American Chemical Society
am3c18693_si_001.pdf (2.65 MB)

Mesoporous Single Atom-Cluster Fe–N/C Oxygen Evolution Electrocatalysts Synthesized with Bottlebrush Block Copolymer-Templated Rapid Thermal Annealing

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journal contribution
posted on 2024-03-08, 20:06 authored by Dipankar Saha, Hsin-Jung Yu, Jiacheng Wang, Prateek, Xiaobo Chen, Chaoyun Tang, Claire Senger, James Nicolas Pagaduan, Reika Katsumata, Kenneth R. Carter, Guangwen Zhou, Peng Bai, Nianqiang Wu, James J. Watkins
Current electrocatalysts for oxygen evolution reaction (OER) are either expensive (such as IrO2, RuO2) or/and exhibit high overpotential as well as sluggish kinetics. This article reports mesoporous earth-abundant iron (Fe)–nitrogen (N) doped carbon electrocatalysts with iron clusters and closely surrounding Fe–N4 active sites. Unique to this work is that the mechanically stable mesoporous carbon-matrix structure (79 nm in pore size) with well-dispersed nitrogen-coordinated Fe single atom-cluster is synthesized via rapid thermal annealing (RTA) within only minutes using a self-assembled bottlebrush block copolymer (BBCP) melamine–formaldehyde resin composite template. The resulting porous structure and domain size can be tuned with the degree of polymerization of the BBCP backbone, which increases the electrochemically active surface area and improves electron transfer and mass transport for an effective OER process. The optimized electrocatalyst shows a required potential of 1.48 V (versus RHE) to obtain the current density of 10 mA/cm2 in 1 M KOH aqueous electrolyte and a small Tafel slope of 55 mV/decade at a given overpotential of 250 mV, which is significantly lower than recently reported earth-abundant electrocatalysts. Importantly, the Fe single-atom nitrogen coordination environment facilitates the surface reconstruction into a highly active oxyhydroxide under OER conditions, as revealed by X-ray photoelectron spectroscopy and in situ Raman spectroscopy, while the atomic clusters boost the single atoms reactive sites to prevent demetalation during the OER process. Density functional theory (DFT) calculations support that the iron nitrogen environment and reconstructed oxyhydroxides are electrocatalytically active sites as the kinetics barrier is largely reduced. This work has opened a new avenue for simple, rapid synthesis of inexpensive, earth-abundant, tailorable, mechanically stable, mesoporous carbon-coordinated single-atom electrocatalysts that can be used for renewable energy production.