Copper Nanoparticles with a Tunable Size: Implications for Plasmonic Catalysis

Abstract

A new access to copper(0) nanoparticles (CuNPs) from readily available organocopper reagents is reported. This original amine-free methodology proves to be practical, fast and highly reproducible. It yields spherical CuNPs with an excellent control of their size and shape. These CuNPs are fully characterized by electronic microscopy (TEM, HRTEM), X-Ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and UV-Vis spectroscopy. The size of the synthesized nanoparticles is in a size range of 5-9 nm. The reactional pathway is studied and shows a two-step process implying the formation of a primitive bulk composed of spheroid CuNPs followed by a reorganization step induced by a thiol additive and leading to the final NPs.The robustness of this convenient protocol enables decigram scale synthesis of CuNPs without altering their size and morphology, which makes it a preparative method of choice for their synthesis. This protocol allows the rational design of future copper-based catalysts. The importance of controlling several physicochemical parameters such as size, composition, and shape in metal nanomaterials is indeed widely reported. The results presented here offer many prospects for the rapidly developing field of copper plasmonic catalysis.

Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide

“…For example, reaction of mesitylcopper(I), [CuMes] z (z=4, 5), with 4 bar hydrogen, and neutral (L‐type) amine ligands, delivered 3–5.5 nm colloidal copper(0) nanoparticles [3–4] . The methodology contrasts with conventional routes to copper nanoparticles, such as chemical reduction of inorganic Cu(I) compounds (e. g. halides) that may be contaminated by salt byproducts, or with hot‐injection methods which require careful control over conditions and temperatures, and make larger particles [5] …”

“…[3][4] The methodology contrasts with conventional routes to copper nanoparticles, such as chemical reduction of inorganic Cu(I) compounds (e. g. halides) that may be contaminated by salt byproducts, or with hot-injection methods which require careful control over conditions and temperatures, and make larger particles. [5] Copper, cuprous oxide (Cu 2 O) and cuprous sulfide (Cu 2 S) nanoparticles are useful for (electro/photo)catalysis, [6] gas sensors, [7] plasmonics, [8] optics/electronics and in biomedical applications. [9] Smaller sizes can tune the surface plasmon resonances (Cu(0)), blue-shift the band-gaps of semi-conducting (cuprous oxide/sulfide) phases, and increase the specific active surface area for catalysis or sensing applications.…”

“…[ 3 , 4 ] The methodology contrasts with conventional routes to copper nanoparticles, such as chemical reduction of inorganic Cu(I) compounds (e. g. halides) that may be contaminated by salt byproducts, or with hot‐injection methods which require careful control over conditions and temperatures, and make larger particles. [5] …”

Unveiling the Long-Lived Emission of Copper Nanoclusters Embedded in a Protein Scaffold

“…However, the reported copper nanoparticles showed a clear plasmonic absorption peak. 35,36 On the contrary, such an absorption feature was not observed for BSA−Cu NCs. As a result, the nanostructure obtained in our case could be assigned as nanoclusters.…”

Atomically dispersed copper catalysts for highly selective CO2reduction

“…6 Additionally, Cu species, as an abundant non-noble metal, have excellent performance in catalytic systems. Some examples include electrochemical CO 2 reduction by Cu-based MOFs and Cu particles, 7 Cu clusters for CO 2 methanation, 8 and single Cu atoms applied to the O 2 evolution reaction. 9 Additionally, the interaction between the catalyst and support is an important factor in the activity of catalysts.…”