Pt Nanoparticle-Mn Single-Atom Pairs for Enhanced Oxygen Reduction

Xiaoqian Wei; Shaojia Song; Weiwei Cai; Yunqing Kang; Qie Fang; Ling Ling; Yingji Zhao; Zexing Wu; Xiaokai Song; Xingtao Xu; Sameh M Osman; Weiyu Song; Toru Asahi; Yusuke Yamauchi; Chengzhou Zhu

doi:10.1021/acsnano.3c09819

Pt Nanoparticle-Mn Single-Atom Pairs for Enhanced Oxygen Reduction

ACS Nano. 2024 Feb 6;18(5):4308-4319. doi: 10.1021/acsnano.3c09819. Epub 2024 Jan 23.

Authors

Xiaoqian Wei^{1

2

3}, Shaojia Song⁴, Weiwei Cai⁵, Yunqing Kang⁶, Qie Fang¹, Ling Ling¹, Yingji Zhao^{2

3}, Zexing Wu⁶, Xiaokai Song⁶, Xingtao Xu⁶, Sameh M Osman⁷, Weiyu Song⁴, Toru Asahi², Yusuke Yamauchi^{3

8

9}, Chengzhou Zhu¹

Affiliations

¹ National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China.
² Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555, Japan.
³ Department of Materials Process Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan.
⁴ State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing, 102249, People's Republic of China.
⁵ Energy Laboratory, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, 430074, People's Republic of China.
⁶ International Center for Materials Nanoarchitechtonics, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
⁷ Chemistry Department, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia.
⁸ Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD 4072, Australia.
⁹ Department of Chemical and Biomolecular Engineering, Yonsei University, Yonsei-ro, Seodaemun-gu, Seoul 03722, South Korea.

PMID: 38261610
DOI: 10.1021/acsnano.3c09819

Abstract

The intrinsic roadblocks for designing promising Pt-based oxygen reduction reaction (ORR) catalysts emanate from the strong scaling relationship and activity-stability-cost trade-offs. Here, a carbon-supported Pt nanoparticle and a Mn single atom (Pt_NP-Mn_SA/C) as in situ constructed Pt_NP-Mn_SA pairs are demonstrated to be an efficient catalyst to circumvent the above seesaws with only ∼4 wt % Pt loadings. Experimental and theoretical investigations suggest that Mn_SA functions not only as the "assist" for Pt sites to cooperatively facilitate the dissociation of O₂ due to the strong electronic polarization, affording the dissociative pathway with reduced H₂O₂ production, but also as an electronic structure "modulator" to downshift the d-band center of Pt sites, alleviating the overbinding of oxygen-containing intermediates. More importantly, Mn_SA also serves as a "stabilizer" to endow Pt_NP-Mn_SA/C with excellent structural stability and low Fenton-like reactivity, resisting the fast demetalation of metal sites. As a result, Pt_NPs-Mn_SA/C shows promising ORR performance with a half-wave potential of 0.93 V vs reversible hydrogen electrode and a high mass activity of 1.77 A/mg_Pt at 0.9 V in acid media, which is 19 times higher than that of commercial Pt/C and only declines by 5% after 80,000 potential cycles. Specifically, Pt_NPs-Mn_SA/C reaches a power density of 1214 mW/cm² at 2.87 A/cm² in an H₂-O₂ fuel cell.

Keywords: Mn single atoms; Pt nanoparticles; atomic pairs; oxygen reduction reactions; synergistic effects.