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"Mannu, Alberto"
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Solvometallurgy as Alternative to Pyro- and Hydrometallurgy for Lithium, Cobalt, Nickel, and Manganese Extraction from Black Mass Processing: State of the Art
by
Cornelio, Antonella
,
Zanoletti, Alessandra
,
Mannu, Alberto
in
Batteries
,
Chemical reaction, Rate of
,
Chemical synthesis
2025
The rapid growth in lithium-ion battery (LIB) demand has underscored the urgent need for sustainable recycling methods to recover critical metals such as lithium, cobalt, nickel, and manganese. Traditional pyrometallurgical and hydrometallurgical approaches often suffer from high energy consumption, environmental impact, and limited metal selectivity. As an emerging alternative, solvometallurgy, and in particular the use of low-melting mixtures solvents, including deep eutectic solvents, offers a low-temperature, tunable, and potentially more environmentally compatible pathway for black mass processing. This review presents a comprehensive assessment of the recent advances (2020–2025) in the application of LoMMSs for metal recovery from LCO and NCM cathodes, analyzing 71 reported systems across binary, ternary, hydrated, and non-ChCl-based solvent families. Extraction efficiencies, reaction kinetics, coordination mechanisms, and solvent recyclability are critically evaluated, highlighting how solvent structure influences performance and selectivity. Particular attention is given to the challenges of lithium recovery, solvent degradation, and environmental trade-offs such as energy usage, waste generation, and chemical stability. A comparative synthesis identifies the most promising systems based on their mechanistic behavior and industrial relevance. The future outlook emphasizes the need for greener formulations, enhanced lithium selectivity, and life-cycle integration to support circular economy goals in battery recycling.
Journal Article
Band-Gap Energies of Choline Chloride and Triphenylmethylphosphoniumbromide-Based Systems
by
Mele, Andrea
,
Mannu, Alberto
,
Di Pietro, Maria Enrica
in
Choline - chemistry
,
deep band-gap systems
,
deep eutectic solvents
2020
UV–VIS spectroscopy analysis of six mixtures containing choline chloride or triphenylmethylphosphonium bromide as the hydrogen bond acceptor (HBA) and different hydrogen bond donors (HBDs, nickel sulphate, imidazole, d-glucose, ethylene glycol, and glycerol) allowed to determine the indirect and direct band-gap energies through the Tauc plot method. Band-gap energies were compared to those relative to known choline chloride-containing deep band-gap systems. The measurements reported here confirmed the tendency of alcohols or Lewis acids to increment band-gap energy when employed as HBDs. Indirect band-gap energy of 3.74 eV was obtained in the case of the triphenylmethylphosphonium bromide/ethylene glycol system, which represents the smallest transition energy ever reported to date for such kind of systems.
Journal Article
Available Technologies and Materials for Waste Cooking Oil Recycling
by
Mannu, Alberto
,
Garroni, Sebastiano
,
Mele, Andrea
in
Biodiesel fuels
,
Biofuels
,
Biomedical materials
2020
Recently, the interest in converting waste cooking oils (WCOs) to raw materials has grown exponentially. The driving force of such a trend is mainly represented by the increasing number of WCO applications, combined with the definition, in many countries, of new regulations on waste management. From an industrial perspective, the simple chemical composition of WCOs make them suitable as valuable chemical building blocks, in fuel, materials, and lubricant productions. The sustainability of such applications is sprightly related to proper recycling procedures. In this context, the development of new recycling processes, as well as the optimization of the existing ones, represents a priority for applied chemistry, chemical engineering, and material science. With the aim of providing useful updates to the scientific community involved in vegetable oil processing, the current available technologies for WCO recycling are herein reported, described, and discussed. In detail, two main types of WCO treatments will be considered: chemical transformations, to exploit the chemical functional groups present in the waste for the synthesis of added value products, and physical treatments as extraction, filtration, and distillation procedures. The first part, regarding chemical synthesis, will be connected mostly to the production of fuels. The second part, concerning physical treatments, will focus on bio-lubricant production. Moreover, during the description of filtering procedures, a special focus will be given to the development and applicability of new materials and technologies for WCO treatments.
Journal Article
Innovative applications of waste cooking oil as raw material
by
Mannu, Alberto
,
Di Pietro, Maria Enrica
,
Mele, Andrea
in
Authorship
,
Biodiesel fuels
,
Biofuels
2019
The consideration towards waste cooking oils is changing from hazardous waste to valuable raw material for industrial application. During the last 5 years, some innovative processes based on the employment of recycled waste cooking oil have appeared in the literature. In this review article, the most recent and innovative applications of recycled waste cooking oil are reported and discussed. These include the production of bioplasticizers, the application of chemicals derived from waste cooking oils as energy vectors and the use of waste cooking oils as a solvent for pollutant agents.
Journal Article
Optimization of Nazarov Cyclization of 2,4-Dimethyl-1,5-diphenylpenta-1,4-dien-3-one in Deep Eutectic Solvents by a Design of Experiments Approach
by
Blangetti, Marco
,
Nejrotti, Stefano
,
Mannu, Alberto
in
Acetic Acid - chemistry
,
Acids
,
Box-Behnken design
2020
The unprecedented Nazarov cyclization of a model divinyl ketone using phosphonium-based Deep Eutectic Solvents as sustainable non-innocent reaction media is described. A two-level full factorial Design of Experiments was conducted for elucidating the effect of the components of the eutectic mixture and optimizing the reaction conditions in terms of temperature, time, and substrate concentration. In the presence of the Deep Eutectic Solvent (DES) triphenylmethylphosphonium bromide/ethylene glycol, it was possible to convert more than 80% of the 2,4-dimethyl-1,5-diphenylpenta-1,4-dien-3-one, with a specific conversion, into the cyclopentenone Nazarov derivative of 62% (16 h, 60 °C). For the reactions conducted in the DES triphenylmethylphosphonium bromide/acetic acid, quantitative conversions were obtained with percentages of the Nazarov product above 95% even at 25 °C. Surface Responding Analysis of the optimized data furnished a useful tool to determine the best operating conditions leading to quantitative conversion of the starting material, with complete suppression of undesired side-reactions, high yields and selectivity. After optimization, it was possible to convert more than 90% of the model substrate into the desired cyclopentenone with cis percentages up to 77%. Experimental validation of the implemented model confirmed the robustness and the suitability of the procedure, leading to possible further extension to this specific combination of experimental designs to other substrates or even to other synthetic processes of industrial interest.
Journal Article
Statistical Analysis Applied to the Production of Mirto Liqueur
by
Mannu, Alberto
,
Pintore, Giorgio
,
Addis, Roberta
in
anthocyanin
,
antioxidant activity
,
Berries
2024
Preparation of myrtle liqueur through ethanol-based extraction is a widely employed methodology. Nevertheless, optimization of existing processes is possible, especially through a modern statistical multivariate approach. In this context, a Design of Experiments (DoE) approach was used to quantitatively assess for the first time the effect of the time, ethanol concentration, temperature, and the ratio between the Myrtus communis berries’ weight and the extractant volume (v/w) on the amounts of anthocyanins, volatile compounds and dry residues in the liqueur. The kinetic profile relative to the volatile fraction variation during the process was described by gas chromatography (GC), while spectrophotometric analysis allowed quantification of the total anthocyanins and total polyphenols. Multiple response analysis showed that the maximum efficiencies in terms of the considered parameters (desirability function) were reached by setting the temperature to 25 °C and the ethanol percentage to 96% after 20 days of processing. Some hints as to the chemical instability and not negligible sensitivity of anthocyanins in relation to the experimental conditions for longer extraction times were also observed. The statistical model represents a novel tool for industrial production of myrtle liqueur.
Journal Article
Decoloration of Waste Cooking Oil by Maghnia Algerian Clays via Ion Exchange and Surface Adsorption
by
Garroni, Sebastiano
,
Taleb, Zoubida
,
Kedir, Chahineze Nawel
in
Adsorbents
,
Adsorption
,
Bentonite
2025
The purification of waste cooking oils (WCOs) through clay-based adsorption is an established recycling method, yet the relationship between clay composition and adsorption efficiency remains an area of active research. The aim of the present research work was to assess the performance of Maghnia bentonite in WCO decoloration and to gain information about the specific refining process. Thus, natural bentonite from the Maghnia region (Algeria) was investigated as an adsorbent for WCO refining for biolubricant production. The adsorption efficiency was evaluated under different conditions, achieving up to 70% decolorization at 10 wt% clay after 4 h of treatment. Structural characterization of the bentonite before and after adsorption was conducted using FT-IR spectroscopy, powder X-ray diffraction (XRD), and X-ray fluorescence (XRF) to assess compositional and morphological changes. FT-IR analysis confirmed the adsorption of organic compounds, XRD indicated minor alterations in interlayer spacing, and XRF revealed ion exchange mechanisms, including a reduction in sodium and magnesium and an increase in calcium and potassium. Adsorption kinetics followed a pseudo-second-order model, with desorption effects observed at prolonged contact times. The pHPZC of 8.3 suggested that bentonite adsorption efficiency is enhanced under acidic conditions. The high decoloration capacity of Maghnia bentonite, combined with the availability and the low cost of the material, suggests a possible industrial application of this material for WCO refinement, especially in lubricant production.
Journal Article
Antimicrobial Activity and Chemical Characterization of a Non-Polar Extract of Saffron Stamens in Food Matrix
by
Zara, Giacomo
,
Mannazzu, Ilaria
,
Zara, Severino
in
Antibacterial activity
,
antibacterial properties
,
Antimicrobial activity
2021
The production of saffron spice generates large quantities of plant by-products: over 90% of the plant material collected is discarded, and a consideration fraction of this waste is plant stamens. This work investigated the chemical composition and the antimicrobial activities of the non-polar fraction extracted from four different saffron flower stamens. The chemical composition of ethereal extracts of the saffron stamens was qualitatively assessed by means of gas–chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) analyses. These analyses revealed ethereal extracts to possess a high polyunsaturated fatty acid content. In vitro antibacterial activity of stamen extracts showed no large differences between Gram-positive and Gram-negative bacteria in terms of minimal inhibitory concentration (MIC). In food matrix microbial analysis of the bacterial strains belonging to the main foodborne pathogen species, including Staphylococcus aureus DSM 20231, Escherichia coli DSM 30083, and Listeria monocytogenes DSM 20600, using low-fat UHT milk, revealed a statistically significant reduction in the number of cells (particularly for E. coli and S. aureus with a complete elimination of the population of the two target bacteria following incubation in diethyl ether extracts of saffron stamen (DES) at high concentrations tested, both at 37 °C and 6 °C (for 48 h and 7 days, respectively). A synergic effect was observed when the pathogens were incubated at 6 °C with DES. This work shows these by-products to be excellent sources of bioactive compounds, which could be exploited in high-added-value products, such as food, cosmetics, and drugs.
Journal Article
Classification of Pummelo (Citrus grandis) Extracts through UV-VIS-Based Chemical Fingerprint
by
Pintore, Giorgio
,
Mannu, Alberto
,
Di Pietro, Maria Enrica
in
ambient temperature
,
Chemical composition
,
Chemical fingerprinting
2022
Cold extraction methods with ethanol applied to the flavedo of Citrus fruits have been commonly applied for the preparation of several liquors. In order to obtain the extraction optimization and then the best ratio of functional ingredients in the extract, the flavedo of Citrus grandis Osbeck (pummelo) was subjected to a maceration with absolute ethanol at room temperature as well as at 40 °C. The kinetics of the extraction methods were monitored by UV–VIS spectroscopy, and a chemical fingerprint characteristic of each extract was determined by statistical multivariate analysis of the UV–VIS raw data. Additionally, the extracts were qualitatively characterized by NMR spectroscopy as well as by solid phase micro extraction followed by gas chromatography/mass spectrometry (GC/MS). NMR analysis confirmed the presence of the typical flavanones of Citrus such as naringin and naringenin, while the GC/MS analysis showed that the headspace of the liquor is characterized by two main compounds represented by β-myrcene and limonene. At the end, the temperature seems to not affect the time of extraction, which is complete after 25 h; however, UV–VIS-based multivariate analysis revealed that a different overall chemical composition is obtained depending on the temperature, probably due to the extraction of minor chemicals as well as due to different levels of the same compounds in the two extracts.
Journal Article
Fischer-Speier Esterification and Beyond: Recent Mechanicistic Advances
2024
Over the past 130 years, Fischer-Speier esterification has been established as the benchmark method for synthesizing esters from organic acids and alcohols. The reaction’s versatility, arising from the vast combinations of starting materials and the numerous catalytic alternatives to the traditional H2SO4, has maintained its relevance, with a steady flow of publications addressing new developments. This review highlights the most significant contributions to Fischer-Speier esterification over the past five years, with a particular emphasis on mechanistic advancements and innovative catalytic systems. Both homogeneous and heterogeneous catalytic approaches are discussed, including novel catalysts leveraging hydrogen-bonding interactions and systems offering fresh insights into specific reaction mechanisms and atypical methodologies. Some of these catalytic systems, as ionic liquids or sulfonated heterogeneous catalytic precursors, reached excellent yields (>90%), e.g., in the synthesis of fatty acids methyl esters. Also, classic catalysts such as H2SO4 and para-toluen sulfonic acid were optimized for quantitative conversions (e.g., in the esterification of trans-cinnamic acid with methanol). A consistent number of catalysts was studied with model substrates (as benzoic acid in combination with methanol, ethanol, and ethylene glycol), and new activation pathways were presented.
Journal Article