Sulfur-doped graphene anchoring of ultrafine Au<sub>25</sub> nanoclusters for electrocatalysis

Mufan Li; Bei Zhang; Tao Cheng; Sunmoon Yu; Sheena Louisia; Chubai Chen; Shouping Chen; Stefano Cestellos-Blanco; William A. Goddard III; Peidong Yang

doi:10.1007/s12274-021-3561-2

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Research Article

Sulfur-doped graphene anchoring of ultrafine Au₂₅ nanoclusters for electrocatalysis

Mufan Li^{¹^,³^,^§}, Bei Zhang^{¹^,^§}, Tao Cheng^⁵, Sunmoon Yu^{²^,³}, Sheena Louisia^{¹^,³}, Chubai Chen^¹, Shouping Chen^², Stefano Cestellos-Blanco^², William A. Goddard III^⁵, Peidong Yang^{¹^,²^,³^,⁴}()

1 Department of Chemistry, ,University of California,Berkeley, California,94720,USA;

2 Materials Science and Engineering,University of California, Berkeley,California,94720,USA;

3 Chemical Science Division,Lawrence Berkeley National Laboratory,Berkeley, California,94720,USA;

4 Kavli Energy NanoScience Institute,Berkeley, California,94720,USA;

5Materials and Process Simulation Center,California Institute of Technology,Pasadena, California,91125,USA;

^§ Mufan Li and Bei Zhang contributed equally to this work.

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The biggest challenge of exploring the catalytic properties of under-coordinated nanoclusters is the issue of stability. We demonstrate herein that chemical dopants on sulfur-doped graphene (S-G) can be utilized to stabilize ultrafine (sub-2 nm) Au₂₅(PET)₁₈ clusters to enable stable nitrogen reduction reaction (NRR) without significant structural degradation. The Au₂₅@S-G exhibits an ammonia yield rate of 27.5 μg_NH₃·mg_Au^-1·h^-1 at -0.5 V with faradic efficiency of 2.3%. More importantly, the anchored clusters preserve ~ 80% NRR activity after four days of continuous operation, a significant improvement over the 15% remaining ammonia production rate for clusters loaded on undoped graphene tested under the same conditions. Isotope labeling experiments confirmed the ammonia was a direct reaction product of N₂ feeding gas instead of other chemical contaminations. Ex-situ X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy of post-reaction catalysts reveal that the sulfur dopant plays a critical role in stabilizing the chemical state and coordination environment of Au atoms in clusters. Further ReaxFF molecular dynamics (RMD) simulation confirmed the strong interaction between Au nanoclusters (NCs) and S-G. This substrate-anchoring process could serve as an effective strategy to study ultrafine nanoclusters' electrocatalytic behavior while minimizing the destruction of the under-coordinated surface motif under harsh electrochemical reaction conditions.

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gold nanoclusters sulfur-doped graphene nitrogen reduction reaction electrocatalysis anchoring effect

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References

Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981-5079.

Sulfur-doped graphene anchoring of ultrafine Au25 nanoclusters for electrocatalysis

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Sulfur-doped graphene anchoring of ultrafine Au₂₅ nanoclusters for electrocatalysis