Regulating Surface Charge by Embedding Ru Nanoparticles over 2D Hydroxides toward Water Oxidation

Exploring highly active and earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is considered one of the prime prerequisites for generating green hydrogen. Herein, a competent microwave-assisted decoration of Ru nanoparticles (NPs) over the bimetallic layered double hydroxide (LDH) material is proposed. The same has been used as an OER catalyst in a 1 M KOH solution. The catalyst shows an interesting Ru NP loading dependency toward the OER, and a concentration-dependent volcanic relationship between electronic charge and thermoneutral current densities has been observed. This volcanic relation shows that with an optimum concentration of Ru NPs, the catalyst could effectively catalyze the OER by obeying the Sabatier principle of ion adsorption. The optimized Ru@CoFe-LDH(3%) demands an overpotential value of only 249 mV to drive a current density value of 10 mA/cm² with the highest TOF value of 14.4 s^-1 as compared to similar CoFe-LDH-based materials. In situ impedance experiments and DFT studies demonstrated that incorporating the Ru NPs boosts the intrinsic OER activity of the CoFe-LDH on account of sufficient activated redox reactivities for both Co and lattice oxygen of the CoFe-LDH. As a result, compared with the pristine CoFe-LDH, the current density of Ru@CoFe-LDH(3%) at 1.55 V vs RHE normalized by ECSA increased by 86.58%. First-principles DFT analysis shows that the optimized Ru@CoFe-LDH(3%) possesses a lower d-band center that indicates weaker and more optimal binding characteristics for OER intermediates, improving the overall OER performance. Overall, this report displays an excellent correlation between the decorated concentration of NPs over the LDH surface which can tune the OER activity as verified by both experimental and theoretical calculations.