Mohamed Abboud, Siti Fatimah, Abdelkarim Chaouiki, Maryam Chafiq, Noureddine Elboughdiri, Jee-Hyun Kang, Young Gun Ko
Metal aggregates (MA) at the nanoscale, including nanoparticles and nanoclusters, serve as crucial active components in various technological applications. However, to preserve their functional properties and prevent agglomeration, these aggregates require stabilization through appropriate anchoring. Metal–organic frameworks (MOFs) have emerged as highly promising host materials due to their structural tunability and porosity, allowing for precise control over MA incorporation. MOFs offer several advantages as encapsulating matrices: their uniform, long-range ordered cavities facilitate efficient mass transfer and diffusion of substrates and products, while their diverse metal nodes and tunable organic linkers enable synergistic interactions with the encapsulated metal aggregates. Despite significant progress, key challenges remain, including achieving atomically precise encapsulation, ensuring long-term stability, and scaling up synthesis for practical applications. Recent advancements in in-situ growth, post-synthetic modification, and template-assisted approaches have improved control over aggregate localization within MOF cavities. However, fundamental structure–property relationships remain underexplored. Additionally, the catalytic activity and selectivity of these composites can be enhanced through synergistic interactions between the encapsulated MA and the MOF matrix, as well as the molecular sieving properties of the host material. Achieving atom-efficient synthesis of MA@MOF composites is essential for establishing precise structure–property relationships and tailoring functionalities at the molecular level. The ’ship-in-a-bottle’ and ’bottle-around-the-ship’ approaches represent distinct strategies for encapsulating MA within MOFs, differing from conventional methods. In principle, the ’ship-in-a-bottle’ method involves the incorporation of metal guest species within a pre-formed MOF matrix, while the ’bottle-around-the-ship’ approach entails the assembly of the MOF framework around pre-synthesized and stabilized MA. These approaches represent advanced strategies for developing host@MOF materials. However, the controlled synthesis of MA within MOFs remains challenging, having been successfully demonstrated in only a few cases, and requires precise optimization of synthesis parameters. While MA@MOF materials are well-established in catalysis, their potential applications in advanced fields are gaining increasing attention. This review article examines the latest strategies for synthesizing MA@MOF composites, constructing hierarchical architectures, and addressing existing limitations. Furthermore, we highlight critical research gaps, particularly the need for advanced characterization techniques and deeper theoretical insights into atomically precise MA confined within MOFs. Addressing these challenges will unlock new opportunities for tailored functionalities and expand the application scope of MA@MOF materials. © 2025 Elsevier B.V.
Catalysis Research Group (CRG), Department of Chemistry, College of Science, King Khalid University, Abha, Saudi Arabia; School of Materials Science and Engineering, Yeungnam University, Gyeongsan, 38541, South Korea; Chemical Engineering Department, College of Engineering, University of Ha'il, P.O. Box 2440, Ha'il, 81441, Saudi Arabia; Chemistry Program, Universitas Pendidikan Indonesia, Bandung, 40154, Indonesia
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