Key Takeaways & Executive Findings
- •• Summarizes recent advances in the synthesis and catalytic applications of atomically precise Cu nanoclusters. • Elucidates the structure–property–functionality relationship at the atomic level. • Highlights the unique characteristics of Cu nanoclusters, including low cost and superior catalytic performance. • Provides critical analysis of current challenges and future perspectives in this rapidly evolving field.
Abstract
Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal–ligand coordination motifs that can significantly affect their physicochemical properties and functionalities. Among that, Cu nanoclusters have been gaining continuous increasing research attentions, thanks to the low cost, diversified structures, and superior catalytic performance for various reactions. In this review, we first summarize the recent progress regarding the synthetic methods of atomically precise Cu nanoclusters and the coordination modes between Cu and several typical ligands and then discuss the catalytic applications of these Cu nanoclusters with some explicit examples to explain the atomical-level structure–performance relationship. Finally, the current challenges and future research perspectives with some critical thoughts are elaborated. We hope this review can not only provide a whole picture of the current advances regarding the synthesis and catalytic applications of atomically precise Cu nanoclusters, but also points out some future research visions in this rapidly booming field.
1. Introduction
The last decade has witnessed the great success of nanoscience and nanotechnology, yet ideal research model with well-defined composition and structure is still lacking. Specifically, most of the studied nanomaterials are quite polydisperse, that means, in most studied systems, the nano-scientists are extremely difficult to find two same nanoparticles with identical size, morphology, composition, and structure. To advance nanoscience and nanotechnology, one of the ultimate goals for the nano-scientists is to find a truly uniform system, in another word, atomically precise nanoparticles as research models [1, 2].
The emergence of atomically precise coinage metal (Au, Ag, Cu, and its alloy, etc.) nanoclusters can realize such goal [1]. Atomically precise metal nanocluster is a novel type of nanomaterial with the size in the sub-nanometer regime, normally 1–3 nm in diameter. It usually comprises 10–300 metal atoms with surface ligand as the protecting agents capping on the metal core. Note that as the nanoparticle size decreases downward to the sub-nanometer range, due to the strong quantum confinement effect, distinctly different physicochemical properties of metal nanoclusters from relatively large metal nanoparticles are observed [3]. For instance, discrete optical absorbance features can be readily identified in molecular Au nanoclusters, but such feature is absent in larger Au nanoparticle counterparts [4]. More importantly, the sub-nanometer size of the metal nanocluster is still within the resolving limitation of single crystal X-ray diffraction (SC-XRD), that allows nano-chemists to resolve their structure with atomic precision [5]. Such precise structure cannot be available for many other nanomaterials, which render metal nanoclusters unique advantages to comprehensively study the structure–property relationship in various fields, such as sensing [6, 7], assembly [8, 9], catalysis [10–12], optoelectronic [13, 14], and cancer therapy [15–17]. Furthermore, the chemical stability of these metal nanoclusters in terms of electronic structure can be explained by the “superatom” theory, where the electrons are confined in the spherical metal core of a jellium model [18]. It is believed that if the free electron number of a cluster is in good agreement of inert gas atoms (e.g., 2, 8, 18, 34, 52 electrons in the outmost orbital for He, Ne, Ar, Kr, Xe), it can be considered as a superatom having robust stability [18]. Meanwhile, the thermodynamic stability of thiolate metal nanoclusters is associated with the energy balance between the adsorption strength of the ligand shell to the metal core and the cohesive energy of the metal core [19]. In addition, for the non-magic number metal nanoclusters, the Wang group developed a superatomic orbital splitting (SOS) theory to understand the electronic configuration, where the shape of the metal core is considered in determining the order of the group orbital levels [20].
It is worth noting that, compared with noble metal nanoclusters such as Au, Ag, Pd, and Pt, Cu nanoclusters possess some unique characteristics. First, Cu is more earth abundant hence c
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Mengyao Chen, Chengyu Guo, Lubing Qin, Lei Wang, Liang Qiao, Kebin Chi, Zhenghua Tang (2024). Atomically Precise Cu Nanoclusters: Recent Advances, Challenges, and Perspectives in Synthesis and Catalytic Applications. Nano-Micro Letters. https://doi.org/10.1007/s40820-024-01555-6
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Frequently Asked Questions
What are atomically precise Cu nanoclusters?
Atomically precise Cu nanoclusters are sub-nanometer-sized particles composed of 10-300 copper atoms, protected by surface ligands, with well-defined composition and structure resolvable by single-crystal X-ray diffraction.
Why are Cu nanoclusters important in catalysis?
Cu nanoclusters are important in catalysis due to their low cost, earth abundance, diverse structures, and superior catalytic performance for various reactions, offering atomic-level insights into structure-performance relationships.
What are the main synthesis methods for Cu nanoclusters?
The review summarizes recent progress in synthetic methods for atomically precise Cu nanoclusters, including coordination modes between Cu and typical ligands, though specific methods are detailed in the full text.
What are the current challenges in Cu nanocluster research?
Challenges include achieving precise control over size and structure, understanding the structure-property relationships, and developing scalable synthesis methods, as discussed in the review's critical analysis.
What future perspectives are highlighted for Cu nanoclusters?
Future perspectives include exploring new catalytic applications, improving stability, and leveraging atomic-level understanding to design advanced nanomaterials, as outlined in the review.
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