Selective recovery of copper from copper tailings and wastewater using chelating resins with bis-picolylamine functional groups.

Industrial and mining wastewater, along with copper tailings, are typically highly acidic and contain copper and other heavy metals, which may contaminate and damage the environment. Copper (Cu) is, however, a valuable metal, making its removal and recovery from such wastewater and tailings environmentally and economically advantageous. Chelating ion exchange resins featuring bis-picolylamine functional groups are especially suitable for application requiring selective recovery of Cu(II) from highly acidic media. In this study, and for the first time, the kinetics, binding capacity and selectivity of Lewatit MDS TP 220 chelating resin towards Cu(II) are reported. The resin was characterized by Zeta potential, scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Factors including pH, initial concentration, contact time, temperature, and selectivity were investigated to assess the adsorption performance of the chelating resin. The adsorption kinetics tests revealed fast adsorption within the first 5-30 min and fitted the pseudo-second-order model, signifying chemisorption process. The adsorption isotherm followed the Langmuir model, implying monolayer adsorption process. The maximum adsorption capacity (qm) for Cu(II) determined by the Langmuir model was 103.9 mg/g. The adsorption thermodynamics showed an endothermic and spontaneous adsorption. FTIR and XPS studies suggested coordination or chelation as the possible adsorption mechanism. Lewatit MDS TP 220 exhibited excellent Cu(II) adsorption, desorption with 2 M ammonium hydroxide (NH4OH), and selectivity in multi-metal ions solution. Additionally, the resin demonstrated excellent reusability after five regeneration steps. This chelating resin is a potential adsorbent for effective and recurrent recovery of Cu(II) from copper tailings and wastewater, thereby contributing to environmental remediation.

Laser irradiation of photothermal precursors - a novel approach to produce carbon materials for supercapacitors.

A wide array of carbon materials finds extensive utility across various industrial applications today. Nonetheless, the production processes for these materials continue to entail elevated temperatures, necessitate the use of inert atmospheres, and often involve the handling of aggressive and toxic chemicals. The prevalent method for large-scale carbon material production, namely the pyrolysis of waste biomass and polymers, typically unfolds within the temperature range of 500-700 °C under a nitrogen (N2) atmosphere. Unfortunately, this approach suffers from significant energy inefficiency due to substantial heat loss over extended processing durations. In this work, we propose an interesting alternative: the carbonization of photothermal nanocellulose/polypyrrole composite films through CO2 laser irradiation in the presence of air. This innovative technique offers a swift and energy-efficient means of preparing carbon materials. The unique interaction between nanocellulose and polypyrrole imparts the film with sufficient stability to retain its structural integrity post-carbonization. This breakthrough opens up new avenues for producing binder-free electrodes using a rapid and straightforward approach. Furthermore, the irradiated film demonstrates specific and areal capacitances of 159 F g-1 and 62 µF cm-2, respectively, when immersed in a 2 M NaOH electrolyte. These values significantly surpass those achieved by current commercial activated carbons. Together, these attributes render CO2-laser carbonization an environmentally sustainable and ecologically friendly method for carbon material production.

The effect of the pyrolysis temperature and biomass type on the biocarbons characteristics.

The conversion of biomass and natural wastes into carbon-based materials for various applications such as catalysts and energy-related materials is a fascinating and sustainable approach emerged during recent years. Precursor nature and characteristics are complex, hence, their effect on the properties of resulting materials is still unclear. In this work, we have investigated the effect of different precursors and pyrolysis temperature on the properties of produced carbon materials and their potential application as negative electrode materials in Li-ion batteries. Three biomasses, lignocellulosic brewery spent grain from a local brewery, catechol-rich lignin and tannins, were selected for investigations. We show that such end-product carbon characteristic as functional and elemental composition, porosity, specific surface area, defectiveness level, and morphology strictly depend on the precursor composition, chemical structure, and pyrolysis temperature. The electrochemical characteristics of produced carbon materials correlate with the characteristics of the produced materials. A higher pyrolysis temperature is shown to be favourable for production of carbon material for the Li-ion battery application in terms of both specific capacity and long-term cycling stability.

Comparative Study of the Structural Features and Electrochemical Properties of Nitrogen-Containing Multi-Walled Carbon Nanotubes after Ion-Beam Irradiation and Hydrochloric Acid Treatment.

Using a set of microscopic, spectroscopic, and electrochemical methods, a detailed study of the interrelation between the structural and electrochemical properties of the as-prepared nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) and their modified derivatives is carried out. It was found that after treatment of nanotubes with hydrochloric acid, their structure is improved by removing amorphous carbon from the outer layers of N-MWCNTs. On the contrary, ion bombardment leads to the formation of vacancy-type structural defects both on the surface and in the bulk of N-MWCNTs. It is shown that the treated nanotubes have an increased specific capacitance (up to 27 F·g-1) compared to the as-prepared nanotubes (13 F·g-1). This is due to an increase in the redox capacitance. It is associated with the reversible Faraday reactions with the participation of electrochemically active pyridinic and pyrrolic nitrogen inclusions and oxygen-containing functional groups (OCFG). Based on the comparison between cyclic voltammograms of N-MWCNTs treated in HCl and with an ion beam, the peaks on these curves were separated and assigned to specific nitrogen inclusions and OCFGs. It is shown that the rate of redox reactions with the participation of OCFGs is significantly higher than that of reactions with nitrogen inclusions in the pyridinic and pyrrolic forms. Moreover, it was established that treatment of N-MWCNTs in HCl is accompanied by a significant increase in the activity of nitrogen centers, which, in turn, leads to an increase in the rate of redox reactions involving OCFGs. Due to the significant contribution of redox capacitance, the obtained results can be used to develop supercapacitors with increased total specific capacitance.

How intramolecular coordination bonding (ICB) controls the homolysis of the C-ON bond in alkoxyamines.

Because the C-ON bond homolysis rate constant k d is an essential parameter of alkoxyamine reactivity, it is especially important to tune k d without a major alteration of the structure of the molecule. Recently, several approaches have become known, e.g., protonation of functional groups and formation of metal complexes. In this paper, coordination reactions of [Zn(hfac)2(H2O)2] with a series of new SG1-based alkoxyamines affording complexes with different structures are presented. The k d values of the complexed forms of the alkoxyamines were compared to those of free and protonated ones to reveal the contribution of the electron-withdrawing property and structure stabilization. Together with previously published data, this work provides clues to the design of alkoxyamines that can be effectively activated upon coordination with metal ions. Furthermore, our results provide insight into the mechanism underlying the influence of complexation on the reactivity of alkoxyamines. This led us to describe different types of coordination: intramolecular in nitroxyl fragment, intramolecular in alkyl fragment, intramolecular between alkyl and nitroxyl fragment, and intermolecular one. All of them exhibit different trends which are dramatically altered by changes in conformation.

Versatile approach to activation of alkoxyamine homolysis by 1,3-dipolar cycloaddition for efficient and safe nitroxide mediated polymerization.

An alkoxyamine was prepared from a cyclic aldonitrone nitroxide. The resulting alkoxyamine containing an aldonitrone functional substituent is relatively stable but can react readily with vinyl monomers to form a cycloadduct that has a much higher C-ON homolysis rate. This type of in situ activation converts the aldonitrone alkoxyamine into an efficient controlling agent for nitroxide-mediated polymerization. Here we present a study on this reaction of C-ON bond homolysis and application of such an alkoxyamine as an in situ-activated initiator.