Synthesis Of Cu Research Articles

Synthesis and cytotoxicity studies of Cu(I) and Ag(I) complexes based on sterically hindered β-diketonates with different degrees of fluorination.

Design, synthesis, and in vitro antitumor properties of Cu(I) and Ag(I) phosphane complexes supported by the anions of sterically hindered β-diketone ligands, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3) featuring trifluoromethyl or methyl groups on the phenyl moieties have been reported. In order to compare the biological effects of substituents on the phenyl moieties, the analogous copper(I) and silver(I) complexes of the anion of the parent 1,3-diphenylpropane-1,3-dione (HLPh) ligand were also synthesized and included in the study. In the syntheses of the Cu(I) and Ag(I) complexes, the phosphane coligands triphenylphosphine (PPh3) and 1,3,5-triaza-7-phosphaadamantane (PTA) were used to stabilize silver and copper in the +1 oxidation state, preventing the metal ion reduction to Ag(0) or oxidation to Cu(II), respectively. X-ray crystal structures of HLCF3 and the metal adducts [Cu(LCF3)(PPh3)2] and [Ag(LPh)(PPh3)2] are also presented. The antitumor properties of both classes of metal complexes were evaluated against a series of human tumor cell lines derived from different solid tumors, by means of both 2D and 3D cell viability studies. They display noteworthy antitumor properties and are more potent than cisplatin in inhibiting cancer cell growth.

Controlled synthesis of Cu,Fe dual-atom catalysts restrained on metal–organic frameworks for efficient O2 activation

We present the precise synthesis of Cu,Fe DACs supported on UiO-66-NH2. The DACs show high selectivity towards benzaldehyde in photocatalytic styrene oxidation by efficient O2 activation.

Influence of anions on the synthesis of Cu(i)-based coordination polymers along with a series of derived materials for selective photocatalytic properties

Two anion-regulated Cu-CPs were employed as sacrificial precursors for the synthesis of derived materials by a pyrolysis method. The photocatalytic performances emphasized that anions and doping elements play vital roles in the derived materials.

In situ synthesis of Cu(II) dicarboxylate metal organic frameworks (MOFs) and their application as battery materials.

New materials for battery electrodes are paramount to ensuring future battery supply can meet the ever-increasing demand for energy storage. Furthermore, detailed investigation on the various physical and chemical aspects of these materials is required to allow the same level of nuanced microstructural and electrochemical tuning that is available for conventional electrode materials. Here a comprehensive investigation is undertaken on the poorly understood in situ reaction between dicarboxylic acids and the copper current collector that occurs during electrode formulation, using a series of simple dicarboxylic acids. Specifically, we focus on the relationship between the extent of the reaction and the properties of the acid. Additionally, the extent of the reaction was demonstrated to affect both the electrode microstructure and the electrochemical performance. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and small and ultra-small angle neutron scattering (U/SANS) are used to provide unprecedented detail on the microstructure ultimately leading to a deeper understanding of formulation based performance enhancing techniques. Ultimately, it was determined that the copper-carboxylates are the active material, not the parent acid, and in some cases i.e., copper malate, capacities as high as 828 mA h g-1 were achieved. This work lays the foundation for future studies that use the current collector as an "active" component in electrode formulation and function rather than simply an inactive component of a battery.

Metal assisted chemical etching of silicon and solution synthesis of Cu-=SUB=-2-=/SUB=-O/Si radial nanowire array heterojunctions

Cu2O/Si radial nanowire (NWs) array heterojunctions were prepared by depositing Cu2O nanoparticles via chemical bath deposition on n-Si nanowire arrays that were fabricated by metal-assisted electroless etching. After 20 cycles of deposition, large numbers of Cu2O nanoparticles with form shells that wrap the upper segment of each Si nanowire. This method of etching offers exceptional simplicity, flexibility, environmental friendliness, and scalability for the fabrication of three-dimensional silicon nanostructures with considerable depths, because of replacement of harsh oxidants such as H2O2 and AgNO3. Keywords: Cu2O/Si NWs heterojunctions, Cu2O nanoparticles, metal-assisted electroless etching.

One-step green synthesis of Cu2O/CuO@rGO composites for ppt level detection of NO2 at room temperature

A ppt level NO2 sensor with high sensitivity, selectivity and stability based on one-step room temperature green synthesized 550Cu2O/CuO@rGO-5 composites.

Design and syntheses of Cu–Fe3O4@Fe electrode with needle-like structure and electric field potential: Remediation of nitrate contamination and action in protein wastewater

As nitrate is highly stabilised in solution, its removal is a constant challenge. Electrochemical reduction of nitrate is considered a promising treatment, but most strategies only concern reduction rate without current efficiency and practical application prospects. In this work,a binary non-precious metal needle-like Cu–Fe3O4@Fe electrode was synthesized from by a two-step in situ growth method using Fe foam as raw material, and its feasibility for nitrate reduction was investigated. The Cu–Fe3O4@Fe electrode exhibits 92.01% nitrate removal and 50.3% current efficiency in 150 min electrocatalysis, which is 2.82 and 2.18 times more effective than Fe foam, respectively. The excellent nitrate removal performance of Cu–Fe3O4@Fe is credited to the electricity field and the needle-like structure. The needle-like structure improves mass transfer, while the electricity field enhances the efficiency of electron transfer. The electrode Cu–Fe3O4@Fe maintains excellent stability over six cycles and the leaching rates of Cu and Fe are far less than the electrodes Fe and Cu@Fe. The electrode was used to treat protein wastewater with significant removal of nitrate, total nitrogen (TN) and Chemical oxygen demand (COD). All the results have proved that the binary non-precious metal needle-like Cu–Fe3O4@Fe electrode is a cost-effective, efficient and stable, environmentally friendly electrode material for the deep purification of protein wastewater.

One pot synthesis of Cu–Ni–S@Ni foam for the simultaneous removal and detection of norfloxacin

The residual antibiotics in the environment will pose a threat to the environment and human health. Thus, it is imperative to develop a smart water treatment material to remove and detect antibiotics from aqueous environment simultaneously. In this study, magnetic Cu–Ni–S@Ni foam was synthesized by liquid phase vulcanization method to in-situ load Cu–Ni–S nanostructures on the surface of Ni foam. The novelty of this material is the combination of adsorption-flocculation technology and semi-quantitative detection technology. Batch experiments showed that Cu–Ni–S@Ni foam has a high removal rate of norfloxacin (NOR) (96.92%), wide pH adaptability (pH = 4.0–10.0) and strong ion interference resistance (0.1–100 mmol/L). According to the Langmuir isotherm, the removal capacity can reach 417.4 mg/g at 25 °C, which is much higher than that of other water treatment agents reported in most studies. Characterization analysis indicated that the main removal mechanisms are surface complexation, cation bridging, electrostatic attraction, precipitation and flocculation. Transmission FTIR detection experiments showed that NOR on Cu–Ni–S@Ni foam has easily recognizable FTIR fingerprints; the intensity of characteristic peaks roughly reflects the concentration information of NOR to some extent. This semi-quantitative detection method, requiring simple operation without the fabrication of KBr tablet, has a wide linear range (5–100 mg/L) and a low limit of detection (4.6 mg/L). Therefore, Cu–Ni–S@Ni foam can be used for simultaneous removal and semi-quantitative detection of NOR in wastewater. It has potential application value in wastewater treatment and water quality monitoring.

Copper carbide composite catalyst for hydrogenolysis of glycerol to 1,2-propanediol

The hydrogenolysis of renewable glycerol towards 1,2-propanediol (abbreviate as 1,2-PDO) has been a promising approach. In this work, high-performance catalysts containing copper carbide (CuxC) were prepared by the following procedure: (1) synthesis of Cu(OH)2-Zn(OH)2 mixture via a microchannel reaction system, (2) thermal treatment at 100 °C in 0.50 vol% C2H2/Ar gas, and (3) reduction at 300 °C under H2 atmosphere. The continuous synthesis of Cu(OH)2-Zn(OH)2 mixture in a microchannel reaction system yielded highly dispersed precursors, and the addition of ZnO led to improved dispersion of copper species with enhanced acidity. The new crystal phase, copper carbide (CuxC), was generated through reacting Cu(OH)2 particles with C2H2/Ar and subsequent hydrogen reduction. CuxC exhibited significantly higher hydrogenation activity than Cu metal, and contributed to enhanced catalytic activity for continuous glycerol hydrogenolysis in the fixed-bed reactor. Copper carbide composite catalyst (Cu/Zn = 8) afforded 100 % glycerol conversion and high selectivity (92.3 %) towards 1,2-PDO at 240 °C, 2.0 MPa and WHSV 3 h−1.

In situ synthesis of cuprous oxide on cotton fiber for developing functional textile with broad-spectrum antibacterial activity

The development of cotton fabrics with broad-spectrum antibacterial properties utilizing rapid and facile strategies remains an enormous challenge. The immobilization of cuprous oxide (Cu 2 O) onto cotton fiber is a promising method for develpoing organic-inorganic hybrid functional textile. Herein, aiming at designing an antibacterial nanolayer on the micro-dissolved cotton fiber surface, a novel method for rapid in-situ synthesis of Cu 2 O particles on cotton fibers in polydimethylsiloxane was proposed. In the instantaneous high temperature of polydimethylsiloxane with glucose reduction, the Cu 2 O particles could be constructed on the cotton fiber surface rapidly. Furthermore, the antibacterial cotton fabrics exhibited excellent broad-spectrum antibacterial performance against both the Gram-negative bacterium ( E. coli and P. aeruginosa ) and Gram-positive bacterium ( S. aureus and B. subtilis ). Therefore, the proposed method may be a promising strategy for the rapid preparation of antibacterial cotton fabric, which may provide an indispensability application on functional cellulose materials. • An antimicrobial layer was in-situ synthesized in an organic solvent system. • Cu 2 O particles could be rapidly synthesized on the cotton fiber surface. • Excellent antibacterial performance was achieved for typical bacterium.

Synthesis of CuII and CdII Metal-Organic Frameworks Based on 4,5-Bis(1-hydroxytetrazol-5-yl)-1,2,3-triazole and Their Effects as the Catalyst in Ammonium Perchlorate Thermal Decomposition.

Two new three-dimensional (3D) energetic metal-organic frameworks (EMOFs), namely, [Cu(OBTT)(NC2H8)2]n (1) and [Cd3(OBTT)2(H2O)2]n·4H2O (2), where H3OBTT = 4,5-bis(1-hydroxytetrazol-5-yl)-1,2,3-triazole, were prepared, and their structures were characterized by single-crystal X-ray diffraction analysis, which revealed that the EMOFs feature a rigid 3D framework architecture. The possibility of these two EMOFs as potential catalysts for the thermal decomposition of ammonium perchlorate (AP) was investigated. The results show that they have significant catalytic activity, up to reducing the peak temperature of AP decomposition from 704.0 to 613.6 K and contracting the decomposition temperature range from 451 to 320 K, which is almost one-third less than the decomposition temperature range of pure AP. The Kissinger and Ozawa-Doyle methods were used to calculate the kinetic parameters of the thermal decomposition of pure and mixed AP samples. The experimental results suggest that compound 1 has potential applications in the field of explosives and propellants. All properties suggest that compound 1 can be used as a potential catalyst.

Heterogeneous to homogeneous Cu–Ag nanoparticles by laser reduction in liquid

Controlling the compositional structure of Cu–Ag bimetallic nanoparticles (NPs) is challenging due to the immiscibility of copper and silver. We report synthesis of Cu–Ag NPs with tunable compositions and structures using femtosecond laser reduction in liquid (LRL) of solutions containing copper and silver complexes dispersed in a mixture of methanol and isopropyl alcohol. Either janus or homogeneous alloy structure of Cu–Ag NPs are produced, depending on the concentration of precursors in solution. The synthesized NPs also exhibit elemental compositions in line with Cu and Ag precursor ratios. The nonequilibrium reaction conditions of LRL produce a high density of randomly distributed Ag and Cu atoms that undergo rapid cooling as they coalesce into NPs, making LRL one of the few methods for the synthesis of homogeneous CuAg alloy NPs.

Fabrication of polyhedral Cu–Zn oxide nanoparticles by dealloying and anodic oxidation of German silver alloy for photoelectrochemical water splitting

A significant effort has been dedicated to the synthesis of Cu–Zn oxide nanoparticles as a robust photocathode material for photoelectrochemical water splitting. Cu–Zn oxide nanoparticles were formed by controlled anodization of German silver (Cu–Zn–Ni) alloy in an aqueous electrolyte. Scanning electron microscopy (SEM) demonstrates the dependence of the obtained nanostructures on the anodization time. The X-ray diffraction (XRD) patterns showed the formation of copper oxide (CuO) and zinc oxide (ZnO) nanoparticles with good stability. This was also confirmed by the compositional X-ray photoelectron spectroscopy (XPS) analysis. The obtained polyhedral nanoparticles showed high optical activity with adequate bandgap energy. These optimized nanoparticles achieved boosted photocurrent of − 0.55 mA/cm2 at − 0.6 V vs. SCE under AM 1.5 illumination, confirming the role of the optimized dealloying and thermal treatment in tuning the photoelectrochemical performance of the material.

The Synthesis of Cu–Mn–Al Mixed-Oxide Combustion Catalysts by Co-Precipitation in the Presence of Starch: A Comparison of NaOH with Organic Precipitants

Cu–Mn mixed oxides are well known as active combustion catalysts. The common method for their synthesis is based on co-precipitation, with NaOH as a precipitant, and is burdened with the possibility of introducing undesired Na contamination. This work describes the use of two organic bases, tetrabutylammonium hydroxide and choline hydroxide, as precipitating agents in a novel alkali-free route for Cu–Mn–Al catalyst synthesis. To obtain fine crystalline precursors, which are considered advantageous for the preparation of active catalysts, co-precipitation was carried out in the presence of starch gel. Reference materials prepared with NaOH in the absence of starch were also obtained. Mixed oxides were produced by calcination at 450 °C. The precursors contained MnCO3 doped with Cu and Al, and an admixture of amorphous phases. Those prepared in the presence of starch were less crystalline and retained biopolymer residues. The combustion of these residues during calcination enhanced the formation of larger amounts of the Cu1.5Mn1.5O4 spinel phase, with better crystallinity in comparison to catalysts prepared from conventionally synthesized precursors. Tests of toluene combustion demonstrated that the catalysts prepared with starch performed better than those obtained in starch-free syntheses, and that the mixed oxides obtained by the alkali-free route were more active than catalysts prepared with NaOH. Catalytic data are discussed in terms of property–performance relationships.

Facile synthesis of Cu NPs@Fe3O4-lignosulfonate: Study of catalytic and antibacterial/antioxidant activities.

Environmental pollution is one of the important concerns for human health. There are different types of pollutants and techniques to eliminate them from the environment. We hereby report an efficient method for the remediation of environmental contaminants through the catalytic reduction of the selected pollutants. A green method has been developed for the immobilization of copper nanoparticles on magnetic lignosulfonate (Cu NPs@Fe3O4-LS) using the aqueous extract of Filago arvensis L. as a non-toxic reducing and stabilizing agent. The characterization of the prepared Cu NPs@Fe3O4-LS was achieved by vibrating sample magnetometer (VSM), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), high resolution TEM (HRTEM), X-ray diffraction (XRD), scanning TEM (STEM), thermogravimetry-differential thermal analysis (TG/DTA), fast Fourier transform (FFT), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron (XPS) analyses. The synthesized Cu NPs@Fe3O4-LS was applied as a magnetic and green catalyst in the reduction of congo red (CR), 4-nitrophenol (4-NP), and methylene blue (MB). The progress of the reduction reactions was monitored by UV-Vis spectroscopy. Finally, the biological properties of Cu NPs@Fe3O4-LS were investigated. The prepared catalyst demonstrated excellent catalytic efficiency in the reduction of CR, 4-NP, and MB in the presence of sodium borohydride (NaBH4) as the reducing agent. The appropriate magnetism of Cu NPs@Fe3O4-LS made its recovery very simple. The advantages of this process include a simple reaction set-up, high and catalytic antibacterial/antioxidant activities, short reaction time, environmentally friendliness, high stability, and easy separation of the catalyst. In addition, the prepared Cu NPs@Fe3O4-LS could be reused for four cycles with no significant decline in performance.

Combination of chemo and bio-based materials for the synthesis of Cu- Persimmon tannin -Perlite catalyst and its application for organic reaction

Cu-Persimmon tannin-Perlite (Cu-PT-P) composite was synthesized as a novel heterogenous organocatalyst by cross-linking reaction and using bio-based materials such as perlite and Persimmon tannin. The synthesis of Cu-PT-P composite was confirmed by several analyses, and the results were shown high stability of this catalyst. One of the important reactions in organic chemistry is Knoevenagel condensation reaction, which used for the synthesis of biologically compounds, and Cu-PT-P composite was applied to catalyze several aromatic aldehydes and malononitrile. The conditions of reaction were optimized under various solvents, catalyst-loading amounts, and time reaction. When ethanol was mixed to other compounds, maximum catalytic activity was obtained with high yield and short time, and Cu-PT-P composite can be recycled for five times without decrease of its activity. Based on the findings, Cu-PT-P composite can be applied for organic reaction as an inexpensive and benefit catalyst.

Cu–Au nanoparticles produced by the aggregation of gas‐phase metal atoms for CO oxidation

AbstractAlloy nanoparticles (nanoalloys) are widely applied in heterogeneous catalysts, advanced electrodes, biomaterials, and other areas. The properties of nanoalloys can be tuned to a significant extent by their structures and compositions, which are governed by the employed synthetic procedure. Often such synthesis occurs in non‐equilibrium conditions and yields nanoalloys with structures and properties that are different from those obtained in thermodynamic equilibrium. In this work, we characterize how the non‐equilibrium conditions during the synthesis of Cu–Au alloys via physical vapor deposition (PVD) affect their morphology, composition, electronic structure, and reactivity in CO oxidation. We used molecular dynamics to simulate the PVD synthesis of Cu–Au nanoalloys through the non‐isothermal aggregation of Cu and Au atoms at a 3:1 ratio in the Ar atmosphere to obtain realistic structures of Cu–Au nanoparticles. Due to the different aggregation kinetics of Au and Cu atoms, the average Au concentration in the obtained Cu–Au particles varied between 14% and 50% depending on the nanoparticle size and the aggregation time. Density functional simulations revealed that the reactivity of the obtained Cu–Au clusters toward CO and oxygen as well as Brønsted–Evans–Polanyi relations for CO oxidation significantly depend on whether the clusters had fcc, icosahedral, or amorphous structures and do not strongly correlate with the d‐band centers of the adsorption sites. Our study highlights the importance of the non‐equilibrium character of nanoalloy structure and composition for their electronic structure and catalytic properties. The performed analysis of the reactivity of Cu–Au clusters with realistic structures in CO oxidation will help the optimization of Cu–Au catalysts for this societally important reaction.

Synthesis of Cu–TiO2/CuS p-n heterojunction via in situ sulfidation for highly efficient photocatalytic NO removal

Cu doped TiO2/CuS (Cu–TiO2/CuS) p-n heterojunction was synthesized via in situ sulfidation method for efficient photocatalytic removal of NO at ppb-level. The results show that optimized Cu–TiO2/CuS heterojunction possessed a maximum efficiency of 85% for the removal of NO under visible light irradiation, which was approximately 8.5, 4.3 and 1.2 times that of CuS, TiO2 and Cu–TiO2, respectively. The improved photocatalytic performance is attributed to the enhancement of visible light absorption and charge carrier separation induced by the construction of p-n heterojunction. Meanwhile, the p-n heterojunction charge transfer mechanism of Cu–TiO2/CuS was verified by systematic investigations. The appropriate band structures of the two components and the internal electric field formed at the interface of the heterojunction were two factors for this charge transfer mechanism. Furthermore, the role of active species in NO removal was explored, and the corresponding mechanism for NO removal of the heterojunction was proposed. This work provides a promising approach for the synthesis of heterojunction photocatalysts and facilitates the application of photocatalysts in sustainable and efficient pollutant removal.

Triazole-Based Cu(I) Cationic Metal–Organic Frameworks with Lewis Basic Pyridine Sites for Selective Detection of Ce3+ Ions

A highly symmetric bis-triazole-pyridine-based organic ligand, i.e., 3,5-di(4H-1,2,4-triazol-4-yl)pyridine (L), and Cu(II) salts were used to synthesize three cationic Cu(I) metal-organic frameworks (MOFs), namely, {[Cu(L)]·(NO3)·(H2O)}n (1), {[Cu(L)]·(BF4)·0.5H2O}n (2), and {[Cu1.25(L)]·1.25(ClO4)·H2O}n (3). All three MOFs have nonbonded anions situated inside the pore spaces. Both 1 and 2 have a two-dimensional network structure, while 3 has a three-dimensional structure. All three MOFs were characterized using Fourier transform infrared spectroscopy, elemental (C, H, and N) analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. Due to the presence of a Lewis basic pyridine moiety, these MOFs could serve as luminescent probes for the selective detection of Ce3+ ions with excellent efficiency (10-7 M). The synthesis of Cu(I)-based MOFs and their use to detect Ce3+ ions in water via a turn-on fluorescence process have rarely been reported. These MOFs are highly stable in water, are recyclable, and function efficiently at different pH values.

One-step synthesis of Cu(OH)2-Cu/Ni foam cathode for electrochemical reduction of nitrate

Nitrate (NO3−) pollution in natural water is severe and brings serious environmental and human health problems. With the rise of electrocatalytic NO3− reduction, highly reactive and selective electrodes are essential for the electrochemical reduction of NO3−. In this study, a one-step hydrothermal method was used to load Cu and Cu(OH)2 on Ni foam (NF) (Cu(OH)2-Cu/NF) as a cathode. The system’s unique design includes: Cu and Ni can promote the reduction of NO3− and the generation of active hydrogen atom (H*) as a reducing agent. Then, Cu(OH)2 is beneficial to NO2− adsorption and promotes the reduction of NO2− intermediate. Finally, NH4+ is oxidized to N2 by reactive chlorine generated at the anode. The Cu(OH)2-Cu/NF electrode exhibits a 91.5 % conversion of NO3−-N in 90 min, which is 44 times higher than that of NF. Under 2000 mg/L Cl−, NH4+ finally oxidizes to N2 within 360 min, and N2 selectivity is 95.60 %. In addition, the Cu(OH)2-Cu/NF electrode maintained an excellent electrochemical performance after 20 cycles. This study provided a new idea for designing efficient, stable, and inexpensive NO3− reduction electrodes.