Abstract
The heterogeneous metal-based molecular electrocatalyst can typically exhibit attractive features compared to its homogeneous analogue including recoverability and durability. As such, it is necessary to evaluate the electrocatalytic behavior of heterogenized molecular catalysts of interest toward gaining insights concerning the retainability of such behaviors while benefiting from heterogenization. In this work, we examined computationally the electrochemical properties of nanographene-based heterogenized molecular complexes of Rhodium. We assessed, as well, the electrocatalytic behavior of the heterogenized molecular catalyst for hydrogen evolution reaction (HER). Two electrochemical pathways were examined, namely one- and two-electron electrochemical reduction pathways. Interestingly, it is computationally demonstrated that [RhIII(Cp*)(phen)Cl]+-Gr can exhibit redox and electrocatalytic properties for HER that are comparable to its homogeneous analogue via a two-electron reduction pathway. On the other hand, the one-electron reduction pathway is notably found to be less favorable kinetically and thermodynamically. Furthermore, molecular insights are provided with respect to the HER employing molecular orbitals analyses and mechanistic aspects. Importantly, our findings may provide insights toward designing more efficient graphene-based molecular heterogeneous electrocatalysts for more efficient energy production.
Highlights
Covalent attachment of the molecular homogeneous catalysts to the surface of electrochemically active carbon materials
The analyses of interest here are focused on insighting the redox and the corresponding electrocatalytic behaviors of the metal-based heterogenized molecular catalysts of selected Rhodium complexes compared to the homogenous analogue in terms of structural properties, mechanistic aspects, and molecular orbitals
It must be mentioned that performing such evaluating protocols requires initially performing accurate Density Functional Theory (DFT)-based geometry optimizations for all species that are involved in the electrochemical reduction and catalytic cycle of interest
Summary
Covalent attachment of the molecular homogeneous catalysts to the surface of electrochemically active carbon materials. In the light of the importance of heterogenization of transition metal-based molecular electrocatalysts and inspired by the recent work of Surendranath et al, we aimed in this work using Density Functional Theory (DFT) to computationally evaluate the redox behavior of selected graphene-based heterogenized molecular Rh complexes ([RhIII(Cp*)(L)Cl]1+) and the corresponding electrocatalytic activity for the HER. Both behaviors of interest, namely redox and electrocatalysis of the HER, are comparatively evaluated for both phases at the molecular levels. The findings of this study may help in developing new heterogenized molecular catalysts or enhancing the electrocatalytic performance of existing ones
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