Immobilizing molecular catalysts on electrodes is vital for electrochemical applications. However, creating robust electrode-catalyst interactions while maintaining good catalytic performance and rapid electron transfer is challenging. Here, without introducing any foreign elements, we show a bottom-up synthetic approach of constructing the conjugated C−C bond between the commercial Vulcan carbon electrode and an organometallic catalyst. Characterization results from FTIR, XPS, aberration-corrected TEM and EPR confirmed the successful and uniform heterogenization of the complex. The synthesized Vulcan-LN₄−Co catalyst is highly active and selective in the oxygen reduction reaction in neutral media, showing an 80 % hydrogen peroxide selectivity and a 0.72 V (vs. RHE) onset potential which significantly outperformed the homogenous counterpart. Based on single-crystal XRD and NMR data, we built a model for density functional theory calculations which showed a nearly optimal binding energy for the *OOH intermediate. Our results show that the direct conjugated C−C bonding is an effective approach for heterogenizing molecular catalysts on carbon, opening new opportunities for employing molecular catalysts in electrochemical applications.

Homogeneous ruthenium catalysed methanol dehydrogenation could become a key reaction for hydrogen production in liquid fuel cells. In order to improve existing catalytic systems, mechanistic insight is paramount in directing future studies. Herein, we describe what computational mechanistic research has taught us so far about ruthenium catalysed dehydrogenation reactions. In general, two mechanistic pathways can be operative in these reactions: a metal-centered or a metal-ligand cooperative (Noyori-Morris type) minimum energy reaction pathway (MERP). Discerning between these mechanisms on the basis of computational studies has proven to be highly input dependent, and to circumvent pitfalls it is important to consider several factors, such as solvent effects, metal-ligand cooperativity, alternative geometries, and complex electronic structures of metal centres. This Frontiers article summarizes the reported computational research performed on ruthenium catalyzed dehydrogenation reactions performed in the past decade, and serves as a guide for future research.