Tailored Design of Mesoporous Metal Organic Framework Single Crystals by Kinetics-Mediated Micelle Assembly for Efficient Asymmetrical Single-Atom Catalysis

Xin Wang; Siyuan Zhang; Musen Li; Ying Wan; Zhihao Sun; Ruchen Li; Zijia Zhu; Hao Wu; Zaiwang Zhao; Shunbo Hu; Fanxing Bu; Dongliang Chao; Wei Luo

doi:10.1002/adma.202500370

Tailored Design of Mesoporous Metal Organic Framework Single Crystals by Kinetics-Mediated Micelle Assembly for Efficient Asymmetrical Single-Atom Catalysis

Adv Mater. 2025 Jun 2:e2500370. doi: 10.1002/adma.202500370. Online ahead of print.

Authors

Xin Wang^{1

2}, Siyuan Zhang², Musen Li¹, Ying Wan², Zhihao Sun³, Ruchen Li¹, Zijia Zhu¹, Hao Wu¹, Zaiwang Zhao³, Shunbo Hu¹, Fanxing Bu¹, Dongliang Chao³, Wei Luo²

Affiliations

¹ Key Laboratory of Silicate Cultural Relics Conservation, Ministry of Education, Institute for the Conservation of Cultural Heritage, School of Cultural Heritage and Information Management, Shanghai University, Shanghai, 200444, P. R. China.
² State Key Laboratory of Advanced Fiber Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.
³ Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, School of Chemistry and Materials, Fudan University, Shanghai, 200433, P. R. China.

PMID: 40457656
DOI: 10.1002/adma.202500370

Abstract

Constructing mesoporous metal organic frameworks (MesoMOFs) with customizable meso- and micro-environment is pivotal for asymmetric single-atom catalysis, yet it is impeded by the strong self-growth tendency of MOFs. In this work, a novel kinetics-mediated micelle assembly strategy is introduced to realize the general fabrication of mesoporous zeolitic imidazolate framework (ZIF) single crystals. Spectroscopic characterizations and cryo-electron cryomicroscopy reveal that the strategic use of water accelerates the MOFs kinetics-mediated micelle assembly via enhancing ligand deprotonation, which suppresses the MOFs self-growth, facilitating the cooperative assembly of micelles and MOFs. Furthermore, the water amount can modulate the Flory-Huggins interaction parameters between the solvents and micelles, thereby precisely controlling the pore architectures from spherical, cylindrical to vesicular. Such versatile synthesis creates a new class of mesoporous asymmetric CoN₃O single-atom catalyst. Synchrotron spectral characterizations and theoretical calculations uncover that this asymmetric geometry localizes more electrons around Co center and upshift the d-band center, stabilizing O* intermediates and promoting the oxygen reduction reaction (ORR). Consequently, the asymmetric mesoporous catalyst exhibits a half-wave potential (0.91 V in alkaline media) and a high power density (185 mW cm^-2) in a zinc-air battery. This work provides a new approach for designing MesoMOFs for asymmetric single-atom catalysis.

Keywords: asymmetrical single‐atom; kinetics‐mediated micelle assembly; mesoporous materials; metal organic frameworks; oxygen reduction reaction (ORR).

Abstract

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