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Sulfur-doped graphene anchoring of ultrafine Au₂₅ nanoclusters for electrocatalysis

Li, Mufan and Zhang, Bei and Cheng, Tao and Yu, Sunmoon and Louisia, Sheena and Chen, Chubai and Chen, Shouping and Cestellos-Blanco, Stefano and Goddard, William A., III and Yang, Peidong (2021) Sulfur-doped graphene anchoring of ultrafine Au₂₅ nanoclusters for electrocatalysis. Nano Research . ISSN 1998-0124. doi:10.1007/s12274-021-3561-2. (In Press) https://resolver.caltech.edu/CaltechAUTHORS:20210608-130600287

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Abstract

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 27.5μg_(NH₃)⋅mgAu⁻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.


Item Type:Article
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URLURL TypeDescription
https://doi.org/10.1007/s12274-021-3561-2DOIArticle
https://rdcu.be/cmaJEPublisherFree ReadCube access
ORCID:
AuthorORCID
Li, Mufan0000-0002-4575-4055
Cheng, Tao0000-0003-4830-177X
Goddard, William A., III0000-0003-0097-5716
Yang, Peidong0000-0003-4799-1684
Alternate Title:Sulfur-doped graphene anchoring of ultrafine Au25 nanoclusters for electrocatalysis
Additional Information:© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021. Received 20 February 2021; Revised 23 April 2021; Accepted 01 May 2021; Published 03 June 2021. This research was supported by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, & Biosciences Division, of the US Department of Energy under Contract DEAC02-05CH11231, FWP CH030201 (Catalysis Research Program). The Advanced Light Source was supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract DE-AC02-05CH11231. This work made use of the facilities at the NMR Facility, College of Chemistry, University of California, Berkeley. Inductively coupled plasma optical emission spectrometry was supported by the Microanalytical Facility, College of Chemistry, University of California, Berkeley. Part of this material (WAG, TC) was based on work performed by the Liquid Sunlight Alliance, which was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. This work is dedicated to the occasion of 80th birthday for Prof. Yitai Qian. As the undergraduate advisor for one of the authors (P. D. Y.), Prof. Qian has had profound impact on this author’s career in the field of materials chemistry. P. D. Y. would like to acknowledge the unconditional support, encouragement and guidance from Prof. Qian back in the early 1990s. It was during that time P. D. Y. started his journey in solid state chemistry, by working on high temperature cuprate superconductors and finishing his undergraduate thesis on this exciting topic. The title page of this thesis was attached here (dated June 10, 1993).
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-05CH11231
Department of Energy (DOE)DE-SC0021266
Subject Keywords:gold nanoclusters, sulfur-doped graphene, nitrogen reduction reaction, electrocatalysis, anchoring effect
DOI:10.1007/s12274-021-3561-2
Record Number:CaltechAUTHORS:20210608-130600287
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210608-130600287
Official Citation:Li, M., Zhang, B., Cheng, T. et al. Sulfur-doped graphene anchoring of ultrafine Au25 nanoclusters for electrocatalysis. Nano Res. (2021). https://doi.org/10.1007/s12274-021-3561-2
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109446
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:09 Jun 2021 18:18
Last Modified:09 Jun 2021 18:18

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