Cu-doped ZnO Nanoparticles Research Articles

Effect of Cu Doping on ZnO Nanoparticles as a Photocatalyst for the Removal of Organic Wastewater.

Environmental problems with chemical and biological water pollution have become a major concern for society. Providing people with safe and affordable water is a grand challenge of the 21st century. The study investigates the photocatalytic degradation capabilities of hydrothermally prepared pure and Cu-doped ZnO nanoparticles (NPs) for the elimination of dye pollutants. A simple, cost-effective hydrothermal process is employed to synthesize the Cu-doped ZnO NPs. The photocatalytic dye degradation activity of the synthesized Cu-doped ZnO NPs is tested by using methylene blue (MB) dye. In addition, the parameters that affect photodegradation efficiency, such as catalyst concentration, starting potential of hydrogen (pH), and dye concentration, were also assessed. The dye degradation is found to be directly proportional to the irradiation time, as 94% of the MB dye is degraded in 2 hrs. Similarly, the dye degradation shows an inverse relation to the MB dye concentration, as the degradation reduced from 94% to 20% when the MB concentration increases from 5 ppm to 80 ppm. The synthesized cost-effective and environmentally friendly Cu-doped ZnO NPs exhibit improved photocatalytic activity against MB dye and can therefore be employed in wastewater treatment materials.

Use of tools of NLD in analysis and calibration of Cu-doped ZnO nanoparticles (NPs) for biological applications

Use of tools of NLD in analysis and calibration of Cu-doped ZnO nanoparticles (NPs) for biological applications

Green synthesis of Cu-doped ZnO nanoparticles and its application for the photocatalytic degradation of hazardous organic pollutants

In recent times, the synthesis of metal nanoparticles (NPs) using plant extracts has recently emerged as an intriguing issue in the field of nanoscience and nanobiotechnology, with numerous advantages over conventional physicochemical approaches. In the current study, ZnO NPs were synthesized from Synadium grantii leaf extricate with varying Cu-dopant concentrations. In order to the synthesis of the pure and Cu-doped ZnO NPs, zinc nitrate hexahydrate and copper nitrate trihydrate were used as a precursor in leaf extracts of the plant. XRD, TEM, FTIR, XPS, and PL measurements were carried out to examine the physical and optical properties of the synthesized samples. The photocatalytic studies of the prepared samples were studied using Methylene blue (MB), Indigo Carmine (IC), and Rhodamine B (RhB) organic pollutants. The wurtzite crystal structure of synthesized samples was confirmed by XRD and TEM analysis. Further, the presence of functional groups in the prepared samples was confirmed by FTIR analysis. XPS analysis confirmed that the binding energies of a host material and dopant ions. The emission peaks identified at 424, 446 and 573 nm are associated with the electron movement from the deep donor level, zinc interstitial to the zinc vacancy and oxygen vacancy. 3% and 5% Cu-doped samples exhibited superior photocatalytic activity for MB, IC, and RhB dyes. The green synthesized ZnO NPs showed enriched photocatalytic performance, signifying that bio-synthesis can be an outstanding approach to develop versatile and environmental products.

Investigation of the effect of amino-alcohol stabilizers on crystal structure, band gap and blue luminescence of Cu-doped ZnO nanoparticles prepared by sol-gel method

Investigation of the effect of amino-alcohol stabilizers on crystal structure, band gap and blue luminescence of Cu-doped ZnO nanoparticles prepared by sol-gel method

Cu-Doped ZnO Nanoparticles for Non-Enzymatic Glucose Sensing.

Copper-doped zinc oxide nanoparticles (NPs) CuxZn1−xO (x = 0, 0.01, 0.02, 0.03, and 0.04) were synthesized via a sol-gel process and used as an active electrode material to fabricate a non-enzymatic electrochemical sensor for the detection of glucose. Their structure, composition, and chemical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) and Raman spectroscopies, and zeta potential measurements. The electrochemical characterization of the sensors was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). Cu doping was shown to improve the electrocatalytic activity for the oxidation of glucose, which resulted from the accelerated electron transfer and greatly improved electrochemical conductivity. The experimental conditions for the detection of glucose were optimized: a linear dependence between the glucose concentration and current intensity was established in the range from 1 nM to 100 μM with a limit of detection of 0.7 nM. The proposed sensor exhibited high selectivity for glucose in the presence of various interfering species. The developed sensor was also successfully tested for the detection of glucose in human serum samples.

Preparation of Cu-doped ZnO nanoparticles via layered double hydroxide and application for dye-sensitized solar cells

It has been reported that doping ZnO with metal ions can alter the band gap and immensely enhance electron transport. In this regard, to increase the efficiency of cost-effective dye-sensitized solar cells (DSSCs), we synthesized Cu-doped ZnO nanocomposites from layered double hydroxide (LDH) precursors via a facile method. LDH layers were homogeneously doped with Cu ions, and mixed metal oxides (MMOs) were obtained after annealing. The morphology and optical and electrochemical properties of the as-synthesized Cu-doped ZnO nanocomposites were systematically studied. The introduction of Cu ions increases the specific surface area of ZnO and increases light absorption in the visible region. The Cu-doped ZnO MMOs were used as the photoanode of DSSCs, and the effect of the amount of the Cu dopant on the performance of the solar cells was studied. At the optimal doping weight percentage of Cu (0.25 wt%), the solar cell based on Cu-doped ZnO MMO and D149 dye achieved the highest short-circuit current of 7.12 mA cm−2 and the highest power conversion efficiency of 1.50%.

Improvement of dielectric properties of ZnO nanoparticles by Cu doping for tunable microwave devices

We report a facile chemical polyol method to synthesize Cu-doped ZnO nanoparticles with various levels of Cu. X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV–Visible diffuse reflectance spectroscopy techniques were used to analyze the structural and optical properties of Zn1−xCuxO nanoparticles. The crystallite size varies between 9.8 and 18.9 nm and decreased with the increase of Cu doping. The band energy gaps of pure and Cu-doped ZnO samples are in the range 2.5–3.1 eV. The dielectric properties, ac conductivity and impedance analysis of Zn1−xCuxO nanoparticles were systematically investigated. It was revealed that the doping of ZnO by Cu (with low Cu molar content) leads to obtain high dielectric constant and low tangent loss, which are very encouraging for microwave semiconductor devices.

Cu-Doped ZnO Nanoparticles as an Electrochemical Sensing Electrode for Cardiac Biomarker Myoglobin Detection

Cu-doped ZnO nanoparticles were used in the form of a screen-printed electrode on a prefabricated gold-plated electrode for electrochemically determining the concentration of nanomolar myoglobin (Mb), a cardiac biomarker. Initially, Cu-doped ZnO nanoparticles were synthesised through the sol gel method by using three Cu-doping concentrations (varying number of Cu atoms). Then, the synthesised material was analysed using X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and field emission secondary electron microscopy. Analysis revealed a mixed phase of ZnO and CuO, whereas the vibration band in the range of 650-700 cm -1 indicated metal oxide formation. Morphological observation showed uniform-sized spherical particles of approximately 15-20 nm (as nanoparticles) that were evenly distributed, which were also confirmed based on the average particle size estimated using XRD data. The developed electrodes were tested for biomarker concentration from 3 to 15 nM based on cyclic voltammogram and impedance spectroscopic curves, where the redox potential/current/charge transfer resistance changed linearly with Mb and dopant (Cu) concentration. The sensitivity was estimated as 2.13-10.14~μAnM -1 cm -2 with dopant concentration of approximately 0.46 nM as the limit of detection.

Dependence of the electrical properties of Cu-doped ZnO nanoparticles decorated by Ag atoms

Abstract Silver decorated copper doped zinc oxide nanoparticles (Ag@Cu-ZnO) were successfully prepared via sol gel method. X-ray diffraction analysis revealed ZnO wurtzite crystalline structure with the existence of minor peaks attributed to Cu and Ag. The presence of Cu and Ag in addition to ZnO lattice was supplementary verified by EDS data while the shift in the FTIR band confirmed the Cu incorporation within the ZnO host lattice. Both SEM and XRD revealed an increase in particle size with Ag loading. At different frequencies, electrical measurements demonstrated a decrement in the dielectric constant, dielectric loss and AC conductivity with the increment of Ag content. Meanwhile, the Nyquist plots of the impedance measurement showed a single semicircle arc indicating the predominance of grain boundary resistance. This study elucidated the great influence of Ag on Cu-doped ZnO nanoparticles’ structural, dielectric constant and electrical conductivity which make it a promising candidate for catalytic, photocatalytic and adsorption applications.

Dependence of the electrical properties of Cu-doped ZnO nanoparticles decorated by Ag atoms

Abstract Silver decorated copper doped zinc oxide nanoparticles (Ag@Cu-ZnO) were successfully prepared via sol gel method. X-ray diffraction analysis revealed ZnO wurtzite crystalline structure with the existence of minor peaks attributed to Cu and Ag. The presence of Cu and Ag in addition to ZnO lattice was supplementary verified by EDS data while the shift in the FTIR band confirmed the Cu incorporation within the ZnO host lattice. Both SEM and XRD revealed an increase in particle size with Ag loading. At different frequencies, electrical measurements demonstrated a decrement in the dielectric constant, dielectric loss and AC conductivity with the increment of Ag content. Meanwhile, the Nyquist plots of the impedance measurement showed a single semicircle arc indicating the predominance of grain boundary resistance. This study elucidated the great influence of Ag on Cu-doped ZnO nanoparticles’ structural, dielectric constant and electrical conductivity which make it a promising candidate for catalytic, photocatalytic and adsorption applications.

Visible light sensitive Cu doped ZnO: Facile synthesis, characterization and high photocatalytic response

The different concentrations of 0.0, 1.0, 2.5 and 5.0 wt% Cu-doped ZnO (Cu@ZnO) nanoparticles (NPs) have been synthesized for opto-photocatalytic applications by a facile and cost-effective route. The formation and structural analyses of Cu@ZnO NPs was recognized by X-ray diffraction (XRD), Fourier transform (FT)-Raman and Transmission electron microscopy (TEM). The average crystallite size of 28.9, 27.4 and 26.4 nm was calculated for (101) intense peak and found to be decreased with increasing the contents of Cu. The residual microstrain values are noted ~3.84 × 10−3, 4.03 × 10−3 and 4.19 × 10−3. The particle size of 170, 109, 127 and 175 nm is obtained for undoped and Cu doped ZnO NPs from FESEM. The optical band gap of Cu@ ZnO NPs were estimated through Kubelka-Munk theory and noted ~3.225, 3.150, 3.100 and 2.995 eV for 0.0, 1.0, 2.5 and 5.0 wt% Cu@ZnO NPs; this shows decreases with increasing the Cu contests in ZnO lattice. Photoluminescence (PL) spectra of Cu@ZnO NPs shows near band edge emission at 407–411 nm with emission band 565-572 nm correspond to intrinsic defects in ZnO lattice. The photocatalytic performance of Cu@ZnO NPs was assessed through decolourizing of methyl green beneath the visible light illumination (λ = 425–460 nm). Photocatalytic action of Cu@ZnO samples was 3.5 times greater to neat ZnO. Photocatalytic properties of Cu@ZnO NPs can be used for water purification in environmental applications.

Synthesis, Characterization and Evaluation of Antimicrobial, Antioxidant & Anticancer Activities of Copper Doped Zinc Oxide Nanoparticles

The present work reveals the influence of copper (Cu) doping in band gap energy level as well as selective cytotoxicity of ZnO nanoparticles against human breast cancer cells (MCF7), human cervical carcinoma (HeLa), and one normal (Vero) cell line. Cu-doped ZnO nanoparticles (Cu-ZnO NPs) were synthesized and validated by UV-Vis, FT-IR, XRD, SEM and EDX. Cu-doping diminished the band gap energy of ZnO NPs from 3.54 eV to 3.29 eV. Antimicrobial activity has been evaluated against three bacterial and fungal strains. Antioxidant activity was examined using a DPPH free radical, ABTS+ radicals, hydroxyl radicals and nitric oxide scavenging assay. Cu-ZnO NPs showed anticancer activity with IC50 value of 219.56 µg/mL against MCF7 and 137.27 µg/mL against HeLa cell lines. The doping of Cu with ZnO improved the selective cytotoxicity of ZnO NPs towards MCF7 and HeLa cells without affecting the normal cells.

Pure and Cu-Doped ZnO Nanoparticles: Hydrothermal Synthesis, Structural, and Optical Properties

Pure and Cu-doped zinc oxide (Zn1 –xCuxO with x = 0.00, 0.05, 0.10, and 0.15) nanoparticles were prepared via hydrothermal synthesis using a solution of zinc sulfate (ZnSO4) as precursor, p-phenylenediamine as structure-directing agent in the presence of different amounts of CuSO4 and NaOH. XRD, Raman, UV–Vis, and PL techniques were used to characterize the as-synthesized samples. The XRD analysis reveals that the average particle size of pure ZnO is 13.50 nm. It decreased to 12.11 nm for the Cu-doped sample Zn0.95Cu0.05O, then to 11.00 nm when x = 0.15 (Zn0.85Cu0.15O). The optical band gap of pure and Cu-doped ZnO nanoparticles was calculated from UV–Vis spectra. It turned out to have decreased from 3.18 to 3.11 eV as the amount of Cu increases up from x = 0 to 0.15. The photoluminescence study shows that the introduction of Cu into pure ZnO causes a decrease in surface defects, such as oxygen vacancy and zinc vacancy.

Designed synthesis of microstructure and defect-controlled Cu-doped ZnO–Ag nanoparticles: exploring high-efficiency sunlight-driven photocatalysts

Cu-doped ZnO nanoparticles composited with Ag were synthesized by a one-step sol-gel method in this work, aiming at highly photocatalytic activity and possible application under sunlight (especially near ultraviolet and visible light regions, 300–760 nm) irradiation. Scanning electron microscopy (SEM) shows that the introduction of Cu inhibits particle aggregation. X-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) reveal that Zn(Cu)O–Ag nanoparticles (CZA NPs) are composed of metallic Ag (Ag0) and Zn(Cu)O nanocrystals; while at the Cu concentration of higher than 2%, a few CuO nanocrystals appear. Transmission electron microscopy (TEM) results evidenced the well-defined formation of Zn(Cu)O–Ag and/or CuO–ZnO–Ag heterojunctions. UV–vis spectra display that the visible absorption of the samples is obviously enhanced after the Cu introduction. At a low Cu doping level (0.2%) and moderate Cu concentration (3%–5%), the blue and green photoluminescence (PL) emission strength of the samples becomes very weak in comparison to other samples, indicative of the high separation of photogenerated electron-hole pairs. Reasonably, the higher photocatalytic degradation (complete degradation of methylene blue (MB) and methyl orange (MO) within 40 min under the simulated sunlight irradiation) are achieved in these cases: low Cu doping level (0.2%) and moderate Cu concentration (3%–5%) in CZA NPs. Further, we checked the effects of other factors on the photocatalytic degradation for possible application. Our results suggest that one well-designed composite type such as element-doped Zn(M)O–Ag nano-heterojunction or complicated metal oxide–ZnO–Ag nanocomposites possessing suitable band structures for the separation and utilization of photo-generated carriers, will remarkably improve the photocatalytic performance of nano-ZnO under sunlight irradiation.

Multifractal analysis of ZnO nanoparticles.

ZnO nanoparticles (NPs) have variety of applications in different fields due to its size, structure, as well as physical and chemical properties. One of its prominent characteristics is its antibacterial behavior. Nonlinear Dynamical Theory (NLD) has a vast scope in the field of material science, especially when subtle correlations are searched for to extract hidden information. Since nano-ZnO materials may be used in inhibiting pathogens, its nonlinear features can be quantified and calibrated with the help of NLD tools. Multi-fractal Analysis (MFA) is an important diagnostic tool of NLD for not only analyzing nonlinear signal or images, but also predicting any spurious events likely to occur in the system under study. Thus, the analysis of the surface texture of the ZnO nano particles formed, using the TEM images and relate it with the variations of the XRD signal using NLD tools, is our first attempt reported here. Further, tools of MFA are used, for the first time, to see if there exists any correlation between the texture of the nano particles formed and the Zone of Inhibition (ZoI) we obtain as an output after allowing certain pathogens inhibit in the presence of the same nano particles. Analysis of TEM images guide us to predict the texture and structure of crystallites of ZnO:Cu samples which are responsible for overall behavior of inhibiting pathogens. In this paper, MFA of ZoI images, TEM images, and signal of four different Cu-doped ZnO nanoparticles are carried out and their outcomes are calibrated for estimating the size and pattern of unknown NPs synthesized under similar physical and chemical condition. Moreover, that MFA can be used reliably to predict spurious or abnormal surface structure or bacterial inhibition is also established.

Facile synthesis of Cu-doped ZnO nanoparticle in triethyleneglycol: photocatalytic activities and aquatic ecotoxicity

ABSTRACT A new synthetisis method of Cu-doped ZnO nanoparticles is presented in this work, this novel approach allow one to produce Zinc oxide nanocristal owing to a modified Polyol process that makes use of triethyleneglycol (TREG) as a solvent. The structure and morphology of the nanoparticles were characterized by high-resolution transmission electron microscopy (HRTEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N2 adsorption study, UV-Vis diffuse reflectance spectroscopy, inductively coupled plasma optical emission spectroscopy and Raman spectroscopy. The lightly doped Zn1-xCuxO photocatalysts consisted in a novel nanorods structure of Zn0.9990Cu0.0010O nanoparticles. Taking the photocatalytic degradation of diuron under solar light as liquid phase test reaction, the lightly doped Zn0.9990Cu0.0010O nanorods photocatalysts showed strongly enhanced photocatalytic activity when compared to the bare ZnO counterpart. The apparent rate constant value of Zn0.9990Cu0.0010O was 22 times higher than that of pure ZnO. In order to study the environmental risk of Cu-ZnO, clams Ruditapes decussatus were exposed to Cu-ZnOC1 = 0.5 mg/L, Cu-ZnOC2 = 1 mg/L and Cu-ZnO C3 = 5 mg/L. Catalase (CAT) activities, malondialdehyde (MDA) content and acetylcholinesterase (AChE) activity were determined in gills and digestive gland of treated and untreated clams. Thus, no significant effects were detected in the gills of exposed clams after 7 days compared to control. Thus, MDA level and CAT activity showed significant differences in digestive glands of groups treated by the highest concentration of Cu-ZnO NPs compared to the control. No adverse effects on AChE activity was detected after Cu-ZnO NPs exposure. These results demonstrated that, although Cu-ZnO NPs is not acutely toxic to Ruditapes decussatus, it does exert oxidative stress on clams. These results are encouraging for the Cu-ZnO NPs use in variety of applications due to its high photocatalytic and low environmental toxicity.

Influence of Cu dopant on the morpho-structural and optical properties ZnO nanoparticles

In the present work, Cu-doped ZnO particles were obtained by a wet chemical method in aqueous medium using Zn(NO3)2, Cu(CH3COO)2 as basic precursors, NaOH as a precipitator material, in the absence and presence of two polymer surfactants (CTAB, PEO). This synthesis technique was selected as a potential method for obtaining Cu-doped ZnO nanoparticles with various stoichiometric ratios. The synthesized nanoparticles were investigated using Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), UV–Vis absorption and Photoluminescence spectroscopy (PL). The results suggest that the process variables together with the type of surfactant are crucial parameters for the physical, chemical and optical properties of Cu-doped ZnO nanoparticles. Moreover, the use of surfactants significantly improves the quality of synthesized particles by stabilizing particle growth, reducing the surface energy, preventing the interactions among the particles and decreasing the tendency of agglomeration.

Altered electrical properties with controlled copper doping in ZnO nanoparticles infers their cytotoxicity in macrophages by ROS induction and apoptosis

The present study reports the regulation of cytotoxicity of Cu doped ZnO nanoparticles in macrophages (RAW 264.7) due to altered physiochemical properties changes like electrical properties by controlled doping of Cu in ZnO. Cu-doped ZnO nanoparticles were prepared by High Energy Ball Milling technique (HEBM) and formed single phase Zn1-xCuxO (x = 0.0, 0.01, 0.02, 0.03) were called as pure ZnO, Cu1%, 2%, 3% respectively. Hexagonal wurtzite structure with size range of 22–26 nm was verified. FE-SEM with EDX analysis indicated the Cu doping effect on the surface morphology of ZnO. Zeta potential of Zn1-xCuxO was found to be elevated with increase in doping percentage of Cu (−36.6 mV to +18.2 mV). Dielectric constant was found to be decreased with increasing doping percentage. Increase in doping percentage enhanced cytotoxicity of Zn1-xCuxO in macrophages with LC50 of 62 μg/ml, 51 μg/ml, 40 μg/ml, 32 μg/ml. Granularity change of macrophages suggested doping influenced cellular uptake as consequence of zeta potential and dielectric properties changes. 3% Cu doped ZnO shown a higher ROS signal and apoptosis than 2% and 1% Cu doping with exhibition of ROS scavenging nature leading to apoptosis of prepared Cu doped ZnO nanoparticles. Our findings revealed mechanism of cytotoxicity of Zn1-xCuxO as a consequence of alteration in electric properties eliciting ROS scavenging leading to higher apoptosis with increasing doping percentage of Cu in ZnO.

High Efficient Visible-Light Photocatalytic Performance of Cu/ZnO/rGO Nanocomposite for Decomposing of Aqueous Ammonia and Treatment of Domestic Wastewater

Photocatalytic removal of ammonium-nitrogen (-N) from water using solar energy is an approach of high interest and applicability due to the convenience in application. ZnO has a great potential in photocatalytic decomposition of -N and conversion of this nutrient to under visible light irradiations. However the applicability of pristine ZnO though is limited due to its reduced capacity to utilize light from natural light. Herein, we report a two-step ZnO-modified strategy (Cu-doped ZnO nanoparticles, immobilized on reduced graphene oxide (rGO) sheets) for the promotion of photocatalytic degradation of -N under visible light. UV-Vis spectra showed that the Cu/ZnO/rGO can be highly efficient in the utilization of photons from the visible region. Hence, Cu/ZnO/rGO managed to demonstrate adequate photocatalytic activity and effective -N removal from water under visible light compared to single ZnO. Specifically, up to 83.1% of -N (initial concentration 50 mg·L−1, catalyst dosage 2 g·L−1, pH 10) was removed within 2 h retention time under Xe lamp irradiation. From the catalysis, the major by-product was N2. The high ammonia degradation efficiency from the ZnO/Cu/rGO is attributed to the improvement of the reactive oxygen species (ROSs) production efficiency and the further activation of the interfacial catalytic sites. This study also demonstrated that such nanocomposite is a recyclable agent. Its -N removal capacity remained effective even after five batch cycles. In addition, Cu/ZnO/rGO was applied to treat real domestic wastewater, and it was found that chemical oxygen demand (COD), total nitrogen (TN) and total phosphorus (TP) removal efficiencies can reach 84.3, 80.7, and 90.3%, respectively. Thus, Cu/ZnO/rGO in the presence of solar light can be a promising photocatalyst in the field of wastewater treatment.

Structural and optical properties of pure and copper doped zinc oxide nanoparticles

Abstract Pure and copper-doped zinc oxide nanoparticles (NPs) have been synthesized via chemical co-precipitation method where hydrazine is used as reducing agent and aqueous extract of Euphorbia milii plant as capping agent. Main objectives of the reported work are to investigate the effect of copper doping on crystal structure of ZnO nanoparticles; to study the effect of copper doping on optical band gap of ZnO nanoparticles and photoluminescence (PL) study of pure and copper-doped ZnO nanoparticles. To achieve the aforementioned objectives, XRD and SEM tests were performed for the identification and confirmation of crystal structure and morphology of the prepared samples. From XRD data the average grain size for pure ZnO was observed to be 24.62 nm which was first decreased to 18.95 nm for 5 wt% Cu-doped sample and then it was found to increase up to 37.80 nm as the Cu doping was increased to 7 wt%. Optical band gap of pure and Cu-doped ZnO nanoparticles was calculated from diffuse reflectance spectroscopy (DRS) spectra and was found to decrease from 3.13 eV to 2.94 eV as the amount of Cu increases up to 7 wt%. In photoluminescence study, PL technique was used and enhanced visible spectrum was observed. For further characterization FT-IR and EDX tests were also carried out.