Multi-Element Containing Precious Group Metal-Free Electrocatalysts for Efficient Hydrogen Evolution Reaction in PEM Water Electrolysis (2020)

Electricity driven proton exchange membrane-based water electrolysis (PEMWE) has demonstrated considerable credibility in recent years, establishing high competency enabling PEMWE technology for rapid generation of clean hydrogen fuel 1-7 . In order to attain the high efficiency needed and successful commercialization of PEMWE, there is a critical need to identify highly active, robust, and earth-abundant electrocatalysts for accelerating the hydrogen evolution reaction (HER) with minimum energy input 8 . In the pursuit of achieving this goal, in the present work, employing the density functional theory (DFT) based calculations for rationalizing the thermodynamics and reaction kinetics of HER, we have investigated the platinum group metal (PGM)-free, earth-abundant, transition metal non-oxide (TMN) based electrocatalysts for acid mediated HER in PEMWE. Based on the theoretical calculations, the as-synthesized TMN electrocatalyst compositions reveal optimized hydrogen adsorption free energies (ΔG H * ) and beneficial electronic structures modification, offering superior charge transfer kinetics, lower reaction barrier, low water contact angle (7 o ) suggesting high wettability ( Fig. 1 ), and high electrocatalytic activity for HER. Furthermore, the highly active electrocatalyst compositions display excellent long term electrochemical HER stability in acidic media, with no significant obvious degradation in current density. The as-synthesized electrocatalysts thus, has propensity for exhibiting robust HER performance with excellent structural and mechanical integrity. The experimental results are in excellent agreement with the DFT calculations which further accentuate the incorporation of suitable PGM-free dopants into the TMN compositions resulting in optimized electronic structures lowering the HER reaction barriers. The system therefore offers improved electrocatalytic performance for HER which is comparable to state-of-the-art Pt/C electrocatalysts. Accordingly, the as-synthesized PGM-free electrocatalysts can be considered as reliable HER candidates, vital for the development of acid mediated PEM based water splitting employing PGM-free electrocatalysts. Results of this study will be presented and discussed. Acknowledgements: Financial support of NSF-CBET grant# 1511390, Edward R. Weidlein Chair Professorship funds and the Center for Complex Engineered Multifunctional Materials (CCEMM) is acknowledged. References: Ghadge, S. D.; Velikokhatnyi, O. I.; Datta, M. K.; Shanthi, P. M.; Tan, S.; Damodaran, K.; Kumta, P. N., Experimental and Theoretical Validation of High Efficiency and Robust Electrocatalytic Response of One-Dimensional (1d) (Mn,Ir)O2:10f Nanorods for the Oxygen Evolution Reaction in Pem-Based Water Electrolysis. ACS Catal. 2019 , 2134-2157. Patel, P. P.; Velikokhatnyi, O. 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N., Computational and Experimental Study of Fluorine Doped (Mn1–Xnbx)O2 Nanorod Electrocatalysts for Acid-Mediated Oxygen Evolution Reaction. ACS Applied Energy Materials 2020, 3 , 541-557. Figure 1