Copper Chalcogenide Nanoparticles Research Articles

Harmonic Generation up to Fifth Order from Al/Au/CuS Nanoparticle Films.

Dual heterostructures integrating noble-metal and copper chalcogenide nanoparticles have attracted a great deal of attention in nonlinear optics, because coupling of their localized surface plasmon resonances (LSPRs) substantially enhances light-matter interactions through local-field effects. Previously, enhanced cascaded third-harmonic generation was demonstrated in Au/CuS heterostructures mediated by harmonically coupled surface plasmon resonances. This suggests a promising approach for extending nonlinear enhancement to higher harmonics by adding an additional nanoparticulate material with higher-frequency harmonic resonances to the hybrid films. Here we report the first observation of enhanced cascaded fourth- and fifth-harmonic generation in Al/Au/CuS driven by coupled LSPRs at the fundamental (1050 nm), second harmonic (525 nm), and third harmonic (350 nm) of the pump frequency. An analytical model based on incoherent dipole-dipole interactions among plasmonic nanoparticles accounts for the observed enhancements. The results suggest a novel design for efficiently generating higher harmonics in resonant plasmonic structures by means of multiple sum-frequency cascades.

Superiority of CuSe as a non-nobel electrocatalyst among copper chalcogens for overall water splitting reactions

Among the transition metals copper is one of the cheapest earth- abandoned elements which can enhance electrocatalytic activity. The Cu-based catalysts are superior for catalytic performance and stability in alkaline media for oxygen evolution reaction (OER) and exhibit high activity in acidic media for hydrogen evolution reaction (HER).Synthesized CuSe nanoparticle is found as the most efficient bifunctional electrocatalyst among the synthesized Cu chalcogenides for water splitting reaction. Electrocatalytic performance for water oxidation was investigated in alkaline solution1(M) KOH for OER and 0.5 (M) H2SO4 for HER. To achieve 10 mA/cm2, it was observed an over potential (mV) of 343 for OER and 126 for HER, which are much smaller than these of CuS (385,320) and CuO (410, 345) studied. In this article, we have elucidated some essential criteria need to be specified to evaluate the water splitting performance including onset potential, overpotential, Tafel slope, turnover frequency (TOF), and stability of the copper chalcogenide nanoparticles.

In Situ Fabrication of Nanoprobes for 19F Magnetic Resonance and Photoacoustic Imaging-Guided Tumor Therapy.

It is challenging to fabricate multimodal imaging nanoprobes with high penetration depth and long blood circulation. Herein, we present multifunctional fluorinated nanoprobes (CFPP NPs) containing in situ formed copper chalcogenide nanoparticles for 19F magnetic resonance imaging (MRI) and photoacoustic imaging (PAI). The formed hydrophilic copper chalcogenide nanoassemblies demonstrated easy excretion stemming from facile disassembly, enhanced photothermal ability, and novel localized surface plasmon resonance (LSPR) absorption (centered at 1064 nm) in the "biological transparent" region. Both 19F MRI and PAI render these CFPP NPs suitable for multimodal imaging with high penetration depth and low background. Moreover, the chemo-photothermal synergistic therapy results suggest great potential in multimodal nanoprobes for imaging-guided tumor therapy applications.

Role of the amine and phosphine groups in oleylamine and trioctylphosphine in the synthesis of copper chalcogenide nanoparticles

The effect of the functional groups of capping agents was investigated in the synthesis of copper selenide, copper sulphide and copper oxide nanoparticles using oleylamine (OLA) and trioctylphosphine (TOP). These capping molecules have demonstrated their ability to act as reducing agents, surfactants, solvents and enhancement of colloidal stabilization. They also offer electron donating abilities from the two group 5A elements, P and N. Nitrogen atom in an amine group possess stronger surface interactions and higher basicity than P atom in the phosphines. Copper chalcogenide nanoparticles were prepared using Hot-injection method and characterized using UV/Vis spectroscopy, TEM and XRD. The optical and structural properties of the yielded nanoparticles showed dependence on the type of capping interactions from the two agents. Nanoparticles synthesized using TOP produced two phases whereas a single phase was observed from OLA as confirmed by XRD. Although TOP and OLA exhibit similar features, but their affinity to metals differs resulting to significant different morphology and crystallinity of the produced nanoparticles. Amine group has higher affinity for protons than phosphine due to the lone pair of electrons it possesses which it easily donates to H+ compared to phosphine. The high proton affinity of oleylamine makes it interact faster than trioctylphosphine. OLA in overall produced larger particle sizes compared to TOP but generated a wider variety of shapes.

The release and detection of copper ions from ultrasmall theranostic Cu2-xSe nanoparticles.

Nanoscale copper chalcogenides have been widely used in nanomedicine, however, their pharmacokinetics, degradation, and biological effects of released copper ions are usually overlooked, which are crucial for their future clinical translation. Herein, we report the in vitro and in vivo release of copper ions from polyvinylpyrrolidone (PVP) functionalized ultrasmall copper selenide (Cu2-xSe) theranostic nanoparticles. We synthesized a Cu2+-specific fluorescent probe (NCM), which can quickly and specifically react with copper ions to exhibit very strong near infrared fluorescence. The in vitro study shows that copper ions can be slowly released from Cu2-xSe nanoparticles in aqueous solution with the progress of their oxidation. The release of copper ions from Cu2-xSe nanoparticles in RAW 264.7 murine macrophages is very fast, evidenced by the gradual increase of fluorescence intensity and the diffusion of fluorescence from cytoplasm into nuclei. We also demonstrate the distribution, degradation, and the metabolism of ultrasmall Cu2-xSe nanoparticles by the in vivo fluorescence imaging, the blood routine test, blood biochemistry and histology analysis, and the characterization of copper transport and binding proteins. The results show that ultrasmall Cu2-xSe nanoparticles were mainly eliminated through feces and urine from the body within 72 h after intravenous injection, and the released copper ions did not cause severe toxicity. Our research highlights the great potential of copper chalcogenide nanoparticles in nanomedicine.

Regioselective Synthesis of N2-Alkylated-1,2,3 Triazoles and N1-Alkylated Benzotriazoles: Cu2S as a Recyclable Nanocatalyst for Oxidative Amination of N, N-Dimethylbenzylamines.

Copper chalcogenide nanoparticles (Cu2S) synthesized for the first time from a single-source precursor, CuSPh, act as highly efficient and reusable heterogeneous catalyst for regioselective amination of N, N-dimethylbenzylamines with various azoles. The reaction involves N-H/C-H cross-dehydrogenative coupling (CDC) and demonstrates wide functional group tolerance. It provides highly selective access to N1-alkylated benzotriazoles, N2-alkylated 1,2,3-triazoles and 4-phenyl-1,2,3-triazoles, and N-alkylated carbazoles in 70-89% yields under solvent-free conditions. The Cu2S nanocatalyst has been characterized by PXRD, XPS, SEM-EDX, and HR-TEM analysis. Mechanistic studies suggest that the reaction follows a radical pathway and involves an iminium ion intermediate.

GO-Cu7S4 catalyzed ortho-aminomethylation of phenol derivatives with N,N-dimethylbenzylamines: site-selective oxidative CDC.

Copper chalcogenide nanoparticles (Cu7S4) supported on graphene oxide (GO) have been synthesized for the first time from Cu2S, and used as highly efficient heterogeneous catalysts for oxidative ortho-selective C-H aminomethylation of phenols with N,N-dimethylbenzylamines. The NPs (30-80 nm) have been characterized by HRTEM, SEM-EDX, PXRD, FTIR, Raman, ICP-AES and XPS analyses. The NP catalyzed sp2-sp3 cross dehydrogenative coupling (CDC) features a broad substrate scope, excellent functional group tolerance, high yields, use of an inexpensive and reusable copper catalyst, mild conditions, and no need for pre-functionalization of substrates.

Tuning the LSPR in copper chalcogenide nanoparticles by cation intercalation, cation exchange and metal growth.

Localized surface plasmon resonances (LSPRs) of degenerately doped copper chalcogenide nanoparticles (NPs) (Cu2-xSe berzelianite and Cu1.1S covellite) have been modified applying different methods. The comparison of the cation exchange (Cu2-xSe) and intercalation (Cu1.1S) of Ag(I) and Cu(I) has shown that Ag(I) causes a non reversible, air stable shift of the LSPR. This was compared to the influence of Au(I) cation exchange into Cu1.1S platelets under the formation of Cu1.1S-Au2S mixed nanoplatelets. Furthermore, we show the growth of Au domains on Cu2-xSe, and discuss the interaction of the two plasmonic parts of the obtained dual plasmonic Cu2-xSe-Au hybrid particles.

Determination of a localized surface plasmon resonance mode of Cu7S4 nanodisks by plasmon coupling.

Plasmon properties such as peak position, extinction cross-section and local electric field intensity are strongly dependent on excited, localized surface plasmon resonance (LSPR) modes. In non-spherical copper chalcogenide nanoparticles, assignment of the LSPR peaks to the corresponding oscillation modes has been controversial and requires experimental verification. We determined the in-plane LSPR mode of roxbyite Cu7S4 nanodisks from the plasmon coupling effect of nanodisks in solution. Compared with individual Cu7S4 nanodisks, self-assembled Cu7S4 nanodisk arrays in chloroform exhibited a blue-shifted LSPR peak with weaker optical density. This strongly suggests that the singular LSPR peak in the near-infrared region mainly originates from the in-plane oscillation mode. In addition, we demonstrate that the same LSPR peak can be readily tuned by controlling the number of disks in the array.

Effect of TGA Concentration on Morphology of Cu<sub>2</sub>S Nanoparticals

Copper chalcogenide nanoparticles (NPs) represent a promising material for solar energy conversion and electrical charge storage. We showed that aqueous synthesis of high quality monodispersed high-chalcocite Cu2S NPs is possible. Here, different thioglycolic acid (TGA) concentrations were employed in studies made to investigate the effects of stabilities ratio on particle morphology. It was found that the stabilizes concentration plays a key role in the synthesis of Cu2S NPs, the reaction rate is fast at low concentrations of TGA, and the size range is lager, while flower-like cluster with sizes of 30 nm were formed at high concentrations of TGA. Rapid availability of our results will provide valuable insight into the controlled growth of aqueous dispersions of ternary copper chalcogenide NPs, stimulating further studies of these materials in green energy conversion technologies and drug delivery applications.

Self-Assembly of Copper Sulfide Nanoparticles into Nanoribbons with Continuous Crystallinity

Copper chalcogenide nanoparticles (NPs) represent a promising material for solar energy conversion, electrical charge storage, and plasmonic devices. However, it is difficult to achieve high-quality NP dispersions in experimentally convenient and technologically preferred aqueous media. Also problematic is the transition from NP dispersion to continuously crystalline nanoscale materials, for instance, nanowires, nanoribbons, or similar high aspect ratio nano/microstructures capable of charge transport necessary for such applications. All previous examples of copper sulfide assemblies contained insulating gaps between NPs. Here we show that aqueous synthesis of high-quality monodispersed high-chalcocite β-Cu2S NPs, with sizes from 2 to 10 nm, is possible. When reaction time increased, the NP shape evolved from nearly spherical particles into disks with predominantly hexagonal shape. Moreover, the monodispersed β-Cu2S NPs were found to spontaneously self-assemble into nanochains and, subsequently, to nanoribbons. The width and length of the nanoribbons were 4-20 nm and 50-950 nm, respectively, depending on the assembly conditions. We observed the formation of the nanoribbons with continuous crystal lattice and charge transport pathways, making possible the utilization of self-assembly processes in the manufacturing of photovoltaic, plasmonic, and charge storage devices.