Search Results (45)

Four new porous homochiral metal–organic frameworks (MOFs), [M₂(camph)₂(bpa)]∙Solv (M = Co(II), Ni(II), Cu(II) and Zn(II)), based on (+)-camphoric acid (H₂camph) and 1,2-bis(4-pyridyl)ethane (bpa) were synthesized and characterized. The crystal structures of [Ni₂(camph)₂(bpa)] and [Zn₂(camph)₂(bpa)] were established by single-crystal X-ray diffraction analysis. Powder X-ray data prove the phase purity and isostructural nature of all four compounds. The thermal stability of [M₂(camph)₂(bpa)] was found to depend on the electronic configuration, as well as on the redox properties of the metal cation, and varied from 225 °C (M = Zn²⁺) to 375 °C (M = Ni²⁺). The reversible, solvent-induced sponge-like dynamics of the coordination frameworks was thoroughly investigated. Changes in the positions of reflexes, related to the length of the flexible bpa linker, were observed by powder XRD, pointing to transitions between an open-framework phase and a squeezed, non-porous phase in a crystal-to-crystal manner, while the integrity and connectivity of the coordination network were maintained. Size-selective adsorption from a benzene–cyclohexane 1:1 mixture on [Zn₂(camph)₂(bpa)] was studied by ¹H NMR analysis. The benzene-favorable composition of guest molecules (C₆H₆:C₆H₁₂ = 5:1) occluded within the host crystalline sponge revealed a preferable adsorption affinity towards smaller benzene compared with larger cyclohexane. High framework stability in various solvents, as well as successful molecular separation in the liquid state, validates the potential utilization of chiral porous metal(II) camphorate MOFs in important stereoselective applications. Full article

Lithium-ion batteries are essential to ensure electric mobility and reduce CO₂ emissions from transportation. One of the most commonly used chemistries is nickel–cobalt–manganese (NMC) batteries, which also have applications beyond the automotive sector. The recycling of these batteries requires the development of technologies to enable the selective separation and recovery of the metals present in the battery. One of these selective technologies involves the use of deep eutectic solvents (DESs). This research study investigates the different parameters that influence the recovery of Co(II) from hydrochloric acid medium using the deep eutectic solvent 3 Aliquat 336:7 L-Menthol. Firstly, using synthetic Co(II) solutions, the parameters influencing the cobalt extraction process are examined, and then these optimal conditions are applied to the recovery of cobalt from solutions obtained by dissolving NMC 622 battery black mass in 10 M HCl. The obtained results show that the DES used is highly selective for Co(II) recovery compared to other metals present in the solution (Ni, Li and Mn), achieving recoveries of up to 90% of the cobalt initially present in solution. Stripping with H₂SO₄ 0.5 M allows the recovery of cobalt as a crystalline monohydrate salt (CoSO₄.H₂O). The optimization of the Co/Cu separation conditions is carried out, achieving the separation of Cu(II) using Aliquat 336 in kerosene. Full article

Brewers’ spent grain (BSG) is the dominant solid side stream from wort separation, generating about 20 kg wet BSG per 100 L of beer and contributing hundreds of millions of tons annually worldwide, and thus a strategic feedstock for circular solutions in the brewing sector. This study situates BSG within that sustainability context and assesses its performance for removing metal ions and organic contaminants. A critical literature review with selected techniques (SEM, NIR/MIR, TGA) has been combined. SEM reveals a rough, fibrous–lamellar microtexture with high pore density, large pore-area fractions, submicron median equivalent diameters, and elevated edge density, consistent with accessible surface and mass-transfer pathways. Compiled adsorption evidence shows that raw and engineered BSG effectively capture diverse cations, including Cu(II), Cr(III/VI), Pb(II), Mn(II), U(VI) and selected rare-earth elements (REEs), demonstrable reusability, and fixed-bed breakthrough on the order of tens to hundreds of hours. Preservation options (drying, cooling/freezing, thermal inactivation, oxygen control) that enable safe storage and logistics for deployment have also been outlined. Overall, BSG emerges as a reliable, scalable biosorbent, with SEM-derived descriptors providing practical tools for performance prediction, while spectroscopic and thermal methods support material monitoring and process integration within a brewery’s circular economy. Full article

Photothermal catalytic CO₂ conversion into chemicals that provide added value represents a promising strategy for sustainable energy utilization, yet the development of highly efficient, stable, and selective catalysts remains a significant challenge. Herein, we report a rationally designed p-n junction heterostructure, T-CZ-PBA (SC), synthesized via controlled pyrolysis of high crystalline Prussian blue analogues (PBA) precursor, which integrates CuCo alloy, ZnO, N-doped carbon (NC), and Zn^II-Co^IIIPBA into a synergistic architecture. This unique configuration offers dual functional advantages: (1) the abundant heterointerfaces provide highly active sites for enhanced CO₂ and H₂ adsorption/activation, and (2) the engineered energy band structure optimizes charge separation and transport efficiency. The optimized T-C₃Z₁-PBA (SC) achieves exceptional photothermal catalytic performance, demonstrating a CO₂ conversion rate of 126.0 mmol gcat⁻¹ h⁻¹ with 98.8% CO selectivity under 350 °C light irradiation, while maintaining robust stability over 50 h of continuous operation. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) investigations have identified COOH* as a critical reaction intermediate and elucidated that photoexcitation accelerates charge carrier dynamics, thereby substantially promoting the conversion of key intermediates (CO₂* and CO*) and overall reaction kinetics. This research provides insights for engineering high-performance heterostructured catalysts by controlling interfacial and electronic structures. Full article

In this paper, polymer inclusion membranes (PIMs) were created using poly(vinyl chloride)-based alkyl sulfonic acid derivatives as ion carriers and dioctyl terephthalate as a plasticizer for the selective separation of Pb(II), Cu(II), and Cd(II) ions from aqueous nitrate solutions. The ion carriers were dinonylnaphthalenesulfonic acid (DNNSA) and nonylbenzenesulfonic acid (NBSA). The influence of the carrier and the plasticizer concentration in the membrane on the transport efficiency was investigated. For the PIM system, 15% wt. of carrier (DNNSA, NBSA), 20% wt. of plasticizer, and 65% wt. of polymer poly(vinyl chloride) PVC were the optimal proportions, with which the process was the most effective. Research on the transport kinetics has shown that the transport of Pb(II) ions through PIMs containing acidic carriers adheres to a first-order kinetics equation, which is characteristic of a facilitated transport mechanism. The activation parameter for these processes suggests that the high performance of these ion carriers is associated with the immobilization of the carrier within the membrane. It was found that PIMs based on DNNSA facilitate the selective separation of Pb(II)/Cu(II) and Pb(II)/Cd(II) mixtures, achieving high separation factors. Full article

The selective adsorption and separation of benzene from structurally similar six-membered hydrocarbons and fluorocarbons remain a significant challenge due to their comparable physical properties. In this study, we investigated the molecular recognition and separation properties of a perfluorinated triketonate Cu(II) complex (1) as a Nonporous Adaptive Crystal (NAC). In addition to the previously reported benzene (2)-encapsulated crystal of 1•(2)₃, we report here the crystal structures of guest-free 1 and cyclohexene (3)-encapsulated 1•(O)₂•3, where (O)₂ represents two water molecules. Single-crystal analysis demonstrated that 1 selectively encapsulates 2 while excluding other hydrocarbons, including 3, cyclohexane (4), trifluorobenzene (5), and hexafluorobenzene (6). Gas adsorption experiments confirmed this high affinity for 2, as reflected in its preferential adsorption behavior in mixed solvent and vapor environments. The molecular selectivity of 1 was attributed to strong π-hole···π and metal···π interactions, which favor electron-rich aromatic guests. Additionally, crystallization experiments in competitive solvent systems consistently led to the formation of 1•(2)₃, reinforcing the high selectivity of 1 for 2. These findings highlight the unique molecular recognition capabilities of NACs, providing valuable insights into the rational design of advanced molecular separation materials for industrial applications involving aromatic hydrocarbons. Hirshfeld surface analysis revealed that the contribution of F···F interactions to crystal packing decreased upon guest recognition (48.8% in 1, 34.2% in 1•(O)₂•3, and 22.2% in 1•(2)₃), while the contribution of F···H/H···F interactions increased (8.6% in 1, 22.2% in 1•(O)₂•3, and 35.4% in 1•(2)₃). Regarding Cu interactions, the self-assembled columnar structure of 1 results in close contacts at the coordination sites, including Cu···Cu (0.1%), Cu···O (0.7%), and Cu···C (1.3%). However, in the guest-incorporated structures 1•(O)₂•3 and 1•(2)₃, the Cu···Cu contribution disappears; instead, 1•(O)₂•3 exhibits a significant increase in Cu···O interactions (1.2%), corresponding to water coordination, while 1•(2)₃ shows an increase in Cu···C interactions (1.5%), indicative of the metal···π interactions of benzene. Full article

Due to the lack of UV-protective properties for cotton textiles and the potential of cotton textiles to cause microbes to their users, we synthesized benzimidazole Schiff base derivative (BZI) namely N-((1H-benzo[d]imidazol-2-yl)methyl)-1-(4-fluorophenyl)methanimine and their V(III), Fe(III), Co(II), Ni(II), and Cu(II) complexes as UV protection and antimicrobial agents for cotton textile. Several techniques investigated these compounds: ¹H, ¹³C NMR, IR, UV–Vis, elemental analysis, DTA, and TGA. The Schiff base ligand behaved as a bidentate ligand. The prepared ligand and its complexes are used to treat the cotton fabrics (CFs) by immersing the fabric in the solution of the samples under ultrasonic. The treated cotton fabrics were investigated using IR and SEM-EDX analysis. The UPF values of the treated cotton fabric were obtained. The results showed that the cotton fabric treated with Fe(III) and Cu(II) complexes had excellent UV protection with UPF values of 50+. The disc diffusion method evaluated the treated cotton fabric’s antimicrobial activity. The antifungal activities of the treated CFs demonstrated that the Co(II)-BZI-CF was active on C. albicans with an inhibition zone of 12 mm, while the other samples were inactive on C. albicans and A. flavus. The V(III)-BZI-CF and Fe(III)-BZI-CF had no activity against S. aureus and E. coli bacteria while the other samples gave an inhibition zone of between 10 to 17 mm. Unlike previous studies that primarily focused on either UV protection or antimicrobial properties of metal complexes separately, this research integrates both functionalities by synthesizing benzimidazole Schiff base metal complexes and applying them to cotton textiles, demonstrating enhanced UV protection and selective antimicrobial activity. Full article

The flotation separation of sphalerite (ZnS) and pyrite (FeS₂) in a copper sulfate (CuSO₄)–butyl xanthate (BX) system is challenging because the indiscriminate activation of Cu²⁺ gives them similar floatability. To this end, the suitability of a novel depressant, luteolin (LUT), on the flotation separation of ZnS from FeS₂ in this system was studied. Micro-flotation tests and contact angle measurement results showed that ZnS could be selectively separated from FeS₂ using LUT as a depressant. At pH 7.0 ± 0.1, a flotation concentrate with a recovery of 93.90% ZnS and 2.84% FeS₂ was obtained after adding LUT in artificial mixed minerals tests. Adsorption differences and characteristics results showed that the affinity of LUT to FeS₂ was considerably higher than that of ZnS, which effectively hindered the subsequent adsorption of xanthate on FeS₂ but had a relatively weak effect on ZnS. Thus, a large floatability difference between ZnS and FeS₂ was achieved. Further analyses revealed that the adsorption behavior of LUT on FeS₂ occurred mainly through the interaction between 4–5 sites and Fe(II) at the solid/liquid interface. These findings shed light for the first time on the suitability of LUT for the successful flotation separation of ZnS from FeS₂, which has important guiding significance for the development of a lime-free depressant of FeS₂. Full article

Immobilized metal ion affinity chromatography (IMAC) adsorbents generally have excellent affinity for histidine-rich proteins. However, the leaching of metal ions from the adsorbent usually affects its adsorption performance, which greatly affects the reusable performance of the adsorbent, resulting in many limitations in practical applications. Herein, a novel IMAC adsorbent, i.e., Cu(II)-loaded polydopamine-coated urchin-like titanate microspheres (Cu-PDA-UTMS), was prepared via metal coordination to make Cu ions uniformly decorate polydopamine-coated titanate microspheres. The as-synthesized microspheres exhibit an urchin-like structure, providing more binding sites for hemoglobin. Cu-PDA-UTMS exhibit favorable selectivity for hemoglobin adsorption and have a desirable adsorption capacity towards hemoglobin up to 2704.6 mg g⁻¹. Using 0.1% CTAB as eluent, the adsorbed hemoglobin was easily eluted with a recovery rate of 86.8%. In addition, Cu-PDA-UTMS shows good reusability up to six cycles. In the end, the adsorption properties by Cu-PDA-UTMS towards hemoglobin from human blood samples were analyzed by SDS-PAGE. The results showed that Cu-PDA-UTMS are a high-performance IMAC adsorbent for hemoglobin separation, which provides a new method for the effective separation and purification of hemoglobin from complex biological samples. Full article

Due to its high acidity and toxic metal content, acid mine drainage (AMD) needs to be properly treated before being discharged into the environment. This study took the AMD collected from one specific mine in China as a sample and investigated the treatment methodology for AMD. The water quality of the AMD was measured, and the sample was treated with caustic soda (NaOH) and shell powder (one kind of conventional neutralizer, mainly composed of CaCO₃) by the neutralization method. The results show that the AMD has a relatively low pH (2.16) and contains high concentrations of Fe (77.54 g/L), Mn (621.29 mg/L), Cu (6.54 mg/L), Ca (12.39 mg/L), and Mg (55.04 mg/L). NaOH was an effective neutralizer to treat the AMD and performed much better than shell powder. Various metals were precipitated, in the order of Fe(III), Cu, Fe(II), Mn, Ca, and Mg. The metal removal mechanisms included precipitation, adsorption, and co-precipitation. The optimal reaction conditions were the reaction duration was selected as 5 min and the mass ratio of NaOH to AMD was 0.16:1 (w:v). By this stage, the pH rapidly increased from 2.16 to 8.53 during AMD-NaOH interactions and various metals were efficiently removed (from 86.71% to 99.99%) by NaOH. The residual mass concentrations of Fe, Mn, Cu, Ca, and Mg after the treatment were 1.52, 1.77, 0.10, 1.65, and 2.17 mg/L, respectively. These data revealed that NaOH was a good treatment regent for this kind of AMD, based on the discharge criteria of China (GB28661 2012). Also, the shell powder was a helpful neutralizer for pH adjustment and copper removal. This neutralization method has the advantages of convenient operation, high speed, good effect, simple equipment, and low infrastructure cost. In addition, the resulting neutralized residue is a valuable and high-quality raw material, which can be used in metal smelting and separation. Full article

The recycling of metals from waste printed circuit boards (WPCBs) has been presented as a solid–liquid extraction process using two deep eutectic solvents (DESs) and four ionic liquids (ILs). The extraction and separation of Cu(II), Ag(I), and other metals, such as Al(III), Fe(II), and Zn(II), from the solid WPCBs (after the physical, mechanical, and thermal pre-treatments) with different solvents are demonstrated. Two popular DESs were used to recover valuable metal ions: (1) choline chloride + malonic acid, 1:1, and (2) choline chloride + ethylene glycol, 1:2. The extraction efficiencies of DES 1 after two extraction and two stripping stages were only 15.7 wt% for Cu(II) and 17.6 wt% for Ag(I). The obtained results were compared with those obtained with four newly synthetized ILs as follows: didecyldimethylammonium propionate ([N_10,10,1,1][C₂H₅COO]), didecylmethylammonium hydrogen sulphate ([N_10,10,1,H][HSO₄]), didecyldimethylammonium dihydrogen phosphate ([N_10,10,1,1][H₂PO₄]), and tetrabutylphosphonium dihydrogen phosphate ([P_4,4,4,4][H₂PO₄]). Various additives, such as didecyldimethyl ammonium chloride surfactant, DDACl; hydrogen peroxide, H₂O₂; trichloroisocyanuric acid, TCCA; and glycine or pentapotassium bis(peroxymonosulphate) bis(sulphate), PHM, were used with ILs during the extraction process. The solvent concentration, quantity of additivities, extraction temperature, pH, and solid/liquid, as well as organic/water ratios, and the selectivity and distribution ratios were described for all of the systems. The utilization of DESs and the new ILs with different additives presented in this work can serve as potential alternative extractants. This will help to compare these extractants, additives, extraction efficiency, temperature, and time of extraction with those of others with different formulas and procedures. The metal ion content in aqueous and stripped organic solutions was determined by the ICP-MS or ICP-OES methods. The obtained results all show that solvent extraction can successfully replace traditional hydrometallurgical and pyrometallurgical methods in new technologies for the extraction of metal ions from a secondary electronic waste, WPCBs. Full article

The paper presents the possibility of recovering metals from printed circuit boards (PCBs) of spent mobile phones using the hydrometallurgical method. Two-stage leaching of Cu(II), Fe(III), Sn(IV), Zn(II), Ni(II) and Pb(II) with H₂SO₄ (2 and 5 M) and HNO₃ (2 M) with the addition of H₂O₂ (10 and 30%) and O₃ (9 or 15 g/h) was conducted at various process conditions (temperature—313, 333 and 353 K, time—60, 120, 240, 300 min, type and concentration of leaching agent, type and concentration of oxidant, solid–liquid ratio (S/L)), allowing for a high or total metals leaching rate. The use of two leaching stages allows for the preservation of selectivity, separation and recovery of metals: in the first stage of Fe(III), Sn(IV) and in the second stage of the remaining tested metal ions, i.e., Cu(II), Zn(II), Ni(II) and Pb(II). Removing Fe from the tested PCBs’ material at the beginning of the process eliminates the need to use magnetic methods, the purpose of which is to separate magnetic metal particles (ferrous) from non-magnetic (non-ferrous) particles; these procedures involve high operating costs. Since the leaching of Cu(II) ions with sulfuric(VI) acid practically does not occur (less than 1%), this allows for almost complete transfer of these ions into the solution in the second stage of leaching. Moreover, to speed up the process and not generate too many waste solutions, oxidants in the form of hydrogen peroxide and ozone were used. The best degree of leaching of all tested metal ions was obtained when 2 M sulfuric(VI) acid at 353 K was used in the 1st research stage, and 2 M nitric(V) acid and 9 g/h O₃ at 298 K in the 2nd stage of leaching, which allowed it to be totally leached 100% of Fe(III), Cu(II), Sn(IV), Zn(II), Ni(II) and 90% Pb(II). Full article

The influence of stable-to-self-condensation Cu(II)-coordinated polyoxyethylene-substituted silicas (ASiP-Cu-0.5) on the synthesis of microporous block copolymers (OBCs) whose structural feature is the existence of coplanar polyisocyanate blocks of acetal nature (O-polyisocyanates) and a flexible-chain component of amphiphilic nature was studied. The use of ASiP-Cu-0.5 increased the yield of O-polyisocyanate blocks and the microphase separation of OBC. The resulting OBCs turned out to be effective sorbents for the analytical reagents PAN and PHENAZO, which, being in the micropore cavity, interacted with copper(II) and magnesium ions. To reduce the thickness of the selective OBC layer ten-fold and simplify the technology for obtaining analytical test systems, polyethylene terephthalate was used as a substrate for applying OBC. It was found that the increased sensitivity of the resulting test systems was due to the fact that in thin reaction layers, the efficiency of the formation of O-polyisocyanate blocks noticeably increased. Full article

In this work, poly(vinyl chloride)-based polymeric ionic liquid inclusion membranes were used in the selective separation of Fe(III), Zn(II), Cd(II), and Cu(II) from hydrochloride aqueous solutions. The ionic liquids under study were 1-octyl-3-methylimidazolium hexafluorophosphate, [omim⁺][PF₆⁻] and methyl trioctyl ammonium chloride, [MTOA⁺][Cl⁻]. For this purpose, stability studies of different IL/base polymer compositions against aqueous phases were carried out. Among all polymer inclusion membranes studied, [omim⁺][PF₆⁻]/PVC membranes at a ratio of 30/70 and [MTOA⁺][Cl⁻]/PVC membranes at a ratio of 70/30 were able to retain up to 82% and 48% of the weight of the initial ionic liquid, respectively, after being exposed to a solution of metal ions in 1 M HCl for 2048 h (85 days). It was found that polymer inclusion membranes based on the ionic liquid methyl trioctyl ammonium chloride allowed the selective separation of Zn(II)/Cu(II) and Zn(II)/Fe(III) mixtures with separation factors of 1996, 606 and, to a lesser extent but also satisfactorily, Cd(II)/Cu(II) mixtures, with a separation factor of 112. Therefore, selecting the appropriate ionic liquid/base polymer mixture makes it possible to create polymeric inclusion membranes capable of selectively separating target metal ions. Full article

The application of a bidentate aromatic N,N’-donor ligand, 2,2′-biimidazole (BIIMH₂), as an extractant in the form of 1-octyl-2,2′-biimidazole (OBIIMH) and related derivatives in the solvent extraction of base metal ions (Mg²⁺, Mn²⁺, Fe³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) from an acidic sulfonate medium using dinonylnaphthalene disulfonic acid (DNNDSA) as a synergist was investigated. OBIIMH with DNNDSA as a co-extractant showed a lack of selectivity for base metals ions (Mg²⁺, Mn²⁺, Fe³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) despite its similarity with a related bidentate aromatic ligand, 2,2′-pyridylimidazole, which showed preference for Ni(II) ions. The nickel(II) specificity, through stereochemical “tailor-making”, was not achieved as expected and the extracted species were isolated to study the underlying chemistry. The homemade metal sulfonate salts, M(RSO₃)₂·6H₂O (R = Toluene and M²⁺ = Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺), were used as precursors of the metal complexes of BIIMH₂ using toluene-4-sulfonic acid as the representative sulfonate. Spectroscopic analysis and single-crystal X-ray analysis supported the formation of similar neutral distorted octahedral sulfonato complexes through the bis coordination of BIIMH₂ and two sulfonate ions rather than the formation of cationic complex species with anion coordination of sulfonates. We attributed the observation of similar complex species and the similar stability constants of the bis-complexes in solution as the cause for the lack of pH-metric separation of the later 3d metal ions. Full article