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 [Rh^III(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.

与基于均质类似物的均相类似物相比，基于异相金属的分子电催化剂通常具有吸引人的特征，包括可回收性和耐用性。因此，有必要评估感兴趣的杂化分子催化剂的电催化行为，以期获得有关此类行为可保留性的见解，同时受益于杂化。在这项工作中，我们在计算上检查了基于纳米石墨烯的铑杂化分子配合物的电化学性能。我们还评估了异质化分子催化剂对析氢反应（HER）的电催化性能。检查了两个电化学途径，即一电子和二电子电化学还原途径。有趣的是，通过计算证明了[Rh^III（Cp *）（phen）Cl] ⁺ -Gr对HER表现出氧化还原和电催化性能，可通过双电子还原途径与其同质类似物相媲美。另一方面，发现单电子还原途径在动力学和热力学上不太有利。此外，利用分子轨道分析和机理方面，提供了关于HER的分子见解。重要的是，我们的发现可能会为设计更有效的基于石墨烯的分子异质电催化剂以提供更有效的能量产生提供见解。