Mesoporous multimetallic nanospheres with exposed highly entropic alloy sites

Yunqing Kang; Ovidiu Cretu; Jun Kikkawa; Koji Kimoto; Hiroki Nara; Asep Sugih Nugraha; Hiroki Kawamoto; Miharu Eguchi; Ting Liao; Ziqi Sun; Toru Asahi; Yusuke Yamauchi

doi:10.1038/s41467-023-39157-2

Mesoporous multimetallic nanospheres with exposed highly entropic alloy sites

Nat Commun. 2023 Jul 13;14(1):4182. doi: 10.1038/s41467-023-39157-2.

Authors

Yunqing Kang^{1

2}, Ovidiu Cretu¹, Jun Kikkawa¹, Koji Kimoto¹, Hiroki Nara¹, Asep Sugih Nugraha³, Hiroki Kawamoto⁴, Miharu Eguchi², Ting Liao⁵, Ziqi Sun⁶, Toru Asahi², Yusuke Yamauchi^{7

8

9}

Affiliations

¹ Research Center for Materials Nanoarchitectonics and Research Center for Advanced Measurement and Characterization, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan.
² Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555, Japan.
³ Australian Institute for Bioengineering and Nanotechnology (AIBN) and School of Chemical Engineering, The University of Queensland, Brisbane, QLD, 4072, Australia.
⁴ Hitachi High-Tech Corporation, 882, Ichige, Hitachinaka-shi, Ibaraki, 312-0033, Japan.
⁵ School of Mechanical, Medical and Process Engineering, Queensland University of Technology, Brisbane, QLD, 4001, Australia. t3.liao@qut.edu.au.
⁶ School of Chemistry and Physics, Queensland University of Technology, Brisbane, QLD, 4001, Australia.
⁷ Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555, Japan. y.yamauchi@uq.edu.au.
⁸ Australian Institute for Bioengineering and Nanotechnology (AIBN) and School of Chemical Engineering, The University of Queensland, Brisbane, QLD, 4072, Australia. y.yamauchi@uq.edu.au.
⁹ Department of Materials Process Engineering, Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan. y.yamauchi@uq.edu.au.

Abstract

Multimetallic alloys (MMAs) with various compositions enrich the materials library with increasing diversity and have received much attention in catalysis applications. However, precisely shaping MMAs in mesoporous nanostructures and mapping the distributions of multiple elements remain big challenge due to the different reduction kinetics of various metal precursors and the complexity of crystal growth. Here we design a one-pot wet-chemical reduction approach to synthesize core-shell motif PtPdRhRuCu mesoporous nanospheres (PtPdRhRuCu MMNs) using a diblock copolymer as the soft template. The PtPdRhRuCu MMNs feature adjustable compositions and exposed porous structures rich in highly entropic alloy sites. The formation processes of the mesoporous structures and the reduction and growth kinetics of different metal precursors of PtPdRhRuCu MMNs are revealed. The PtPdRhRuCu MMNs exhibit robust electrocatalytic hydrogen evolution reaction (HER) activities and low overpotentials of 10, 13, and 28 mV at a current density of 10 mA cm^-2 in alkaline (1.0 M KOH), acidic (0.5 M H₂SO₄), and neutral (1.0 M phosphate buffer solution (PBS)) electrolytes, respectively. The accelerated kinetics of the HER in PtPdRhRuCu MMNs are derived from multiple compositions with synergistic interactions among various metal sites and mesoporous structures with excellent mass/electron transportation characteristics.

MeSH terms

Alloys*
Catalysis
Crystallization
Electrons
Hydrogen
Nanospheres*

Substances

Alloys
Hydrogen