Project description:Electrochemical conversion of nitrate (NO3 -) to ammonia (NH3) is a potential way to produce green NH3 and remediate the nitrogen cycle. In this paper, an efficient catalyst of spherical CuO made by stacking small particles with oxygen-rich vacancies is reported. The NH3 yield and Faraday efficiency are 15.53 mg h-1 mgcat -1 and 90.69%, respectively, in a neutral electrolyte at a voltage of -0.80 V (vs. reversible hydrogen electrode). The high activity of the electrodes results from changes in the phase and structure during electrochemical reduction. Structurally, there is a shift from a spherical structure with dense accumulation of small particles to a layered network structure with uniform distribution of small particles stacked on top of each other, thus exposing more active sites. Furthermore, in terms of phase, the electrode transitions from CuO to Cu/Cu(OH)2. Density functional theory calculations showed that Cu(OH)2 formation enhances NO3- adsorption. Meanwhile, the Cu(OH)2 can inhibit the competing hydrogen evolution reaction, while the formation of Cu (111) crystal surfaces facilitates the hydrogenation reaction. The synergistic effect between the two promotes the NO3- to NH3. Therefore, this study provides a new idea and direction for Cu-based oxides in electrocatalytic NH3 production.
Project description:Sunlight-driven photocatalytic degradation is an effective and eco-friendly technology for the removal of organic pollutants from contaminated water. Herein, we describe the one-step synthesis of Cu-Cu2O-Cu3N nanoparticle mixtures using a novel non-aqueous, sol-gel route and their application in the solar-driven photocatalytic degradation of methylene blue. The crystalline structure and morphology were investigated with XRD, SEM and TEM. The optical properties of the as-prepared photocatalysts were investigated with Raman, FTIR, UV-Vis and photoluminescence spectroscopies. The influence of the phase proportions of Cu, Cu2O and Cu3N in the nanoparticle mixtures on the photocatalytic activity was also investigated. Overall, the sample containing the highest quantity of Cu3N exhibits the highest photocatalytic degradation efficiency (95%). This enhancement is attributed to factors such as absorption range broadening, increased specific surface of the photocatalysts and the downward band bending in the p-type semiconductors, i.e., Cu3N and Cu2O. Two different catalytic dosages were studied, i.e., 5 mg and 10 mg. The higher catalytic dosage exhibited lower photocatalytic degradation efficiency owing to the increase in the turbidity of the solution.
Project description:This comprehensive study explores the kinetics of adsorption and its photocatalytic degradation of methyl orange (MO) using an advanced copper-decorated photocatalyst in the form of hollow fibers (HFs). Designed to boost both adsorption capacity and photocatalytic activity, the photocatalyst was tested in batch experiments to efficiently remove MO from aqueous solutions. Various isotherm models, including Langmuir, Freundlich, Sips, Temkin, and Dubinin-Radushkevich, along with kinetic models like pseudo-first and pseudo-second order, Elovich, Bangham, and Weber-Morris, were utilized to assess adsorption capacity and kinetics at varying initial concentrations. The results indicated a favorable MO physisorption on the nanocomposite photocatalyst under specific conditions. Further analysis of photocatalytic degradation under UV exposure revealed that the material maintained high degradation efficiency and stability across different MO concentrations. Through the facilitation of reactive oxygen species generation, oxygen played a crucial role in enhancing photocatalytic performance, while the degradation process following the Langmuir-Hinshelwood model. The study also confirmed the robustness and sustained activity of the nanocomposite photocatalyst, which could be regenerated and reused over five successive cycles, maintaining 92% of their initial performance at concentrations up to 15 mg/L. Overall, this effective nanocomposite photocatalyst structured in the form of HF shows great promise for effectively removing organic pollutants through combined adsorption and photocatalysis, offering valuable potential in wastewater treatment and environmental remediation.
Project description:Augmenting the oriented attachment (OA) crystal growth phenomena, herein, we demonstrate fabrication of ultrathin CuO nanowires from self-assembled one-dimensional (1D) nanowires of Cu(OH)2 nanocrystals. A facile environmentally benign sol-gel approach, which utilizes base-catalyzed hydrolysis followed by directed self-assembly and crystal growth of nanocrystals, is developed to prepare Cu(OH)2 nanowires. The sol of Cu(OH)2 nanocrystals shows aggregative self-assembly guided by the OA crystal growth process to form ultrathin Cu(OH)2 nanowires, with an average length of 675 ± 4 nm and diameter of 6 ± 2 nm. The time-dependent UV-visible spectral traces, along with real-time imaging of nanocrystals self-assembly and growth under the transmission electron microscope, are evidenced the concept of the OA crystal growth directed self-assembly, yielding 1D colloidal nanoarrays of Cu(OH)2. The powder XRD traces collected during the self-assembly and crystal growth process reveal the directional aggregative crystal growth along the facet of [001], confirming the OA directed crystal growth and fusion of nanocrystals to yield 1D nanostructures. The gradual blue-shift in optical absorption maxima from 770 nm in initial precursor solution, to 670 nm for Cu(OH)2 nanocrystals sol, and finally to 647 nm for self-assembled 1D Cu(OH)2 nanowires have further evidenced the formation of Cu(OH)2 nanowires. Upon subjecting self-assembled Cu(OH)2 nanowires for post-annealing treatment, ultrathin CuO nanowires with average length of 7 ± 0.50 μm and diameter of 27 ± 2 nm is obtained in high purity. The experimental powder XRD patterns of Cu(OH)2 and CuO nanowires match the simulated XRD patterns, indexing the crystal unit cell structures to orthorhombic and monoclinic, respectively. The tailored narrow optical band gaps for Cu(OH)2 and CuO nanowires are found to be 1.51 eV and 1.10 eV. The theoretical band gap predicted for Cu(OH)2 nanowires is 1.52 eV and is in good agreement with its optical band gap, whereas theoretical band computed for CuO nanowires is 0.13 eV lower than from its optical band gap.
Project description:In this work, a series of Cu2O/S (S = α-MnO2, CeO2, ZSM-5, and Fe2O3) supported catalysts with a Cu2O loading amount of 15% were prepared by the facile liquid-phase reduction deposition-precipitation strategy and investigated as CO oxidation catalysts. It was found that the Cu2O/α-MnO2 catalyst exhibits the best catalytic activity for CO oxidation. Additionally, a series of Cu2O-CuO/α-MnO2 heterojunctions with varied proportion of Cu+/Cu2+ were synthesized by further calcining the pristine Cu2O/α-MnO2 catalyst. The ratio of the Cu+/Cu2+ could be facilely regulated by controlling the calcination temperature. It is worth noting that the Cu2O-CuO/α-MnO2-260 catalyst displays the best catalytic performance. Moreover, the kinetic studies manifest that the apparent activation energy could be greatly reduced owing to the excellent redox property and the Cu2O-CuO interface effect. Therefore, the Cu2O-CuO heterojunction catalysts supported on α-MnO2 nanotubes are believed to be the potential catalyst candidates for CO oxidation with advanced performance.
Project description:Hierarchical Cu-Al2O3/biomass-activated carbon composites were successfully prepared by entrapping a biomass-activated carbon powder derived from green algae in the Cu-Al2O3 frame (H-Cu-Al/BC) for the removal of ammonium nitrogen (NH4 +-N) from aqueous solutions. The as-synthesized samples were characterized via XRD, SEM, BET and FTIR spectroscopy. The BET specific surface area of the synthesized H-Cu-Al/BC increased from 175.4 m2 g-1 to 302.3 m2 g-1 upon the incorporation of the Cu-Al oxide nanoparticles in the BC surface channels. The experimental data indicated that the adsorption isotherms were well described by the Langmuir equilibrium isotherm equation and the adsorption kinetics of NH4 +-N obeyed the pseudo-second-order kinetic model. The static maximum adsorption capacity of NH4 +-N on H-Cu-Al/BC was 81.54 mg g-1, which was significantly higher than those of raw BC and H-Al/BC. In addition, the presence of K+, Na+, Ca2+, and Mg2+ ions had no significant impact on the NH4 +-N adsorption, but the presence of Al3+ and humic acid (NOM) obviously affected and inhibited the NH4 +-N adsorption. The thermodynamic analyses indicated that the adsorption process was endothermic and spontaneous in nature. H-Cu-Al/BC exhibited removal efficiency of more than 80% even after five consecutive cycles according to the recycle studies. These findings suggest that H-Cu-Al/BC can serve as a promising adsorbent for the removal of NH4 +-N from aqueous solutions.
Project description:Cu2O/CuO heterostructure is a well-known strategy to improve the performance of Cu2O photocathodes for photoelectrochemical (PEC) water splitting. The CuO thickness in the Cu2O/CuO heterostructure is considered as a critical factor affecting the PEC performance because it is highly related to the light utilization and charge separation/transport. In this study, the Cu2O/CuO photocathode tailoring the CuO thickness was investigated to examine the CuO thickness influence on the PEC performance. Cu2O/CuO photocathodes were prepared by the electrodeposition and subsequent thermal annealing process and the Cu2O/CuO heterostructure was controlled by the annealing temperature and time. It was demonstrated that the increased CuO thickness enhances the light absorption in the long wavelength region and improves the charge separation by the reinforced band bending. However, the thick CuO hinders the efficient charge transport in the Cu2O/CuO heterostructure, resulting in the decreased PEC performance. Therefore, it is necessary to optimize the CuO thickness for the enhanced PEC performance of Cu2O/CuO photocathodes. Consequently, the Cu2O/CuO photocathode consisting of the similar CuO thickness with its minority carrier diffusion length (∼90 nm) was fabricated by annealing at 350 °C for 20 min, and it shows the optimal PEC performance (-1.2 mA cm-2 at 0 V vs. RHE) in pH 6.5 aqueous solution, resulting from the enhanced light utilization and the reinforced band bending.
Project description:Copper based nanoparticles (NPs) are used extensively in industrial and commercial products as sensors, catalysts, surfactants, antimicrobials, and for other purposes. The high production volume and increasing use of copper-based NPs make their ecological risk a concern. Commonly used copper-based NPs are composed of metallic copper or copper oxide (Cu and CuO NPs); however, their environmental toxicity can vary dramatically depending on their physico-chemical properties, such as dissolution, aggregation behavior, and the generation of reactive oxygen species. Here, we investigated the NP dissolution, organismal uptake and aquatic toxicity of Cu and CuO NPs at 0, 0.1, 1, 5 or 10 mg Cu/L using a previously developed multi-species microcosm. This 5-day microcosm assay was comprised of C. reinhardtti, E. coli, D. magna, and D. rerio. We hypothesized that Cu and CuO NPs can elicit differential toxicity to the organisms due to alterations in particle dissolution and variations in organismal uptake. The actual concentrations of dissolved Cu released from the NPs were compared to ionic copper controls (CuCl2) at the same concentrations to determine the relative contribution of particulate and dissolved Cu on organism uptake and toxicity. We found that both NPs had higher uptake in D. magna and zebrafish than equivalent ionic exposures, suggesting that both Cu-based NPs are taken up by organisms. Cu NP exposures significantly inhibited algal growth rate, D. magna survival, and zebrafish hatching while exposure to equivalent concentrations of CuCl2 (dissolved Cu fraction) and CuO NPs did not. This indicates that Cu NPs themselves likely elicited a particle-specific mechanism of toxicity to the test organisms, or a combination effect from ionic Cu and the Cu NPs. Overall, this work was the first study to utilize a small-scale rapid assay designed to evaluate the fate and ecotoxicological impacts of Cu and CuO NPs in a mixed aquatic community.
Project description:The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)2 have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)2 native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 °C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.
Project description:We bombarded [Formula: see text] and [Formula: see text] with a 2.3 eV hyperthermal oxygen molecular beam (HOMB) source, and characterized the corresponding (oxide) surfaces with synchrotron-radiation X-ray photoemission spectroscopy (SR-XPS). At [Formula: see text], CuO forms on both [Formula: see text] and [Formula: see text]. When we increase the surface temperature to [Formula: see text], [Formula: see text] also forms on [Formula: see text], but not on [Formula: see text]. For comparison, [Formula: see text] forms even at [Formula: see text] on Cu(111). On [Formula: see text], [Formula: see text] forms only after [Formula: see text], and no oxides can be found at [Formula: see text]. We ascribe this difference in Cu oxide formation to the mobility of the interfacial species (Cu/Pd/Pt) and charge transfer between the surface Cu oxides and subsurface species (Cu/Pd/Pt).