Electrocatalytic Activity of Delafossite CuCoO₂ for Alkaline Oxygen Evolution Reaction and Acidic Hydrogen Evolution...

Electrochemical water splitting requires electrocatalysts that operate efficiently and durably under disparate electrolyte environments. Herein, pristine CuCoO₂ particles were synthesized via a hydrothermal route as a single-phase rhombohedral (3R) delafossite structure composed of hexagonal, single-crystalline particles (~2.6 μm) with a uniform elemental distribution. The prepared CuCoO₂ was then evaluated as a bifunctional electrocatalyst for the alkaline oxygen evolution reaction (OER) and the acidic hydrogen evolution reaction (HER), with a deliberate separation of electrode-level performance and intrinsic per-site activity. X-ray photoelectron spectroscopy revealed mixed Cu⁺/Cu²⁺ and Co²⁺/Co³⁺ states, together with signatures of copper and oxygen vacancies, indicating a defect-rich surface chemistry. In 1 M KOH, the CuCoO₂ loaded on carbon fiber paper (CFP) delivered an OER overpotential of 404.38 mV at 10 mA/cm² in 1 M KOH (Tafel slope = 102.39 mV/dec; charge-transfer resistance (R_ct) decreased from 19.32 to 5.78 Ω with increasing potential) and an HER overpotential of 246.46 mV at -10 mA/cm² in 0.5 M H₂SO₄, with sluggish kinetics (Tafel slope = 429.17 mV/dec; high R_ct = ~1.0-1.1 kΩ). Despite this, CuCoO₂ exhibited markedly higher intrinsic activity in acidic HER (ECSA = 82.97 cm²; TOF = 0.1432 s^-1 at -0.2 V vs. RHE) than in alkaline OER (ECSA = 9.56 cm²; TOF = 0.079 s^-1 at 1.5 V vs. RHE), indicating that acidic HER performance is primarily limited by electrode-level microstructural factors. This work provides, to the best of our knowledge, the first evaluation of acidic HER activity of delafossite CuCoO₂ and underscores electrode-level microstructural engineering as a key route to better harness its intrinsic activity for practical water electrolysis.