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铜纳米团簇的高产率合成及其在光热转换和催化中的应用

High-Yield Synthesis of Cu Nanoclusters and Their Applications in Photothermal Conversion and Catalysis.

作者信息

Sardar Avirup, Wang Yitong, Mazumder Abhrojyoti, He Guiying, Gianopoulos Christopher G, Kirschbaum Kristin, Jin Rongchao

机构信息

Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.

Department of Chemistry and Biochemistry, University of Toledo, Toledo, Ohio 43606, United States.

出版信息

Inorg Chem. 2025 Sep 8;64(35):17687-17695. doi: 10.1021/acs.inorgchem.5c01411. Epub 2025 Aug 22.

Abstract

Atomically precise copper nanoclusters (NCs) have received considerable interest in recent years. Significant progress is being made in understanding their synthesis, size/shape control, and crystallization techniques. Unlike Au and Ag nanoclusters, zerovalent Cu NCs are much more difficult to synthesize due to the low reduction potential of Cu(II) or Cu(I). However, Cu is unique in its catalytic reactivity and photothermal conversion. This study presents a high-yield procedure for bulk synthesis of a Cu NC (in Cu(I) valence state) coprotected by cyclohexanethiolate (CHT) and triphenylphosphine (TPP), with its crystal structure characterized. The Cu-CHT-TPP is further investigated as an effective photothermal material as well as a catalyst for the azide-alkyne click-chemistry reactions. The Cu NC possesses a good photothermal activity (e.g., a 22.4 °C increase in 450 s for 0.4 OD when irradiated 488 nm laser of 1.75 W/cm) and a photothermal efficiency of 33%, which rivals the best Au NCs reported. In the catalysis, it shows fast reactions and >90% yields under blue LED irradiation, along with good recyclability, when used as a homogeneous catalyst. The findings from this work may promote future explorations of Cu NCs in various applications.

摘要

近年来,原子精确的铜纳米团簇(NCs)受到了广泛关注。在理解其合成、尺寸/形状控制和结晶技术方面取得了重大进展。与金和银纳米团簇不同,由于Cu(II)或Cu(I)的还原电位较低,零价铜纳米团簇更难合成。然而,铜在催化反应性和光热转换方面具有独特性。本研究提出了一种高产率的方法,用于批量合成由环己硫醇盐(CHT)和三苯基膦(TPP)共保护的铜纳米团簇(处于Cu(I)价态),并对其晶体结构进行了表征。进一步研究了Cu-CHT-TPP作为一种有效的光热材料以及叠氮化物-炔烃点击化学反应的催化剂。该铜纳米团簇具有良好的光热活性(例如,在1.75 W/cm的488 nm激光照射下,0.4 OD在450 s内温度升高22.4 °C)和33%的光热效率,与报道的最佳金纳米团簇相当。在催化反应中,当用作均相催化剂时,在蓝色LED照射下显示出快速反应和>90%的产率,并且具有良好的可回收性。这项工作的发现可能会促进未来对铜纳米团簇在各种应用中的探索。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/98cf/12421667/6bbe44706b2c/ic5c01411_0001.jpg

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