Copper Acetylacetonate Research Articles

Fluidized Bed Chemical Vapor Deposition of Copper on Micronic Alumina Powders

AbstractUniformly coating micronic particles with metals is of main interest for a broad range of applications. This study demonstrates the feasibility of depositing pure copper on the surface of micronic alumina particles by the fluidized bed chemical vapor deposition process from the cheap and nontoxic copper acetylacetonate precursor. Thanks to the development of a preconditioning protocol, a complete fluidization of the particles organized as porous agglomerates was reached. The coating of the individual particles was favored by using conditions involving low deposition rates. The influence of key operating parameters on the process behavior and on the characteristics of the deposit was studied. The deposited copper was of cubic crystal structure without carbon nor oxide contamination.

Membrane-Free Selective Semi-Hydrogenation of Alkynes Over an In Situ Formed Copper Nanoparticle Electrode.

Selective semi-hydrogenation of alkynes is a significant reaction for preparing functionalized alkenes. Electrochemical semi-hydrogenation presents a sustainable alternative to the traditional thermal process. In this research, affordable copper acetylacetonate is employed as a catalyst precursor for the electrocatalytic hydrogenation of alkynes, using MeOH as the hydrogen source in an undivided cell. Good to excellent yields for both aromatic and aliphatic internal/terminal alkynes are obtained under constant current conditions. Notably, up to 99% Z selectivity is achieved for various internal alkynes. Mechanistic investigations revealed the formation of copper nanoparticles (NPs) at the cathode during electrolysis, acting as the catalyst for the selective semireduction of alkynes. The copper NPs deposited cathode demonstrated reusable for further hydrogenation.

Influence of pH value of precursor on growth, structural, and optical properties of Cu2O thin films grown in Mist-CVD

The Cu2O thin films were prepared from copper (II) acetylacetonate (Cu(acac)2) by the mist chemical vapor deposition (mist-CVD) method, depending on the pH value of the prepared solution. It was confirmed that the well-oriented Cu2O thin films were grown at a dominant (111) peak according to X-ray diffraction (XRD) measurement using an alkaline precursor solution. The pH of the prepared solution drastically affected the surface morphology of the Cu2O thin films, and the lowest Root Means Square (RMS) was found for pH-10 of the precursor solution. The confocal Raman spectrum confirmed the formation of the cubic Cu2O crystal structures for each pH value of the precursor solution. The very transparent Cu2O thin films that were grown. The highest transmittance, 70%, was obtained at 1100 nm from the absorption spectrum for Sample B. The optical energy band gaps of Cu2O thin films were determined using Tauc's method and found to vary within a range of 2.53 to 2.49 eV, indicating a change in the material's electronic structure. The study demonstrated the crucial role of the pH level of the prepared solution in the growth of the Cu2O thin film. Specifically, it was found that a higher pH level resulted in a greater concentration of hydroxide ions (OH−), which was a crucial factor in the growth process. These findings can be significant in using p-type Cu2O thin films prepared based on mist-CVD for optoelectronic applications.

The Catalytic Curing Reaction and Mechanical Properties of a New Composite Resin Matrix Material for Rocket Fuel Storage Tanks

In this paper, an equimolar blend of bisphenol A dipropargyl ether and cyanate ester was selected to study the effect of different catalysts on the curing reaction of a bisphenol A dipropargyl ether and cyanate ester blended resin system, and the thermal stability and mechanical properties of the catalytically cured blended resin system were investigated. Acetylacetone salts of transition metals and dibutyl ditin laurate reduced the curing temperature of bisphenol AF-type di cyanate ester, and copper acetylacetonate at a mass fraction of 0.3% significantly reduced the curing temperature of bisphenol AF-type di cyanate ester to less than 473 K. Bisphenol A dipropargyl ether pr-polymerized and equimolarly blended with bisphenol A di cyanate ester and bisphenol E-type di cyanate ester also cured below 473 K under the same conditions. Among the cured compounds of the blended resins of bisphenol A dipropargyl ether with bisphenol AF-type di cyanate ester, bisphenol A-type di cyanate ester and bisphenol E-type di cyanate ester, the blended resins of bisphenol A-type di cyanate ester and bisphenol E-type di cyanate ester have better overall performance. The residual rate of 873 K in air was 38%, and the flexural strength, flexural modulus, and impact strength were 129.4 MPa, 4.3 GPa, and 27.3 kJ·m−2, respectively. This kind of blended resin is expected to be used in the liquid oxygen storage tanks of rockets.

Bifunctional Interface Passivation via Copper Acetylacetonate for Efficient and Stable Perovskite Solar Cells.

Manipulating interface defects can minimize interfacial nonradiative recombination, thus increasing the stability and performance of perovskite solar cells (PSCs). Here, copper acetylacetonate [Cu(acac)2] as a passivator is used to treat the interface between Spiro-OMeTAD and perovskite. Owing to the strong chelation, the uncoordinated Pb2+ could react with -C═O/-COH functional groups, firmly anchoring acetylacetonate at this interface or the grain boundaries (GBs) of perovskite films to construct multiple ligand bridges, accompanied by the p-type copper iodide formation with copper substituting lead. Simultaneously, Cu+-Cu2+ pairs transfer electrons from Pb0 to I0, suppressing deep level defects of Pb0 and I0 near the perovskite interface. These can be beneficial to hole-transferring. Moreover, the Schiff base complexes with hydrophobicity, from the reaction of acetylacetonate with perovskite, can lead to tightly packed adjacent perovskite surfaces and self-seal the GBs of the perovskite, inhibiting moisture diffusion for long-term stability. Consequently, the Cu(acac)2-based PSC has achieved more than 24% champion efficiency while retaining ca. 92% of the initial power conversion efficiency after 1680 h of storage.

Acylthiourea oligomers as promising reducing agents for dimethacrylate-based two-component dental materials.

Currently used thiourea-based two-component dental materials may release bitter compounds if they are not properly cured. To address this issue, the objective of this study was to evaluate the potential of acylthiourea oligomers as reducing agents for the development of self-cure composites. Acylthiourea oligomers ATUO1-3 were synthesized via cotelomerization of the acylthiourea methacrylate ATU1 with butyl methacrylate. They were characterized by 1H NMR spectroscopy and size exclusion chromatography. Self-cure composites based on the redox initiator system cumene hydroperoxide/acylthiourea oligomer/copper(II) acetylacetonate were formulated. The flexural strength and modulus were measured using a three-point bending setup. The double bond conversions were determined using NIR spectroscopy. The working time of each self-cure composite was measured using an oscillating rheometer. Leaching experiments using light-cure composites were performed in DMSO-d6. Acylthiourea oligomers ATUO1-3 were successfully synthesized in good yields. Both the oligomer molecular weight and the amount of thiourea groups were varied. Self-cure composites containing ATUO1 or ATUO2 as reducing agents exhibited excellent mechanical properties and high double-bond conversions. The amounts of reducing agent, cumene hydroperoxide and copper(II) acetylacetonate were shown to have a significant impact on the working time. Moreover, a correlation between flexural modulus and the amount of metal salt was clearly established. Self-cure composites containing the oligomer ATUO1 exhibited a longer working time than materials containing ATU1 or acetylthiourea. Contrary to acetylthiourea, ATUO1 was not able to leach out of light-cured composites. Acylthiourea oligomers are promising reducing agents for the formulation of two-component dental materials that do not induce a bitter taste in mouth.

One-Pot Graphene Supported Pt3Cu Nanoparticles—From Theory towards an Effective Molecular Oxygen Reduction Reaction Catalyst

In this work, recent research progresses in the formation of Pt3Cu nanoparticles onto the surface of graphene are described, and the obtained results are contrasted with previously published theoretical studies. To form these nanoparticles, tetrabutylammonium hexachloroplatinate, and copper acetylacetonate are used as platinum and copper precursors, respectively. Oleylamine is used as a reductor and a solvent. The obtained catalyst is characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive spectroscopy X-ray (EDS). To assess the catalytic activity, the graphene-supported Pt3Cu material is tested with cyclic voltammetry, “CO stripping”, and oxygen reduction reaction potentiodynamic curves to find the nature and the intrinsic electrochemical activity of the material. It can be observed that the tetrabutylammonium cation plays a critical role in anchoring and supporting nanoparticles over graphene, from which a broad discussion about the true nature of the anchoring mechanism was derived. The growth mechanism of the nanoparticles on the surface of graphene was observed, supporting the conducted theoretical models. With this study, a reliable, versatile, and efficient synthesis of nanocatalysts is presented, demonstrating the potentiality of Pt3Cu/graphene as an effective cathode catalyst. This study demonstrates the importance of reliable ab inito theoretical results as a useful source of information for the synthesis of the Pt3Cu alloy system.

Selective Oxidation of Cyclohexane to Cyclohexanol/Cyclohexanone by Surface Peroxo Species on Cu-Mesoporous TiO2.

Selective oxidation of cyclohexane to cyclohexanol/cyclohexanone (KA-oil) is an important chemical process, which is still constrained by low conversion and selectivity and high energy consumption. In this study, Cu-doped mesoporous TiO2 (Cu-MT) has been successfully synthesized via calcinating MIL-125(Ti) doped with copper acetylacetonate, which shows high reactivity in selective oxidation of cyclohexane to KA-oil by persulfate (PS) with the desirable cyclohexane conversion of 16.8% and a selectivity of 98.0% under mild conditions and the low ratio of PS/cyclohexane of 1:1. A series of characterizations and density functional theory calculations reveal that the doped Cu(I,II) on Cu-MT is the reactive site for non-radical activation of PS with the moderate elongation of the O-O bond in PS, which then abstracts 1H (1H+ + 1e-) from cyclohexane to form Cy• and eventually KA-oil. This study gives new insight on the importance of moderately activated PS in selective oxidation of C-H.

Atomic layer deposition of Cu2O using copper acetylacetonate

Cu2O is an important p-type semiconductor material with applications in thin-film transistors, photovoltaics, and water splitting. For such applications, pinhole-free and uniform thin films are desirable, thus making atomic layer deposition (ALD) the ideal fabrication technique. However, existing ALD Cu precursors suffer from various problems, including limited thermal stability, fluorination, or narrow temperature windows. Additionally, some processes result in CuO films instead of Cu2O. Therefore, it is important to explore alternative precursors and processes for ALD of Cu2O thin films. In this work, we report the successful deposition of Cu2O using copper acetylacetonate as a precursor and a combination of water and oxygen as reactants at 200 °C. Saturation of the deposition rate with precursor and reactant dose time was observed, indicating self-limiting behavior, with a saturated growth-per-cycle of 0.07 Å. The Cu2O film was polycrystalline and uniform (RMS roughness ∼2 nm), with a direct forbidden bandgap of 2.07 eV and a direct allowed bandgap of 2.60 eV.

Experimental and theoretical studies of carbon monoxide oxidation over W/Cu/Ce trimetallic oxides: the effect of W addition

It is a significant method to prepare highly dispersed polymetallic oxides using in-situ doping metal organic frameworks as precursors. Herein, a series of straw-like W/Cu/Ce trimetallic oxides were prepared by using phosphotungstic ionic liquid@Ce-based metal organic framework adsorbing with copper acetylacetonate as precursors. The effect of W content on catalytic activity of W/Cu/Ce trimetallic oxides for carbon monoxide (CO) oxidation was well-investigated. Comprehensive characterization methods and density functional theory calculations were adopted to reveal the property changes of Cu/CeO2 catalyst by the addition of W. The results demonstrated that W, Cu, and Ce are highly dispersed in the prepared W/Cu/Ce trimetallic oxides, and adding proper amount of W can improve the activity of the catalyst. H2 temperature-program reduction profiles, X-ray photoelectron spectroscopy, in-situ diffuse reflectance infrared Fourier transform spectroscopy, and density functional theory calculations clearly revealed that after the addition of W, the strength of Ce-O bond is weakened, the oxygen vacancy is increased, and the adsorption of CO is enhanced, respectively, which are vital reasons for its high catalytic activity. In addition, the CO oxidation reaction pathway over prepared W/Cu/Ce trimetallic oxides based on the Mars-van Krevelen mechanism was studied, and the results exhibited that CO can wrest the lattice oxygen of W/Cu/Ce trimetallic oxides to form CO2, which is also proved to be the rate-determining step in reaction process.

Solubility of Copper(II) Acetylacetonate in Supercritical Carbon Dioxide as the Basis for Polymer Composite Modification Technology

Solubility of Copper(II) Acetylacetonate in Supercritical Carbon Dioxide as the Basis for Polymer Composite Modification Technology

A novel colorimetric detection of glutathione based on stable free radical TEMPO oxidation of 3,3′,5,5′−tetramethylbenzizine (TMB) via Copper(II) acetylacetonate catalysis

In this work, a new colorimetric method for the determination of Glutathione (GSH) on the basis of stable free radical 2,2,6,6 − tetramethylpiperidine − 1 − oxyl (TEMPO) oxidation of 3,3′,5,5′−tetramethylbenzizine (TMB) via copper(II) acetylacetonate (Cu(acac)2) catalysis was proposed. TEMPO was catalyzed by Cu(acac)2 to produce TEMPO+, then TEMPO+ oxidized TMB to produce oxidized TMB (ox − TMB). The resulting ox − TMB showed blue and possessed a distinct absorption peak about 650 nm. Whereas, GSH prohibited the generation of ox − TMB through inhibiting TMB oxidation. As compared to the case that GSH was absent, significantly enhanced absorption was determined, and was proportional to GSH amount. On this basis, a qualitative and quantitative detection method of GSH with the naked eye and the microplate reader was achieved. The developed TEMPO − based method achieved GSH biosensing with improved sensitivity in a good specificity − manner. The limit of detection (LOD) was 90 μM via naked eye, and the microplate reader was 4.71 μM. And the stable free radical TEMPO possessed higher stability and lower toxicity than traditional oxidant of H2O2. Moreover, this TEMPO − based method achieved good results in the detection of GSH in human serums.

Hyaluronic-Acid-Tagged Cubosomes Deliver Cytotoxics Specifically to CD44-Positive Cancer Cells.

Delivery of chemotherapy drugs specifically to cancer cells raises local drug doses in tumors and therefore kills more cancer cells while reducing side effects in other tissues, thereby improving oncological and quality of life outcomes. Cubosomes, liquid crystalline lipid nanoparticles, are potential vehicles for delivery of chemotherapy drugs, presenting the advantages of biocompatibility, stable encapsulation, and high drug loading of hydrophobic or hydrophilic drugs. However, active targeting of drug-loaded cubosomes to cancer cells, as opposed to passive accumulation, remains relatively underexplored. We formulated and characterized cubosomes loaded with potential cancer drug copper acetylacetonate and functionalized their surfaces using click chemistry coupling with hyaluronic acid (HA), the ligand for the cell surface receptor CD44. CD44 is overexpressed in many cancer types including breast and colorectal. HA-tagged, copper-acetylacetonate-loaded cubosomes have an average hydrodynamic diameter of 152 nm, with an internal nanostructure based on the space group Im3m. These cubosomes were efficiently taken up by two CD44-expressing cancer cell lines (MDA-MB-231 and HT29, representing breast and colon cancer) but not by two CD44-negative cell lines (MCF-7 breast cancer and HEK-293 kidney cells). HA-tagged cubosomes caused significantly more cell death than untargeted cubosomes in the CD44-positive cells, demonstrating the value of the targeting. CD44-negative cells were equally relatively resistant to both, demonstrating the specificity of the targeting. Cell death was characterized as apoptotic. Specific targeting and cell death were evident in both 2D culture and 3D spheroids. We conclude that HA-tagged, copper-acetylacetonate-loaded cubosomes show great potential as an effective therapeutic for selective targeting of CD44-expressing tumors.

Surface modification of nitrile membranes by DBD plasma and their antibacterial properties

Surface modification of nitrile membranes to achieve antibacterial activities is of great importance. In the present study, an atmospheric pressure DBD plasma setup is used for the surface modification of nitrile membranes, where silver nanoparticles and copper oxides particles prove to be generated from silver acetylacetonate (Ag(acac)) and copper acetylacetonate (Cu(acac)2). Complementary characterization has been performed to study the plasma-derived products as well as the modified membranes, such as XRD, TEM, FT-IR, SEM, AFM, EDX, XPS, OES, etc. It is shown crystalline Ag nanoparticles and CuOx particles are directly prepared by the DBD plasma setup, which can be strongly absorbed on the surface of the nitrile membranes. Based on the experiment results and previous studies, the plasma surface modification process is discussed. Antibacterial tests against Escherichia coli (E. coli) and Staphylococcus epidermidis (S. epidermidis) show the AgNPs-deposited nitrile membranes possess apparent antibacterial activities, in contrast to the CuOx particles-deposited membranes. This simple, rapid, and flexible plasma process together with the antibacterial activities of membranes is expected to provide guidance for the surface modification of polymers with desired properties.

Cu-Electrocatalytic Diazidation of Alkenes at ppm Catalyst Loading

The 1,2-diamine motif is prevalent in natural products, small-molecule pharmaceuticals, and catalysts for asymmetric synthesis. Transition metal catalyzed alkene diazidation has evolved to be an attractive strategy to access vicinal primary diamines but remains challenging, especially for practical applications, due to the restriction to a certain type of olefins, the frequent use of chemical oxidants, and the requirement for high loadings of metal catalysts (1 mol % or above). Herein we report a scalable Cu-electrocatalytic alkene diazidation reaction with 0.02 mol % (200 ppm) of copper(II) acetylacetonate as the precatalyst without exogenous ligands. In addition to its use of low catalyst loading, the electrocatalytic method is scalable, compatible with a broad range of functional groups, and applicable to the diazidation of α,β-unsaturated carbonyl compounds and mono-, di-, tri-, and tetrasubstituted unactivated alkenes.

Polymerizable thioureas as innovative reducing agents for self-cured and dual-cured dental materials

ObjectiveTo evaluate polymerizable acylthioureas as reducing agents in two-component dental materials. MethodsAcylthioureas 1 and 2 were synthesized and characterized by 1H and 13C NMR spectroscopy. Self-cured composites based on the redox initiator system cumene hydroperoxide/acylthiourea 1 or 2/copper(II) acetylacetonate were formulated. Various amounts of cumene hydroperoxide, acylthiourea and copper(II) acetylacetonate were used. An equimolar cumene hydroperoxide/acylthiourea ratio was selected for each self-cured composite. The reactivity and the final double-bond conversions obtained with these two-component materials was assessed using RT-FTIR spectroscopy. The flexural strength and modulus were measured using a three-point bending setup, after storage of the specimens for 45 min at 37 °C (dry) and for 24 h in water at 37 °C. The working time of each composite was determined using an oscillating rheometer. ResultsAcylthioureas 1 and 2 were synthesized in three to four steps. In combination with cumene hydroperoxide and copper(II) acetylacetonate, both prepared compounds were found to be effective reducing agents. The higher the amount of cumene hydroperoxide and acylthiourea in the self-cured composite, the higher the flexural modulus and the faster the polymerization (lower working times). Similarly, it was shown that increased copper(II) acetylacetonate amounts result in an acceleration of the curing as well as in an improvement of the mechanical properties. The self-cured composite containing 1.25 wt% of cumene hydroperoxide in the monomer mixture of the first paste and 2.00 wt% of acylthiourea 1 in the monomer mixture of the second one provided excellent mechanical properties as well as an optimal working time. SignificancePolymerizable acylthioureas can be used as reducing agents in two-component dental materials. Due to the presence of the methacrylate group, such structures should be efficiently incorporated into the network during polymerization and should not leach out of the composite after curing. As a result, such dental materials are not expected to exhibit bitterness properties.

An investigation of Cu‐ZrO 2 ‐TiO 2 / CNTs anode material for lithium‐ion batteries

Material Cu-ZrO2-TiO2/CNTs was prepared through the thermal decomposition of metal organic polymer/carbon nanotubes (CNTs) composite [CuxZrmTil(OCH2CH2O)2(m + l) + x]n/CNTs, which was synthesized through the polymerization of ethylene glycol with metal organic compounds titanium tetra-isopropanolate, zirconium tetra-n-butoxide, and copper acetylacetonate in the presence of CNTs. Higher specific capacity and higher rate capability (351 mAh g−1 at 100 mA g−1, 196 mAh g−1 at 2000 mA g−1) were reached. The reasons for the excellent electrochemical performances of the material could be found from the following aspects. In the thermal decomposition process of the metal organic polymer, nano pores were created in the metal oxide phase and at the same time, part of Ti4+ and Cu2+ cations were reduced to Ti3+ ions and metal Cu. The substitution of Ti4+ ions by Ti3+ ions in TiO2 phase could form oxygen vacancies in the bulk of the material. The nano pores and the oxygen vacancies in Cu-ZrO2-TiO2/CNTs could offer large number of diffusion channels for lithium ions and open up more Li+ ion storage positions to receive Li+ ions at high rate. The presences of the oxygen vacancies, the Ti3+ ions, and the metal copper in the material could enhance the electric conductivity of the material. The investigation results show that the presence of Zr4+ ions in the material could stabilize the pore structure. The stable pore structure, the oxygen vacancies, and the good electric conductivity of the material render a highly efficient anode material for Li+ batteries. A cycling life-time test shows that the Cu-ZrO2-TiO2/CNTs anode material gives a specific capacity of 351 mA h g−1 at 100 mA g−1 and a capacity retention rate of 92% after 200 cycles of charge/discharge.

Temperature and Tumor Microenvironment Dual Responsive Mesoporous Magnetic Nanospheres for Magnetothermal Effect-Induced Cancer Theranostics

Temperature and Tumor Microenvironment Dual Responsive Mesoporous Magnetic Nanospheres for Magnetothermal Effect-Induced Cancer Theranostics

An extraction-based facile method for measuring the solubility of organic solid compounds in supercritical carbon dioxide

Due to its dual gas- and liquid-like properties, supercritical carbon dioxide (scCO2) is considered an excellent solvent for dissolving precursors and penetrating nanoscale pores. After subsequent calcination, uniformly dispersed metal or metal oxide nanoparticles or nanowires can be obtained. Organometallic salts are commonly used precursors in this method because they usually have high solubility in scCO2. Therefore, solubility data are essential for the controllable synthesis of such nanocomposites. This work establishes a facile and accessible method for measuring the solubility of organic solids in scCO2. The solubilities of copper acetylacetonate and cobalt acetylacetonate were obtained at temperatures of 313–333 K and pressures of 11–24 MPa. And the solubilities were within 2.3 × 10−2 to 14.1 × 10−2 g/L for Cu(acac)2 and 6.9 × 10−2 to 13.4 × 10−2 g/L for Co(acac)2. The experimental data were fitted to the semi-empirical model with the AARD values of 4.58% and 2.14% for Cu(acac)2 and Co(acac)2, respectively, and the obtained equations could be used to predict solubility of the same systems in the experimental range.

Affimer Tagged Cubosomes: Targeting of Carcinoembryonic Antigen Expressing Colorectal Cancer Cells Using In Vitro and In Vivo Models.

Nanomedicines, while having been approved for cancer therapy, present many challenges such as low stability, rapid clearance, and nonspecificity leading to off-target toxicity. Cubosomes are porous lyotropic liquid crystalline nanoparticles that have shown great premise as drug delivery vehicles; however, their behavior in vivo is largely underexplored, hindering clinical translation. Here, we have engineered cubosomes based on the space group Im3m that are loaded with copper acetylacetonate as a model drug, and their surfaces are functionalized for the first time with Affimer proteins via copper-free click chemistry to actively target overexpressed carcinoembryonic antigens on LS174T colorectal cancer cells. Unlike nontargeted cubosomes, Affimer tagged cubosomes showed preferential accumulation in cancer cells compared to normal cells not only in vitro (2D monolayer cell culture and 3D spheroid models) but also in vivo in colorectal cancer mouse xenografts, while exhibiting low nonspecific absorption and toxicity in other vital organs. Cancerous spheroids had maximum cell death compared to noncancerous cells upon targeted delivery. Xenografts subjected to targeted drug-loaded cubosomes showed a 5–7-fold higher drug accumulation in the tumor tissue compared to the liver, kidneys, and other vital organs, a significant decrease in tumor growth, and an increased survival rate compared to the nontargeted group. This work encompasses the first thorough preclinical investigation of Affimer targeted cubosomes as a cancer therapeutic.