Deciphering the Role of Second Metal in M-Ni (M = Fe, Ni, and Mn) Heterobimetallic Electrocatalysts in Controlling the HAT versus Hydride Transfer Mechanism for the Dehydrogenation of Alcohols

The second 3d-transition metal incorporation in Ni-(oxy)hydroxide has a drastic effect on alkaline OER and alcohol dehydrogenation reactivity. While Mn incorporation suppresses the alkaline OER, it greatly improves the alcohol dehydrogenation reactivity. A complete reversal of reactivity is obtained when Fe is incorporated, which shows better performance for alkaline OER with poor alcohol dehydrogenation reactivity. The role of the second 3d-metal is elusive due to the lack of systematic mechanistic studies. In this report, we thoroughly analyzed a series of M─Ni (M = Fe, Ni, Mn) (oxy)hydroxides derived from electrochemical activation of M-MOF grown on nickel foam for its electrochemical activity in alkaline OER and aliphatic, benzyl alcohol dehydrogenation. With the help of pH-dependence and kinetic isotope effect studies, the potential-determining step (PDS) and the rate-determining step (RDS) have been elucidated. The Hammett analysis revealed critical information about the transition state and offered insight into the hydrogen atom transfer (HAT) versus hydride transfer (HT) for alcohol dehydrogenation operative in various heterobimetallic electrocatalysts. Further, the superior alcohol dehydrogenation reactivity of NiMn catalyst for PET hydrolysate electro-oxidation is extended to afford valuable chemicals with concomitant production of hydrogen.