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Simultaneous oxidative and reductive reactions in one system by atomic design

Abstract

Single-atom catalysts often exhibit unexpected catalytic activity for many important chemical and biological reactions with respect to their bulk counterparts, and have been recognized as potential substitutes for natural enzymes. Here we report a biomimetic composite, yolk–shell Pd1@Fe1, that features two compatible single-atom systems with atomically dispersed Fe1 sites in a N-doped carbon shell and Pd1 sites in a yolk derived from a metal–organic framework. Directly utilizing the O2 and H2 sources generated on-site from the electrocatalytic overall water splitting, the as-synthesized yolk–shell Pd1@Fe1 could simultaneously catalyse nitroaromatic hydrogenation and alkene epoxidation reactions and lead to a cascade synthesis of amino alcohols. Our findings provide a versatile strategy to integrate different single metal sites within one system to allow the continuous and easy synthesis of complex compounds for various challenging reactions.

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Fig. 1: Synthesis and characterization of yolk–shell Pd1@Fe1.
Fig. 2: Chemical state and coordination information of the yolk–shell Pd1@Fe1.
Fig. 3: Illustration of the active site compartmentalization and reaction scheme.
Fig. 4: Production of 1-phenyl-2-(phenylamino)ethanol using CSAS in a homemade device.
Fig. 5: Substrate scope.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key R&D Program of China 2017YFA (0208300 and 0700104), the National Natural Science Foundation of China (21522107, 21671180, 21521091, U1463202 and 21873050). We thank the photoemission endstations BL1W1B at the Beijing Synchrotron Radiation Facility (BSRF), BL14W1 at the Shanghai Synchrotron Radiation Facility (SSRF) and BL10B and BL11U in the National Synchrotron Radiation Laboratory (NSRL) for help in the characterizations.

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Contributions

Y.W. developed the idea and designed experiments. Y.Z. and H.Z. conceived and performed most of the experiments. Y.Q., C.X., Z.X., Q.Z., F.Z., X.M., W.W., M.C., Y.X., X. Lin, H.W. and W.H. participated in some of the experimental work. X.Z. and Y. Li performed the theoretical calculations. L.G., J.L. and Y. Lin performed the aberration-corrected STEM characterizations. X. Liu, W.C., Z.J., L.Z., T.Y., J.D. and S.W. carried out the XFAS characterizations. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yafei Li or Yuen Wu.

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The authors declare no competing interests.

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Peer review information Nature Catalysis thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–43, notes and Tables 1–4.

Source data

Source Data Fig. 1

XRD data for Fig. 2a.

Source Data Fig. 2

57Fe Mössbauer spectra of yolk–shell Pd1@Fe1.

Source Data Fig. 3

EXAFS of single-atom Pd1 sites and Fe1 sites.

Source Data Fig. 4

FT-EXAFS spectra for Fig.2d.

Source Data Fig. 5

The Bader charge of Fe1-CxN4–x (0 ≤ x ≤ 4) and Pd1-CyN4–y (0 ≤ y ≤ 4) structures.

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Zhao, Y., Zhou, H., Zhu, X. et al. Simultaneous oxidative and reductive reactions in one system by atomic design. Nat Catal 4, 134–143 (2021). https://doi.org/10.1038/s41929-020-00563-0

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