Valence Alignment of Mixed Ni-Fe Hydroxide Electrocatalysts through Preferential Templating on Graphene Edges for Enhanced Oxygen Evolution.
Constantine TsounisXunyu LuNicholas M BedfordBijil SubhashLars ThomsenQingran ZhangZhipeng MaKostya Ken OstrikovAvi BendavidJason A ScottRose AmalZhao Jun HanPublished in: ACS nano (2020)
Engineering the metal-carbon heterointerface has become an increasingly important route toward achieving cost-effective and high-performing 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.
Keyphrases
- metal organic framework
- room temperature
- walled carbon nanotubes
- carbon nanotubes
- high resolution
- highly efficient
- transition metal
- reduced graphene oxide
- computed tomography
- visible light
- postmenopausal women
- ms ms
- gold nanoparticles
- carbon dioxide
- breast cancer cells
- contrast enhanced
- bone mineral density
- magnetic resonance