Search Results (161)

Environmental sustainability and responsible resource utilization are critical global challenges. In this work, we present a sustainable and circular-economy-based approach for synthesizing CuFe₂O₄ nanoparticles by directly utilizing copper oxide minerals sourced from Chilean mining operations. Copper sulfate (CuSO₄) was extracted from these minerals through acid leaching and used as a precursor for nanoparticle synthesis via both chemical co-precipitation and microwave-assisted methods. The influence of different precipitating agents—NaOH, Na₂CO₃, and NaF—was systematically evaluated. XRD and FESEM analyses revealed that NaOH produced the most phase-pure and well-dispersed nanoparticles, while NaF resulted in secondary phase formation. The microwave-assisted method further improved particle uniformity and reduced agglomeration due to rapid and homogeneous heating. Electrochemical characterization was conducted to assess the suitability of the synthesized CuFe₂O₄ for supercapacitor applications. Cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) measurements confirmed pseudocapacitive behavior, with a specific capacitance of up to 1000 F/g at 2 A/g. These findings highlight the potential of CuFe₂O₄ as a low-cost, high-performance electrode material for energy storage. This study underscores the feasibility of converting primary mined minerals into functional nanomaterials while promoting sustainable mineral valorization. The approach can be extended to other critical metals and mineral residues, including tailings, supporting the broader goals of a circular economy and environmental remediation. Full article

In this study, 3-chlorothiophene-2-carboxylic acid (HL) was used as a main ligand to successfully synthesize four novel complexes: [Cu(L)₂(Py)₂(OH₂)₂] (1), [Co(L)₂(Py)₂(OH₂)₂] (2) (Py = pyridine), [{Ni(L)₂(OH₂)₄}₂{Ni(L)(OH₂)₅}]L•5H₂O (3), and [{Co(L)₂(OH₂)₄}₂{Co(L)(OH₂)₅}]L•5H₂O (4). All four compounds were identified by elemental analysis and ESI mass spectrometry, and subsequently characterized by IR spectroscopy, UV-visible diffuse reflectance spectroscopy, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography, and cyclic voltammetry. X-ray analyses revealed that complexes 1 and 2 exhibit a centrosymmetric pseudo-octahedral coordination geometry; the copper (II) and cobalt (II) metal ions, respectively, are located at the crystallographic center of inversion. The coordination sphere of the copper (II) complex is axially elongated in accordance with the Jahn–Teller effect. Intriguingly, for charge neutrality, compounds 3 and 4 crystallized as three independent mononuclear octahedrally coordinated metal centers, which are two $\left[\mathrm{M}{\mathrm{L}}_2{\left({\mathrm{O}\mathrm{H}}_2\right)}_4\right]$ complex molecules and one ${\left[\mathrm{M}\mathrm{L}{\left({\mathrm{O}\mathrm{H}}_2\right)}_5\right]}^{+}$ complex cation (M = ${\mathrm{N}\mathrm{i}}^{\mathrm{I}\mathrm{I}}$ and ${\mathrm{C}\mathrm{o}}^{\mathrm{I}\mathrm{I}}$, respectively), with the ligand anion ${\mathrm{L}}^{-}$ serving as the counter ion. The anticancer activities of these complexes were systematically assessed on human leukemia K562 cells, lung cancer A549 cells, liver cancer HepG2 cells, breast cancer MDA-MB-231 cells, and colon cancer SW480 cells. Among them, complex 4 shows significant inhibitory effects on leukemia K562 cells and colon cancer SW480 cells. Full article

Free-standing copper oxide (Cu₂O)-copper hydroxide (Cu(OH)₂) nanocomposites with enhanced catalytic and antibacterial functionalities were synthesized on copper mesh using a green method based on spinach leaf extract and glycerol. EDX, SEM, and TEM analyses confirmed the chemical composition and morphology. The resulting Cu2O-Cu(OH)₂@Cu mesh exhibited notable hydrophobicity, achieving a contact angle of 137.5° ± 0.6, and demonstrated the ability to separate thick oils, such as HD-40 engine oil, from water with a 90% separation efficiency. Concurrently, its photocatalytic performance was evaluated by the degradation of methylene blue (MB) under a weak light intensity of 5 mW/cm², achieving 85.5% degradation within 30 min. Although its application as a functional membrane in water treatment may raise safety concerns, the mesh showed significant antibacterial activity against both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria under both dark and light conditions. Using the disk diffusion method, strong bacterial inhibition was observed after 24 h of exposure in the dark. Upon visible light irradiation, bactericidal efficiency was further enhanced—by 17% for S. aureus and 2% for E. coli. These findings highlight the potential of the Cu₂O-Cu(OH)₂@Cu microfibers as a multifunctional membrane for industrial wastewater treatment, capable of simultaneously removing oil, degrading organic dyes, and inactivating pathogenic bacteria through photo-assisted processes. Full article

Investigating viable processes for the use of lignocellulosic biomass in clean fuels and high-value-added chemical products is essential for sustainable development. Large amounts of lignin are available every year as by-products of the paper and biorefinery industries, causing a series of problems, particularly environmental ones. Its structure and composition make lignin compatible with the concept of sustainability, since it can be used to produce new chemical products with high added value. As such, this study aims to extract lignin from green coconut fiber (LIG), with the subsequent impregnation of a sodium-octanoate-based surfactant (LIG-SUR), and determine its applicability as an adsorbent for removing copper ions from synthetic waste. To this end, the green coconut fiber lignocellulosic biomass was initially subjected to alkaline pre-treatment with 2% (w/v) sodium hydroxide in an autoclave. Next, the surface of the lignin was modified by impregnating it with sodium octanoate, synthesized from the reaction of octanoic acid and NaOH. The physical and chemical traits of the lignin were studied before and after surfactant impregnation, as well as after copper ion adsorption. The lignin was analyzed by X-ray fluorescence (XRF), Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The adsorption tests were carried out using lignin pre-treated with surfactant in a batch system, where the effects of pH and adsorbent concentration were investigated. XRF and SEM analyses confirmed surfactant impregnation, with Na₂O partially replaced by CuO after Cu²⁺ adsorption. FTIR analysis revealed shifts in O–H, C–H, C=O, and C=C bands, indicating electrostatic interactions with lignin. Adsorption kinetics followed the pseudo-second-order model, suggesting chemisorption, with equilibrium reached in approximately 10 and 60 min for LIG-SUR and LIG, respectively. The Langmuir model best described the isotherm data, indicating monolayer adsorption. LIG-SUR removed 91.57% of Cu²⁺ and reached a maximum capacity of 30.7 mg·g⁻¹ at 25 °C and a pH of 6. The results of this research showed that pre-treatment with NaOH, followed by impregnation with surfactant, significantly increased the adsorption capacity of copper ions in solution. This technique is a viable and sustainable alternative to the traditional adsorbents used to treat liquid waste. In addition, by using green coconut fiber lignin more efficiently, the research contributes to adding value to this material and strengthening practices in line with the circular economy and environmental preservation. Full article

Atmospheric aqueous-phase reactions have been recognized as an important source of secondary organic aerosols (SOAs). However, the unclear reaction kinetics and mechanics hinder the in-depth understanding of the SOA sources and formation processes. This study selected ten different substituted phenolic compounds (termed as PhCs) emitted from biomass burning as precursors, to investigate the kinetics using OH oxidation reactions under simulated sunlight. The factors influencing reaction rates were examined, and the contribution of reactive oxygen species (ROS) was evaluated through quenching and kinetic analysis experiments. The results showed that the pseudo-first-order rate constants (k_obs) for the OH oxidation of phenolic compounds ranged from 1.03 × 10⁻⁴ to 7.85 × 10⁻⁴ s⁻¹ under simulated sunlight irradiation with an initial H₂O₂ concentration of 3 mM. Precursors with electron-donating groups (-OH, -OCH₃, -CH₃, etc.) exhibited higher electrophilic radical reactivity due to the enhanced electron density of the benzene ring, leading to higher reaction rates than those with electron-withdrawing groups (-NO₂, -CHO, -COOH). At pH 2, the second-order reaction rate (k_{PhCs, OH}) was lower than at pH 5. However, the k_obs did not show dependence on pH. The presence of O₂ facilitated substituted phenols’ photodecay. Inorganic salts and transition metal ions exhibited varying effects on reaction rates. Specifically, NO₃⁻ and Cu²⁺ promoted k_{PhCs, OH}, Cl⁻ significantly enhanced the reaction at pH 2, while SO₄²⁻ inhibited the reaction. The k_{PhCs, OH} were determined to be in the range of 10⁹~10¹⁰ L mol⁻¹ s⁻¹ via the bimolecular rate method, and a modest relationship with their oxidation potential was found. Additionally, multiple substituents can suppress the reactivity of phenolic compounds toward •OH based on Hammett plots. Quenching experiments revealed that •OH played a dominant role in phenolic compound degradation (exceeding 65%). Electron paramagnetic resonance confirmed the generation of singlet oxygen (¹O₂) in the system, and probe-based quantification further explored the concentrations of •OH and ¹O₂ in the system. Based on reaction rates and concentrations, the atmospheric aqueous-phase lifetimes of phenolic compounds were estimated, providing valuable insights for expanding atmospheric kinetic databases and understanding the chemical transformation and persistence of phenolic substances in the atmosphere. Full article

Catalytic hydrogenolysis of lignin to produce high-value monophenols has emerged as a pivotal strategy in modern biorefineries. In this study, we synthesized spherical nitrogen-doped porous carbon (SNCB) materials by using Al/Co-BTC as a precursor, introducing melamine as a supplementary carbon and nitrogen source, and activating the material with NaOH solution. The SNCB framework was decorated with Cu-Pd bimetallic nanoparticles, exhibiting outstanding catalytic activity in the hydrogenolytic depolymerization of organosolv lignin. The Cu-Pd@SNCB catalyst exhibited remarkable activity, attributed to the hierarchical porous structure of SNCB that facilitated metal nanoparticle dispersion and reactant accessibility. The synergistic effect between Cu as the reactive site for reactant adsorption and Pd as the reactive site for H₂ adsorption enhanced the catalytic activity of the catalyst. Systematically optimized conditions (2 MPa H₂, 270 °C, 3 h) yielded 43.02 wt% phenolic monomers, with 4-(3-hydroxypropyl)-2,6-dimethoxyphenol dominating the product profile at 46.3% selectivity. The catalyst and its reaction products were analyzed using advanced characterization techniques, including XPS, XRD, TEM, SEM, BET, GC-MS, GPC, 2D HSQC NMR, and FT-IR, to elucidate the reaction mechanism. The mechanism proceeds through: (1) nucleophilic substitution of the β-O-4 hydroxyl group by MeOH, followed by (2) simultaneous hydrogenolytic cleavage of C_β-O and C_α-O bonds mediated by Cu-Pd@SNCB under H₂ atmosphere, which selectively produces 4-(3-hydroxypropyl)-2,6-dimethoxyphenol and 4-propyl-2,6-dimethoxyphenol. This study proposes a bimetallic synergistic mechanism, offering a general blueprint for developing selective lignin valorization catalysts. Full article

The reaction of CuCl₂∙2H₂O, (E)-2-hydroxy-1,2-di(pyridin-2-yl)ethanone oxime (α-pyroxH₂) and Et₃N in refluxing MeOH gave complex [Cu₁₂Cl₁₂(mpydol)₄(pydox)₂(MeOH)₄] (1), where mpydol²⁻ is the dianion of 1,2-dimethoxy-1,2-di(pyridin-2-yl)ethane-1,2-diol and pydox²⁻ is the dianion of (E,E)-1,2-di(pyridin-2-yl)ethanedione dioxime. “Blind” experiments have proven that the transformation of α-pyroxH₂ is copper(II)-assisted. By changing the solvent from MeOH to MeCN, the polymeric compound {[Cu₄Cl₄(pic)₄]}_n (2) was isolated; pic⁻ is the pyridine-2-carboxylato(-1) ligand. The observed α-pyroxH₂ → pic⁻ transformation is also copper(II)-assisted. The topology of the metal ions in 1 can be described as consisting of four consecutive isosceles triangles in a zigzag configuration. Complex 2 is a 2D coordination polymer consisting of Cu^II₄ squares. Complete mechanistic views for the α-pyroxH₂ → mpydol²⁻, pydox²⁻ and pic⁻ transformations are critically discussed. In 1, the six Cu^II ions of the “central” triangles seem to be strongly antiferromagnetically coupled, thus cancelling out their spins ($S_{{\mathrm{Cu}}_6}$ = 0). The two local spins of S = 1/2 for each of the antiferromagnetically coupled “terminal” Cu^II₃ triangles result in an overall S = 1 ground state spin value for 1. In 2, the four Cu^II ions within each tetrameric unit are practically isolated and ferromagnetic interactions occur between these units through Cu^II–(μ-Cl)–Cu^II bridges. Full article

The oxidation of 1,2-propanediol (1,2-PDO) under alkaline heterogeneous catalysis can be optimized to produce lactic acid, a valuable commodity chemical. In this study, Pd nanoparticles supported on various metal oxides (CeO₂, CuO, ZrO₂, ZnO, SnO₂) were synthesized via a wet-chemistry method. Furthermore, CeO₂-supported Pd nanoparticle catalysts were prepared using different reduction methods. The catalytic performance for the selective oxidation of 1,2-PDO was evaluated using a range of characterization techniques. Under optimal conditions (120 °C, 1.0 MPa O₂ pressure, 2 h reaction time, and a NaOH/1,2-PDO molar ratio of 3.0), a high lactic acid yield of 62.7% was achieved. Single-factor experiments revealed that lactic acid selectivity decreased with prolonged reaction time. Conversely, increasing temperature, NaOH concentration, and O₂ pressure initially enhanced lactic acid selectivity, but further increases resulted in a decline. Physicochemical characterization revealed that different supports and reduction methods affect the basicity of the catalyst, which subsequently influences the selectivity of the target product, lactic acid. Full article

The organic–inorganic hybrid (BEDT-TTF)₃[Cu₂(μ-C₂O₄)₃·CH₃CH₂OH·1.2H₂O] (I) was obtained using the electrocrystallization method. It comprises a θ²¹-phase organic donor layer and a two-dimensional inorganic antiferromagnetic honeycomb lattice. Cu(II) is octahedrally coordinated by three bisbidenetate oxalates, exhibiting Jahn–Teller distortion. CH₃CH₂OH and H₂O molecules are located within the cavities of the honeycomb lattice. The total formal charge of the three donor molecules was assigned to be +2 based on the bond lengths in the TTF core, which corresponded to the Raman spectra. It is a semiconductor with σ_rt = 0.04 S/cm and E_α = 40 meV. No long-range ordering was observed above 2 K from zero-field cooling/field cooling magnetization, as confirmed by specific heat measurements. The spin frustration with f > 10 from the antiferromagnetic copper-oxalate-framework was observed. It is a candidate quantum spin liquid. Full article

Schiff bases constitute a broad and well-established class of ligands widely utilized in coordination chemistry. To further enrich this family and assess the potential impact of oxalyldihydrazide-derived Schiff bases in the realms of coordination chemistry and molecular magnetism, three novel ligands have been synthesized and investigated. i.e., N′1,N′2-bis((E)-pyridin-2-ylmethylene)oxalohydrazide (H₂L1), N′1-((E)-(3-methylpyridin-2-yl)methylene)-N′2-((E)-(6-methylpyridin-2-yl)methylene)oxalohydrazide (H₂L2) and N′1,N′2-bis((E)-phenyl(pyridin-2-yl)methylene)oxalohydrazide (H₂L3) were synthesized and then combined with various 3d metals, resulting in the formation of five new complexes with formula [Cu₅(L1)₂(H₂O)₈(MeOH)₂(NO₃)₂](NO₃)₄ (1), [Mn₂(HL2)₂(BzO)₂(MeOH)₂]·2MeOH (2), [Ni(HL2)₂]·2MeOH (3), [Ni₄(L2)₄]·4MeOH (4), [Ni₈(L3)₄(AcO)₄(H₂O)₁₂](OAc)₄ (5). These compounds were structurally and magnetically characterized, revealing the various coordination modes exhibited by the ligands and a distinct antiferromagnetic behavior. Alternating current (AC) susceptibility measurements were conducted on complex 1, showing no evidence of Single Molecule Magnet (SMM) behavior. Full article

This study examines the influence of ligand design on the structural, optical, and electrical properties of copper-based coordination complexes. Ligands H₂L¹ and H₂L² were synthesized via the reaction of 5-nitrosalicylaldehyde with 2-hydroxy- or 4-hydroxybenzhydrazide. H₄L³ was obtained from the reaction of carbohydrazide and salicylaldehyde, while H₄L⁴ was prepared by condensing 4-methoxysalicylaldehyde with thiocarbohydrazide. The research focuses on two key design elements: (1) the effect of hydroxyl group positioning on the aroyl ring in hydrazide ligands (H₂L¹ vs. H₂L²) and (2) the impact of carbonyl versus thiocarbonyl groups and aldehyde substituents in hydrazone ligands (H₄L³ vs. H₄L⁴). The resulting complexes, [Cu₂(L¹)₂], [Cu₂(L²)₂(MeOH)₃], [Cu₂(L³)(H₂O)₂], and [Cu₂(L⁴)(H₂O)₂], were synthesized and characterized using attenuated total reflectance infrared (IR-ATR) spectroscopy, thermogravimetric analysis (TG), and UV-Vis diffuse reflectance spectroscopy. Their electrical properties were investigated using solid-state impedance spectroscopy (IS). The crystal and molecular structure of the complex [Cu₂(L²)₂(MeOH)₃]∙MeOH was determined by single-crystal X-ray diffraction (SCXRD). This study underscores the pivotal role of ligand modifications in modulating the functional properties of coordination complexes, offering valuable insights for the advancement of materials chemistry. Full article

The dominant treatment process for removing heavy metals from industrial wastewater is chemical neutralisation precipitation using lime milk as a precipitation agent, resulting in a highly voluminous hydroxide sludge with a low heavy metal concentration. These sludges are predominantly landfilled, and the metals are lost to the circular economy. At the same time, metals are urgently needed as raw materials. A new approach is represented by the low-pressure, low-energy Specific Product-Oriented Precipitation process (SPOP). This approach, however, requires the adjustment of various reaction parameters for optimal operation. This study presents the impacts of the stirring rate during the reaction and the Fe concentration in the solution on the recovery of Cu from Cu-enriched electroplating wastewater. Three different recovery options are described: Option (1), the formation of CuO; Option (2), the generation of brochantite, a Cu-hydroxysulphate; and Option (3), the incorporation of Cu into ferrite. Tenorite (CuO) is precipitated at 40 °C reaction temperature at a low stirring rate of 100–200 rpm. At an accelerated stirring rate of 400–500 rpm, brochantite (Cu₄(OH)₆SO₄) is formed. With high Fe concentrations and a molar ratio of Cu:Fe of 1:2, Cu-ferrite (CuFe₂O₄) is the precipitation product. In any case, the achieved recovery rates in the treated wastewater are better than 99.9%. Full article

Metal–organic frameworks (MOFs) are hybrid inorganic–organic 3D coordination polymers with metal sites and organic linkers, which are a “hot” topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal–organic framework (actAl-MOF-TCPPCu) compound 4 with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound 4 was synthesized by post-synthetic modification (PSM) of Al-MOF-TCPPH₂ compound 2 by inserting Cu²⁺ ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis. Second, the interaction of compound 4 with DES vapor was analyzed dynamically by the novel method of in situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy at controlled humidity levels. The sorbent–adsorbate interactions, as analyzed by the shifts in IR peaks, indicate that the bonding includes the hydroxy O-H, carboxylate COO⁻, and phenyl groups. The kinetics of sorption obeys the Langmuir pseudo-first-order rate law. The pre-adsorption of water vapor by compound 4 at the controlled relative humidity under static (equilibrium) conditions yields the binary stoichiometric adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0. The pre-adsorption of water vapor makes the subsequent sorption of DES slower, while the kinetics obey the same rate law. Then, static pre-adsorption of water vapor was followed by static sorption of DES vapor, and the ternary adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0(DES)₃.₈ was obtained. Despite the pre-adsorption of significant amounts of water, the binary complex adsorbs a large amount of DES: ca. 36.6 wt. % (per compound 4). Finally, the ternary complex is facilely regenerated by gentle heating under vacuum. Compound 4 and related MOFs are promising for adsorptive removal of vapor of DES and related VOSCs from dry and humid air. Full article

Zheshengite (IMA2022-011), Pb₄ZnZn₂(AsO₄)₂(PO₄)₂(OH)₂, is a new mineral from Sanguozhuang Village in the eastern Dongchuan Copper Ore Field, Yunnan Province, China. The new mineral is named after Zhesheng Ma (1937–). Zheshengite occurs as prismatic single crystals with chisel-like terminations on hemimorphite, with crystal sizes ranging from 0.02 to 0.05 mm. It is a brittle mineral with irregular fractures, a Mohs hardness of 2½ to 3, perfect cleavage on {011}, and a calculated density of 6.26 g/cm³. The empirical formula of zheshengite, based on 18 O atoms per formula unit, is (Pb_4.12Ca_0.01)_∑4.13(Zn_0.83Cu_0.23Fe_0.04)_∑1.10Zn_2.00[(As_0.90P_0.10)_∑1.00O₄]₂[(P_0.94Si_0.01)_∑0.95O₄]₂(OH)₂. Zheshengite exhibits a triclinic structure (space group P−1, no. 2), with unit-cell parameters: a = 4.7746(4) Å, b = 8.4920 (7) Å, c = 10.4056 (8) Å, α = 97.087 (7)°, β = 101.060 (7)°, γ = 92.996 (7)°, V = 409.66 (6) ų, and Z = 1. As a member of the dongchuanite group, zheshengite features a dongchuanite-type structure. This study reveals the impact of As–P isomorphic substitution on unit-cell parameters in the dongchuanite group, identifying correlations between As content and changes in parameters a and V, which may serve as diagnostic indicators for dongchuanite group minerals. In addition, the structure studies of zheshengite may have implications for environmental protection. Full article

We have shown that the adsorption of Cu²⁺ ions on various metal oxides, depending on the pH of the solution, can be described assuming the formation of only two surface complexes with surface hydroxyl groups SOH: SOCu(OH) and SOCu⁺. Using an ion-selective electrode for Cu²⁺, we determined the adsorption edges, i.e., the dependence of the amount of adsorbed metal expressed as a percentage depending on the solution pH for three oxides: TiO₂, Al₂O₃, and SiO₂. The measurements were carried out with high surface coverage where the ratio of the adsorption sites/copper ions in the system were from 2 to 3, depending on the oxide. Simultaneously, with the adsorption edge, the hydrogen surface charge density and the electrokinetic potential of the oxide particles were measured as a function of pH. These three types of experimental data were fitted all together using the surface complexation model (2-pK TLM). In modeling, it was not necessary to consider the precipitation of Cu(OH)₂ on the oxide surface to obtain good agreement with the data. Additionally, it was shown that the presence of charged surface species SOCu⁺ (about 10% of total adsorbed copper) was crucial to fit the data for zeta potential. Full article