Single Pt atom catalysts on non-active carbon supports have been key targets for electrochemical reactions because the high exposure of active Pt leads to record-high activities. PtRu alloy catalysts are the most active for the methanol oxidation reaction (MOR) as the Ru atoms decrease CO poisoning of the active Pt. To combine the exceptional activity of single atom Pt catalysts with the bene ts of an active Ru support we must overcome the synthetic challenge of forming single Pt atoms on noble metal nanoparticles. We have developed a concept to grow and spreads Pt islands on faceted Ru branched nanoparticles to make single Pt atom on Ru catalysts. By following the spreading process with in situ TEM, we show that the formation of single atoms is thermodynamically driven by the formation of strong Pt-Ru bonds and a lowering of surface area. The single Pt atom on Ru catalysts successfully limit CO poisoning during MOR to produce record current density and mass activity over time. MainThe methanol oxidation reaction (MOR) is the limiting reaction for the direct methanol fuel cell because CO-poisoning prevents high current densities over time 1 . CO poisoning is one of the most signi cant issues limiting the long-term use of catalysts for reactions such as MOR, ethanol oxidation and formic acid oxidation, where CO intermediates form 2,3 . Pt is the most active MOR catalyst, however CO ads intermediates bind strongly to poison the Pt sites, thus preventing access of methanol to these active sites 4 . CO poisoning occurs by the formation of CO ads bound on top of three Pt atoms in a triangular arrangement 5,6 . As a consequence, single atom catalysts are a promising target to overcome CO poisoning if Pt atoms can be dispersed on a support without formation of these triangular arrangements of Pt atoms.

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.

No abstract

Layered double hydroxides (LDHs) are promising catalysts for the oxygen evolution reaction (OER) given their modular chemistry and ease of synthesis. Herein, we report a facile strategy for inclusion of oxygen vacancies (VO) using Ce as a promoter in Co–Ni LDHs that significantly enhances the activity for OER. In situ X-ray absorption spectroscopy (XAS) uncovers an increase in octahedral Co sites and VO upon addition of Ce that promotes the transformation of the LDH into an oxyhydroxide-reactive phase more readily. The presence of an OER-active oxyhydroxide phase along with the generation of VO facilitated by the partial reduction of Ce4+ to Ce3+ under oxidizing conditions results in a better electrochemical activity of Ce-doped electrocatalysts. Density functional theory calculations further corroborate the in situ XAS experimental findings by showcasing that the presence of both Ce and VO reduces the free-energy barrier of the rate-limiting OH* deprotonation step during OER. This work showcases how an enhanced understanding of the role of VO promoters in LDH electrocatalysts can provide insights for future catalyst design in anodic reactions.