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. 2022 Mar 18;8(11):eabn5091.
doi: 10.1126/sciadv.abn5091. Epub 2022 Mar 16.

A clicking confinement strategy to fabricate transition metal single-atom sites for bifunctional oxygen electrocatalysis

Chang-Xin Zhao  1 , Jia-Ning Liu  1 , Juan Wang  2   3 , Changda Wang  4 , Xin Guo  4 , Xi-Yao Li  1 , Xiao Chen  1 , Li Song  4 , Bo-Quan Li  2   3 , Qiang Zhang  1
Affiliations

A clicking confinement strategy to fabricate transition metal single-atom sites for bifunctional oxygen electrocatalysis

Chang-Xin Zhao et al. Sci Adv. .

Abstract

Rechargeable zinc-air batteries call for high-performance bifunctional oxygen electrocatalysts. Transition metal single-atom catalysts constitute a promising candidate considering their maximum atom efficiency and high intrinsic activity. However, the fabrication of atomically dispersed transition metal sites is highly challenging, creating a need for for new design strategies and synthesis methods. Here, a clicking confinement strategy is proposed to efficiently predisperse transitional metal atoms in a precursor directed by click chemistry and ensure successful construction of abundant single-atom sites. Concretely, cobalt-coordinated porphyrin units are covalently clicked on the substrate for the confinement of the cobalt atoms and affording a Co-N-C electrocatalyst. The Co-N-C electrocatalyst exhibits impressive bifunctional oxygen electrocatalytic performances with an activity indicator ΔE of 0.79 V. This work extends the approach to prepare transition metal single-atom sites for efficient bifunctional oxygen electrocatalysis and inspires the methodology on precise synthesis of catalytic materials.

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Figures

Fig. 1.
Fig. 1.. Different confinement strategies to fabricate M-N-C SACs.
Schematic representation of the precursor design strategies to fabricate M-N-C SACs regarding (A) the chamber confinement strategy, (B) the reticular confinement strategy, and (C) the clicking confinement strategy.
Fig. 2.
Fig. 2.. Material characterization of CoNC SAC.
(A) Schematic of the synthesis procedure of CoNC SAC. (B) SEM, (C) TEM, and (D) HAADF-STEM images and corresponding EDS mapping of CoNC SAC. (E) High-resolution HAADF-STEM image of CoNC SAC, where the cobalt single atoms are marked with yellow circles. The inset in (E) is the linear scan analysis along the arrow. (F) N 1 s XPS spectrum of CoNC SAC. a.u., arbitrary unit.
Fig. 3.
Fig. 3.. Bifunctional performance evaluation.
(A) ORR and (C) OER LSV profiles of the CoNC SAC and Pt/C + It/C electrocatalysts. (B) and (D) are the corresponding Tafel plots for ORR and OER, respectively. (E) Bifunctional LSV curves of the CoNC SAC and Pt/C + It/C electrocatalysts. (F) Diagram for comparing the bifunctional performance of the CoNC SAC, Pt/C + It/C, and other reported electrocatalysts based on M-N-C SACs.
Fig. 4.
Fig. 4.. Mechanism investigation for the clicking confining strategy.
(A) TEM image of CoPor + CNT-amino. The insert is the Fourier-transformed crystalline lattice. (B) XRD patterns of CoNC SAC, CoPor + CNT-amino, and CoPor + CNT. (C) ORR and (D) OER LSV curves of the CoNC SAC, CoPor + CNT-amino, and CoPor + CNT electrocatalysts.
Fig. 5.
Fig. 5.. Performance of rechargeable ZABs.
(A) LSV profiles and discharge power density and (B) rate performances of ZABs with the CoNC SAC and Pt/C + It/C electrocatalysts. Galvanostatic cycling curves of ZABs with the CoNC SAC and Pt/C + It/C electrocatalysts at the cycling current density of (C) 5.0 and (D) 25 mA cm−2. (E) Rechargeable ZAB performance comparison regarding the cycling current density, voltage gap, and cycle number of the CoNC SAC electrocatalyst and other reported electrocatalysts.
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References

    1. Mizushima K., Jones P. C., Wiseman P. J., Goodenough J. B., LixCoO2 (0<x<−1): A new cathode material for batteries of high energy density. Mater. Res. Bull. 15, 783–789 (1980).
    1. Kim J. M., Jo A., Lee K. A., Han H. J., Kim Y. J., Kim H. Y., Lee G. R., Kim M., Park Y., Kang Y. S., Jung J., Chae K. H., Lee E., Ham H. C., Ju H., Jung Y. S., Kim J. Y., Conformation-modulated three-dimensional electrocatalysts for high-performance fuel cell electrodes. Sci. Adv. 7, eabk0919 (2021). - PMC - PubMed
    1. Manthiram A., Yu X., Wang S., Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017).
    1. Kundu D., Talaie E., Duffort V., Nazar L. F., The emerging chemistry of sodium ion batteries for electrochemical energy storage. Angew. Chem. Int. Ed. 54, 3431–3448 (2015). - PubMed
    1. Cheng W., Zhang H., Luan D., Lou X. W., Exposing unsaturated Cu1–O2 sites in nanoscale Cu-MOF for efficient electrocatalytic hydrogen evolution. Sci. Adv. 7, eabg2580 (2021). - PMC - PubMed