Photoreforming is a process that harnesses the redox ability of photocatalysts upon illumination, to simultaneously drive the reduction of H+ into hydrogen gas and oxidation of organic compounds. Over the...

Electrochemical oxygen reduction reaction (ORR) in acids via a selective 2e- pathway offers great opportunities for electrosynthesis of H2O2, allowing on-site environmental treatment in industry. Unfortunately, despite some progress, the...

Engineering the metal−carbon heterointerface has become an increasingly important route toward achieving cost-effective and highperforming electrocatalysts. The specific properties of graphene edge sites, such as the high available density of states and extended unpaired π-bonding, make it a promising candidate to tune the electronic properties of metal catalysts. However, to date, understanding and leveraging graphene edge− metal catalysts for improved electrocatalytic performance remains largely elusive. Herein, edge-rich vertical graphene (er-VG) was synthesized and used as a catalyst support for Ni−Fe hydroxides for the oxygen evolution reaction (OER). The hybrid Ni−Fe/er-VG catalyst exhibits excellent OER performance with a mass current of 4051 A g −1 (at overpotential η = 300 mV) and turnover frequency (TOF) of 4.8 s −1 (η = 400 mV), outperforming Ni−Fe deposited on pristine VG and other metal foam supports. Angle-dependent X-ray absorption spectroscopy shows that the edge-rich VG support can preferentially template Fe−O units with a specific valence orbital alignment interacting with the unoccupied density of states on the graphene edges. This graphene edge−metal interaction was shown to facilitate the formation of undersaturated and strained Fe-sites with high valence states, while promoting the formation of redox-activated Ni species, thus improving OER performance. These findings demonstrate rational design of the graphene edge−metal interface in electrocatalysts which can be used for various energy conversion and chemical synthesis reactions.

Graphene edges exhibit a highly localized density of states that result in increased reactivity compared to its basal plane. However, exploiting this increased reactivity to anchor and tune the electronic states of single atom catalysts (SACs) remains elusive. To investigate this, a method to anchor Pt SACs with ultra‐low mass loadings at the edges of edge‐rich vertically aligned graphene (as low as 0.71 µg Pt cm–2) is developed. Angle‐dependent X‐ray absorption spectroscopy and density‐functional theory calculations reveal that edge‐anchored Pt SACs has a robust coupling with the π‐electrons of graphene. This interaction results in a higher occupancy of the Pt 5d orbital, shifting the d‐band center toward the Fermi level, improving the adsorption of *H for the hydrogen evolution reaction (HER). Pt primarily coordinated to the graphene edge shows improved alkaline HER performance compared to Pt coordinated in mixed environments (turnover frequencies of 22.6 and 10.9 s–1 at an overpotential of 150 mV, respectively). This work demonstrates an effective route to engineering the coordination environment of Pt SACs by using the graphene edge for enhanced energy conversion reactions.