Silica Confinement for Stable and Magnetic Co-Cu Alloy Nanoparticles in Nitrogen-Doped Carbon for Enhanced Hydrogen Evolution

Chao Wan; Rong Li; Jiapei Wang; Dang-Guo Cheng; Fengqiu Chen; Lixin Xu; Mingbin Gao; Yunqing Kang; Miharu Eguchi; Yusuke Yamauchi

doi:10.1002/anie.202404505

Silica Confinement for Stable and Magnetic Co-Cu Alloy Nanoparticles in Nitrogen-Doped Carbon for Enhanced Hydrogen Evolution

Angew Chem Int Ed Engl. 2024 Apr 10:e202404505. doi: 10.1002/anie.202404505. Online ahead of print.

Authors

Chao Wan^{1

2

3}, Rong Li¹, Jiapei Wang¹, Dang-Guo Cheng², Fengqiu Chen², Lixin Xu¹, Mingbin Gao⁴, Yunqing Kang^{3

5}, Miharu Eguchi^{6

7}, Yusuke Yamauchi^{7

8

9}

Affiliations

¹ School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma'anshan, 243002, China.
² College of Chemical and Biological Engineering, Zhejiang University, 866 Yuhangtang Road, Hangzhou, 310058, China.
³ Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan.
⁴ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
⁵ Nanozyme Laboratory in Zhongyuan, Henan Academy of Innovations in Medical Science Zhengzhou, Henan, 451163, China.
⁶ Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555, Japan.
⁷ Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, Queensland, 4072, Australia.
⁸ Department of Materials Process Engineering, Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan.
⁹ Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul, 03722, South Korea.

PMID: 38598471
DOI: 10.1002/anie.202404505

Abstract

Ammonia borane (AB) with 19.6 wt % H₂ content is widely considered a safe and efficient medium for H₂ storage and release. Co-based nanocatalysts present strong contenders for replacing precious metal-based catalysts in AB hydrolysis due to their high activity and cost-effectiveness. However, precisely adjusting the active centers and surface properties of Co-based nanomaterials to enhance their activity, as well as suppressing the migration and loss of metal atoms to improve their stability, presents many challenges. In this study, mesoporous-silica-confined bimetallic Co-Cu nanoparticles embedded in nitrogen-doped carbon (Co_xCu_1-x@NC@mSiO₂) were synthesized using a facile mSiO₂-confined thermal pyrolysis strategy. The obtained product, an optimized Co_0.8Cu_0.2@NC@mSiO₂ catalyst, exhibits enhanced performance with a turnover frequency of 240.9 mol_H2 ⋅ mol_metal ⋅ min^-1 for AB hydrolysis at 298 K, surpassing most noble-metal-free catalysts. Moreover, Co_0.8Cu_0.2@NC@mSiO₂ demonstrates magnetic recyclability and extraordinary stability, with a negligible decline of only 0.8 % over 30 cycles of use. This enhanced performance was attributed to the synergistic effect between Co and Cu, as well as silica confinement. This work proposes a promising method for constructing noble-metal-free catalysts for AB hydrolysis.

Keywords: Ammonia borane hydrolysis; Cobalt-Copper alloy nanoparticles; Hydrogen evolution; Metal–organic frameworks; Silica confinement.

Abstract

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