Etching for Water Oxidation Studies in Alkaline and Neutral Media

Internal Ni-vacancy-enriched spherical AuNi nanoalloys (AuNi_1-2-T) have been prepared via a noble electrochemical etching method. AuNi_1.5-T showed the highest oxygen evolution reaction (OER) activity compared to bare AuNi_1.5, and it demands only 239 mV overpotential, which was 134 mV lesser than the overpotential required by commercial RuO₂ at 10 mA cm^-2 current density in a 1 M KOH solution (pH = 14). The calculated turnover frequency (TOF) value for AuNi_1.5-T (0.0229 s^-1) was 11.74 times higher than that of AuNi_1.5 (0.00195 s^-1). Also, the electrochemically activated AuNi_1.5-T showed superior neutral water oxidation activity by demanding only 335 mV overpotential with a TOF value of 0.000135 s^-1 in a 1 M Na₂SO₄ solution (pH = 7) at 10 mA cm^-2. The long-term stability studies (over 60 h) reveal the excellent robustness of an electrochemically treated alloy system. Density functional theory based electronic structure calculations showed that in the case of AuNi and AuNi_1.5, Au d, Au s, and Ni d orbitals have significant contributions, whereas in the Ni-vacant systems, the density of states is mainly governed by d orbitals of Au and Ni. Also, the Ni-vacant system possesses a work function value of 4.96 eV, which is lower than that of the pristine system (5.27 eV) and thereby favored OH^- binding with an optimum adsorption energy. This result is in reasonable agreement with the experimental outcome of an accelerated OER in a vacancy-enriched Ni-rich AuNi alloy system. Also, mechanistic analysis reveals that the creation of a Ni vacancy can effectively alter the overall mechanism of the OER and thereby facilitate the same with a lower applied energy.