Research activity in the Academic Year 2024-25 of PhD students is below briefly summarized.
As regards to the first year students (40th cycle) activity:
- During this first PhD year of the thesis: Development of microbiological electrolytic cell technologies for hydrogen production, a two-chambers continuous flow planar Microbial Electrolysis Cell (MEC) was studied for hydrogen production. The anode consisted of granular graphite and the cathode in stainless steel. Two runs were carried out applying two different OLR values, 0.50 g COD/Ld (Run I) and 2.0 g COD/Ld (Run II), respectively. The substrate consisted of a synthetic mixture simulating the effluent from the acidogenic fermentation of cheese whey. Results were analyzed in terms of COD removal efficiency, coulombic efficiency, hydrogen production and cathode capture efficiency. This key parameters for both anodic and cathodic processes were regularly monitored. At the same time, acclimatization tests were set up with the aim to select a microbial consortium capable of oxidizing slowly degradable molecules like propionic and butyric acid. The experiments of acclimatation were conducted in H-type cells with inoculation of digestate and marine sediment. In this experiment the anode consisted of carbon brush and the cathode Nichel foaming.
- During the academic year 2024–25, the research on: “Sustainable processes for the remediation of historically polluted sites” focused on sustainable remediation processes integrating biological and adsorptive mechanisms. A comprehensive bibliographic study was conducted to analyze the target contaminants and suitable treatment strategies. Experimental activities involved the analysis and application of Polyhydroxyalkanoates (PHA) for environmental remediation, including biomass characterization, fermentation at different PHA contents, and evaluation of their performance in biological reductive dechlorination evaluating the effect of the temperature. Adsorption tests compared biochar and activated carbon, also assessing temperature effects (20 °C and 30 °C) and the potential reuse of excess heat from thermal desorption processes.
- During the first year, the project on “Sintetic enzyme mediated solvent enanched weathernig for CO2 capture and reutilization” focused on preliminary activities. A review of the literature was conducted to map the state of the art on CA-inspired solvents and CCUS technologies. Several biomimetic DES systems (His–Zn with ChCl/urea and Ch/PG) were prepared and subjected to initial physicochemical characterization. Early experimental tests were performed to verify and calibrate the semi-batch apparatus for CO₂ capture. Preliminary UV-Vis and FTIR analyses were initiated to confirm metal–ligand complex formation. The methodological framework for a subsequent techno-economic feasibility study was established. Dissemination activities included the preparation of a review paper on the topic, which is currently under peer review.
- The project “Biotechnological processes employing mixed microbial cultures for the treatment and simultaneous valorization of organic waste streams” was based on the study of an innovative biotechnological continuous-flow process for polyhdroxyalkanoates (PHA) production with mixed microbial culture (MMC), with particular interest at both PHA production and downstream processing. Three reactors (i.e. Feast, Famine and Accumulation reactor) were proposed. The downstream processing was carried out with a non-toxic procedure implying the alkaline digestion of the Non-PHA Cell Mass (NPCM) component with sodium hydroxide (NaOH) with a further purification with Hydrogen peroxide. The recovery of high value-added co-product from the downstream processing side-stream was also investigate. As regards to the results in the AY 2024-25, the MMC-PHA continuous flow process resulted in an intracellular PHA content of 55 ± 2% (wt/wt) in the accumulation reactor at an applied organic loading rate (OLR) of 7.20 g COD/L using a synthetic mixture of acetic and propionic acids. Alkaline digestion of the NPCM with 0.3 M NaOH, followed by purification with 1.5 wt/v hydrogen peroxide, can achieve a final PHA purity of 97 ± 2% (wt/wt). Proteins and carbohydrates can be successfully recovered from the alkaline side stream via acidic precipitation (pH = 2) with respective recovery rates of 72 ± 1% (wt/wt) and 43 ± 1% (wt/wt). The recovered co-product (i.e., the mixture of precipitated proteins and carbohydrates) exhibits gel-forming properties in the presence of a divalent cation and surfactant behavior with a polar solvent, such as hexane or xylene, which could lead to applications in the agricultural sector and water remediation.
- In the framework of the project: “Impurities Management and Performance Assessment in Cathode Technologies from Recycling”, During the 2024–25 academic year, the research focused on synthesizing cathode materials (NMC811) with individual metallic impurities to simulate contamination from industrial recycling processes. A series of controlled samples were prepared, each containing a specific impurity at varying concentrations. Advanced structural and electrochemical characterizations were conducted to assess the impact of each impurity on material stability and battery performance. The characterization phase is currently at an advanced stage. Additionally, complementary analyses were performed to optimize synthesis parameters and enhance material performance. These efforts aim to establish a robust methodology for quantifying impurity effects. The results will serve as a foundation for the next project phase, which will address complex impurity mixtures.
- As regards to the project: “Synthesis and optimization of novel lithium-rich transition metal oxides”, the goal of the first year was therefore to optimize the synthesis conditions to obtain the desired lithium-rich cathode material. The objectives of the following years will be to improve stability and electrochemical performance, and deepen structural characterization techniques, to obtain cathode material that is improved in every respect and ready for commercialization. The solid-state synthesis conditions have been defined and optimized to obtain the desired lithium-rich cathode material. Subsequently, the optimal annealing parameters were identified to enable the controlled formation of the different crystalline phases. In particular, a disordered rock-salt phase with cubic symmetry, described by the space group Fm-3m, was obtained, along with layered phases characterized by hexagonal (R-3m) and monoclinic (C2/m) symmetries. These preliminary results lay the groundwork for the activities planned for the second year of research, which will focus on improving the electrochemical performance and conductivity of the materials, as well as on an in-depth investigation of their structural evolution.
- As regards to the project: “Black Mass Engineering: Development of Innovative Recycling Processes for Electrode Powders from End-of-Life Batteries”, the research focused on black mass engineering for the sustainable recycling of end-of-life batteries, with the aim of reducing reagent consumption and improving process circularity. The work involved developing a hydrometallurgical dual-stream process in which LiFePO₄ (LFP) scraps acts as a reductant to selectively dissolve Ni–Mn–Co (NMC) black mass without the addition of external reducing agents. Experimental activity included optimizing leaching parameters such as temperature, acid concentration, and solid-to-liquid ratio, while monitoring metal dissolution by ICP and characterizing residues by XRD, SEM, and laser granulometry. The Fe–P solids obtained from leaching were converted into FePO₄·2H₂O through hydrothermal synthesis and subsequently relithiated to regenerate LiFePO₄ under controlled pH and redox conditions. Parallel tests on alkaline black mass were initiated to evaluate the recovery of manganese and zinc and to compare the reactivity of oxidized species with that of Li-ion residues. These results provide the experimental basis for defining integrated recycling strategies and for understanding redox interactions between different battery chemistries within a circular economy framework.
- During the first PhD year, of the project: “Chemical recycling of mixed plastic waste by thermochemical processes to produce fuels and fine chemicals”, a literature review on chemical recycling of mixed plastics focused on hydrothermal liquefaction (HTL), pyrolysis, and their integration. Experimental work on plasmix waste from COREPLA involved characterization (FTIR, TGA, elemental analysis) and HTL tests at 280–330 °C for 10–30 min. The main polymers were PE, PP, PET, PVC, and PS. HTL degraded all heteroatom-containing plastics, leaving only PE and PP, confirming its potential as a pretreatment before pyrolysis. The recovery of pure terephthalic acid (TPA) from PET was also evaluated.
- During the first year of the PhD program: “Development of sustainable nano and biomaterials for the conservation of cultural heritage”, activities included: (i) Bibliographic analysis on wood degradation and both traditional and innovative restoration techniques. (ii) Design of green synthesis protocols for nanoparticles based on chitosan, lignin, PLGA, and metal oxides, using plant extracts and agro-industrial waste. (iii) Optimization of synthesis parameters (concentration, solvent, type of extract) to control particle size and colloidal stability. (iv) Material characterization through DLS analysis. (v) Comparison between traditional and green methods: syntheses using plant extracts yielded smaller and more stable particles (below 100 nm). (vi) Delivery of selected samples to the Istituto Superiore per la Conservazione e il Restauro (ICR) for testing on ancient wood.
- During the first academic year of the project: “Technical and economic sustainability analysis of Hydrogen Valley through process simulations and the use of machine learning tools”, the research focused on consolidating the methodological and modeling framework. A literature review on Hydrogen Valleys and hydrogen technologies was completed. A database of Italian Hydrogen Valley projects funded under the PNRR was developed. Process models of AEL and PEM electrolyzers were implemented in Aspen Custom Modeler and coupled with Aspen Plus. The models were applied to a glass industry case study, assessing decarbonization through green hydrogen–methane blending. Preliminary results are being prepared for a scientific article on hydrogen use in the glass sector.
- During the first academic year of the project: “Digital innovation for remediation: 3D models, machine learning, and virtual reality for the management and remediation of contaminated sites”, Reconstruction of multidisciplinary relational geodatabases for multiple contaminated industrial sites across Italy particularly for the Mantua Lakes, combined with various field data collection campaigns. Development of three-dimensional digital models incorporating all available information for the different contaminated sites, complemented by technical reports prepared for the various stakeholders. Within the digital models, the 3D geological model, the reconstruction of the piezometric surface or the bathymetry, and the site’s hydrogeochemical and biological characteristics were integrated. Development of a methodology to recover, valorize and exploit of non-digital and appearently lost data and for the calculation of contaminant masses within environmental matrices, such as surface water and soil, proposing a conservative and rigorous estimate within a non-dynamic system.
As regards to the second year students (39th cycle) activity:
- The second-year activities in the framework of “Ecological and digital transition in the requalification of polluted sites: development of guidelines and vademecum for public administration” the possibility of reactivating biological process after a long term use of combined technologies (i.e. Biological reductive dichlorination coupled with adsorption onto waste material) were investigated; for the remediation of chlorinated solvents-contaminated groundwater possible novel electron donor were studied, which usually are used for other purposes in remediation strategies (i.e. citric acid to avoid metal precipitation in well. Finally, the development of guidelines for public and private actors in remediation started, focusing on ecological innovation and digital technologies for more sustainable and efficient management.
- The second year of “Study of the electrochemical activity of oxygen in Lithium and Nickel rich layered oxides (Li1.2-1.08Mn0.56-0.52Ni0.2-0.4O2) for applications in aprotic lithium-ion batteries”, was focused on the characterization of layered oxides with electrochemical applications as positive electrodes for aprotic lithium-ion batteries. The contribution to the European project SIGNE (Horizon Europe) continued, which involves the study of separators, electrolytes, and nickel-manganese-cobalt (NMC) oxides for 3b generation batteries. In parallel with these tasks, the research activity also aimed at the synthesis and investigation of a new class of compounds referred to as "Lithium-Nickel rich (LN-r)." These materials belong to the broader family of Lithium-rich layered oxides (LRLO), and our contribution focuses on studying the influence of stoichiometry on the complex redox activity of lattice oxygen. To this end, several materials were synthesized and analyzed them at the BESSY II synchrotron in Berlin.
- In the framework of the research “ Project and optimization of a prototype system operating in continuous mode for the re-synthesis of cathode materials of lithium-ion batteries”, particles with good morphology and chemical composition are obtained in a lab-scale reactor. Then, moving to a larger apparatus, the fluid dynamics are monitored, and the characteristic convective time is identified as the rescaling parameter to recover the same aggregation phenomena as the previous equipment.
After identifying the best operating conditions, the apparatus was used in continuous mode to monitor the reactor dynamics. The reactor reaches steady state after five characteristic times.
- In the framework of the thesis: Experimental and study activities of the catalytic conversion processes of CO2 into e-fuels, Process simulation and techno-economic analysis of PtG (biological and catalytic integration) and PtL (syncrude upgrading to kerosene fraction) technologies. Pilot plant tests with Ni- and Ru-based pellet catalysts for CO₂ hydrogenation to methane at ENEA laboratories. Development of pellet and honeycomb Ru-based catalysts for CO₂ hydrogenation to methane at BASF laboratories. Development and investigation of bi-functional Fe-based catalysts for CO₂ hydrogenation to hydrocarbons through colloidal synthesis, aimed at studying C–C coupling, at Stanford University.
- In the framework of the thesis: “Li electrochemical extraction and direct synthesis of new-generation electrode materials from end-of-life lithium-ion batteries”, cathode materials were synthesized from different black mass samples, which varied according to the pretreatment applied. The results highlighted the effect of pretreatment on the recycling process. The synthesized cathode materials were then electrochemically cycled. Anode materials, including graphene, were also cycled and compared with other anode materials. Lithium recovered from the process was collected and characterized. After purification, it was converted into battery-grade LiOH. These experiments allowed evaluation of both material performance and the efficiency of the recycling and recovery processes.
- During the second year of the thesis “Innovative applications of biochar, obtained from agro-industrial wastes”, activities focused on both the characterization and application of biochar. Characterization work included BET surface area analysis and ash content quantification for the various biochar samples, completing the work started in the
previous year. On the application side, several biochars were tested for their adsorption capacity towards dyes (Rhodamine B and Methyl Orange) and metals (Cu and Cd). Adsorption experiments were carried out in both stirred batch reactors and a continuous flow system using a packed column. Preliminary results were also obtained regarding the use of biochar as a booster for anaerobic digestion. Batch reactors filled with sludge and fed with a glucose solution were used, and the produced gases were analyzed using a Quadrupole Gas Analyzer (QGA). Finally, an activity was carried out to investigate the use of biochar as a graphite substitute in the synthesis of graphene oxide via the Hummers method.
- The research “Evaluating Multi-salt Electrolytes and “Anode-less” Supports for Lithium Metal Batteries“ focused on the development of liquid electrolytes and nanostructured metal substrates for lithium metal batteries in “Anode-less/Zero-Excess” configuration.
During this academic year, the following topics were mainly studied:
• First lithium-ion solvation shell visualization of DME-based electrolytes, through ex situ Raman spectroscopy
• Electrochemical performance in lithium half-cell of different liquid electrolytes
• The influence of the electrolyte composition in the first lithium formation on smooth copper substrates, through electron and optical microscopy
• The performance of textured copper substrates in lithium half-cells
• The influence of support surface texturing on first lithium metal formation, through electron and optical microscopy
• Trivials of operando method to characterize liquid electrolytes based on Raman spectroscopy and opto-microscopy
- In the second year of the thesis “Extraction and characterization of bioactive compounds: a comprehensive study”, During the second year, laboratory activities focused on optimizing MAE parameters for protein extraction using a Central Composite Design and extending the work to combined EAE-MAE systems. Preliminary screening confirmed the enhancement of protein yields with enzyme addition, followed by optimization of enzyme mixtures and process conditions. In parallel, DES-based extraction of polyphenols and flavonoids was explored using choline chloride-lactic acid, optimized by Box-Behnken design. Optimal extraction conditions were validated experimentally.
- During the first year of the PhD program of the PNRR grant entitled: “Synthesis of nanostructured electrodes for the electrochemical reduction of carbon dioxide”, Zinc-based electrodes were synthesized by bubbling electrodeposition. To achieve the formation of a zinc-copper foam and improve the catalytic activity of the electrode, copper was added to the deposition bath. Electrodeposition tests were carried out by varying the copper concentration in the bath and the morphology and surface composition of the fabricated electrodes were characterized by SEM and EDS. The pore size increased from 50 to 100 μm by increasing the amount of copper in the deposition bath. By carrying out catalytic CO2 electroreduction tests at three different potentials (-1.5, -1.7, -1.9 V vs. Ag/AgCl), it was observed that the highest faradaic efficiency to carbon monoxide (about 80%) was obtained with the electrode containing the highest amount of copper in the deposition bath (18mM). Subsequently, the effect of electrodeposition current and transferred charge on the electrode morphology was investigated. By doubling both the current and the charge, the pore size decreased from 50 μm to 20 μm. Subsequently, catalytic tests were carried out at three different cathode potentials to verify the effect on faradaic efficiency against CO. It was noted that the highest faradaic efficiency against CO (approximately 95%) was obtained for electrodes with 50-60 μm pores. The catalysts were then deposited on carbon paper. To adjust the wettability of the catalyst layer, electrodeposition was performed using electrolytic baths with suspended PTFE particles, which, being hydrophobic, alter the surface composition of the electrodes. The different morphologies obtained by varying the concentration of PTFE nanoparticles were studied using SEM and EDS. H-cell tests were carried out at different potentials (-1.5, -1.7, -1.9 V vs. Ag/AgCl) to evaluate the production of CO and H2. A laboratory system has been developed and installed, which is currently being used to conduct fuel cell tests.
The activities carried out this year on the “Development of multicomponent lipid nanocarriers via microfluidics for the delivery of genetic material and drugs: characterization and optimization”, focused on the analysis of the data collected during the first academic year, the goal set for the second year was to try to model the mechanism of formation of the aforementioned systems, with the aim ofexplain the mechanism behind the formation of these systems. At the same time, another objective is to create a predictive model capable of optimizing the production of these systems in terms of maximizing molecule encapsulation, optimizing size relative to a target, and minimizing polydispersity. To do this, new operating conditions for the system were investigated compared to those studied last year.
- During the second year of the PhD thesis in "Carbon dioxide sequestration from cement plant fumes and other hard-to-abate industry sectors using reversible molten carbonate fuel cells: development of the simulation model and implementation in the process cycle," During the second year, the research focused on both experimental and modeling activities related to molten carbonate electrolysis cells (MCECs). A paper titled “Effect of Operating Conditions on Molten Carbonate Electrolysis Cell Performance: An Experimental Study” was published in Journal of Power Sources (2025), while a second manuscript on cement industry decarbonization using reversible MCCs and hybrid storage is under review at Nature Communications Sustainability. A three-month research stay at the Korea Institute of Science and Technology (KIST) allowed for experimental work on molten carbonate cell stacks. The candidate also presented results at ICSET 2025, illustrating the use of MCECs for syngas conditioning from gasification. Finally, an Aspen Plus model of MCCs was developed, integrating chemical and thermal aspects to support future electrochemical coupling studies.
- In the first-year doctoral research on “Innovative and eco-sustainable materials, for aprotic sodium ion batteries” aimed at the synthesis and study of nanostructured carbon materials for use as anodes in sodium-ion batteries, the ZTC synthesis was optimized to achieve the desired product with the appropriate mesoporous range and without inorganic residues. The elimination process was verified through thermogravimetric analysis (TGA) in air up to 800 °C. A residue of 83% was measured before elimination, compared to 0% afterward, confirming the complete removal of inorganic phases.
The amorphous carbon obtained was compared with classical hard carbon produced by simple pyrolysis of hazelnut shells. X-ray diffraction (XRD) and Raman spectroscopy showed similar structural parameters for both samples, while scanning electron microscopy (SEM) revealed major morphological differences. HC displayed a smooth surface with no visible pores at 200–20 nm magnification, whereas ZTC exhibited a rough surface with diffuse porosity at the same scale.
Further investigation using small-angle X-ray scattering (SAXS) defined the porosity ranges. HC exhibited predominant microporosity between 1 and 6 nm, while ZTC showed a wider range from 0.5 to 37 nm, centered within the mesoporous domain.
Two types of electrode mixtures were prepared: one containing only HC as the active material, and another with HC plus ZTC as a low-concentration additive.
Galvanostatic cycling showed similar performance at a low current rate of 10 mA/g, with both electrodes achieving a reversible capacity of 250 mAh/g. As expected, the additive-containing electrode displayed higher irreversible capacity in the first cycle, due to its increased surface area.
At higher currents (25, 50, and 250 mA/g), the additive demonstrated clear benefits. Performance systematically improved for the ZTC-containing electrode across all current rates, reaching a plateau capacity retention of 100 mAh/g after 40 cycles, compared to 30 mAh/g for plain HC.
The mechanisms behind this improvement were examined through apparent diffusion coefficient analysis. All electrochemical tests consistently showed higher Na⁺ diffusion rates in electrodes containing the additive.
These results strongly support the initial hypothesis: reducing the HC tortuosity factor with a mesoporous, highly conductive additive featuring a well-connected channel framework improves electrochemical performance.
- In the thesis “Decarbonization of the cement and iron-steel production sectors and enhancement of CO2 through green hydrogen and/or mineralization”, This study investigates how titanium dioxide (TiO₂) nanoparticles improve solvent regeneration in post-combustion CO₂ capture using a 25 wt% potassium carbonate (K₂CO₃) solution. A small amount (0.06 wt%) of TiO₂ was added to enhance desorption efficiency, with nanoparticles ultrasonically dispersed to prevent agglomeration. Experiments in a stirred cell reactor under controlled temperature and nitrogen flow showed slightly higher CO₂ loading with nanoparticles. Desorption tests at various temperatures were monitored in real time using an IR analyzer to study kinetics. Modeling assumed ideal gas behavior and negligible gas-phase resistance to calculate
mass transfer coefficients and diffusivity. Results showed improved desorption performance and mass transfer with nanoparticles, along with reduced energy consumption per unit of CO₂ desorbed.
- The research activities conducted during the second year of the thesis, titled "Microbial Electrochemical Technologies for Cheese Whey Valorization in a Circular Bio-Economy Perspective," Starting from the results obtained during the first year, a synthetic substrate mimicking the effluent from cheese whey (CW) fermentation with conductive materials was prepared and continuously fed (1 gCOD/L acetate) to the bioelectrochemical reactor. Several operational configurations were tested, applying potential differences of 0.8, 1.0, and 1.4 V in a twoelectrode setup. The graphite anode, later supplemented with activated carbon, was inoculated with activated sludge, while the cathode consisted of a stainless-steel mesh. System performance was assessed by monitoring COD removal, gas production (H₂ and CH₄), and pH variations. Two catholytes—anaerobic mineral and saline media—were compared to evaluate ionic effects on cathodic reactions. In parallel, experiments in H-type cells investigated halophilic bacterial consortia under 5% NaCl to assess hydrogen production under saline conditions.
- As regards to the thesis: “Analisi teorica e sperimentale di processi termochimici innovativi alimentati da impianti solari termici a concentrazione” perovskites were synthesized using pechini method, and were characterized via XRD and SEM, while their cyclability and thermal stability were assessed through TGA/DSC analysis. A model was developed to study the equilibrium conditions of the two semi-reactions in the water-splitting process on selected perovskites, and the output of the model was compared to the experimental results. While the model showed good agreement with experiments at high temperatures, its performance at lower temperatures necessitates further improvement. Methane pyrolysis was conducted in a lab-scale reactor using a molten quinary chloride salt, selected for its favorable thermophysical properties. Results establish a baseline for process optimization. Accompanying corrosion tests underscored the critical need for more durable reactor materials.
- In the framework of the thesis: “Combined chemical-physical and biological processes for the remediation of contaminated groundwater”, the research on co-contamination demonstrated that bioelectrochemical systems (BES) can achieve almost complete removal of TCE (>99%) and full reduction of Cr (VI), even under conditions where chromium initially exerted an inhibitory effect on dechlorinating microorganisms. Over time, the microbial community adapted and recovered its dechlorination efficiency, confirming the robustness of the process. The distribution of degradation by-products was shown to depend on operating conditions, providing valuable insights into the interactions between contaminants and microbial populations
In parallel, three column reactors were tested to evaluate the combination of BES with carbonaceous adsorbents. A reactor with only BES, one with only biochar, and a combined BES–biochar system were compared. The combined system outperformed the single technologies, highlighting a synergistic effect. BES activity degraded pollutants adsorbed on biochar, regenerating active sorption sites and prolonging material efficiency, while biochar increased contact time between microorganisms and contaminants, leading to lower effluent concentrations. These outcomes confirm the feasibility of integrating BES with conventional adsorptive technologies, offering new design principles for remediation strategies applicable to complex groundwater contamination.
- The research activity carried out during the first year of the Ph.D. “Development of a Sustainable Biotechnological Process in an Urban Biorefinery Perspective” focused on the management of semi-pilot reactors, in terms of feeding and purging, and the analysis of key chemical and environmental parameters and organic and inorganic constituents (solids, total and soluble COD, alkalinity, total and ammonia nitrogen, phosphorus, carbohydrates, proteins) to evaluate processes status. Analytical instruments like GC and HPLC were used for the determination and quantification of compounds of interest such as lactic acid and carboxylic acids, and to state the composition of produced gases (H2 and CH4).
- The second-year activity on Innovative technology for producing clean H2 involved preparing the HC carbon support from hazelnut shells and the three catalysts, Ni-HC, NiFe-HC, and NiCu-HC, respectively, the second year initially focused on characterizing the materials using Raman, SEM, XRD, TGA, and BET to understand their composition, morphology, and structure. The testing phase then moved on to monitor the catalytic activity. The tests consisted of catalytic cracking of methane in a thermal balance, where carbon growth was monitored during 3 and 6 hours of reaction. These were also compared with a set of catalysts prepared according to a methodology already defined in the literature. Finally, the reaction products were characterized using SEM, XRD, and Raman to assess the nature of the carbonaceous products.
- The study on “Electrochemical storage sytems” During this period, the research focused on improving lithium-ion battery safety through both modeling and data-driven approaches. A literature review was conducted to assess thermal runaway (TR) mechanisms and aging effects, and risk assessment. Electrochemical-thermal simulations were developed to study TR and propagation in single cell and multi-cell modules with normal and abuse condition applied. Machine learning models such as RF, XGBR, GPR, GRU and LSTM were implemented for State of Health (SOH) prediction using the NASA dataset. Data preprocessing and feature extraction were carried out to identify key health indicators. The impact of noisy and incomplete data was analyzed. Physics-informed neural networks were explored. These combined approaches support early failure prediction and safer battery operation.
As regards to the activity of students at the third year (38th cycle):
- In the framework of the thesis “Valorisation of biogenic waste via thermochemical processes for liquid biofuel production: a study on hydrothermal liquefaction of sewage sludge”, the research activity during the third year has been focused on the development of a kinetic model capable of predicting the product yields and the thermal character of hydrothermal liquefaction (HTL) process of sewage sludge, basing on its marco-chemical composition. To validate the model, a screening experimental campaign and calorimetric tests on the HTL of sewage sludge were conducted, during a period of hospitality abroad in M2P2 laboratories of Aix-Marseille university (France). A one-year visiting research fellowship in ENEA research centre of Casaccia has been started, with the aim of optimizing the pyrolysis process on sewage sludge, in the framework of “piano Triennale della Ricerca del Sistema Elettrico Nazionale 2022-2024”. Co-pyrolysis solutions of sewage sludge and polystyrene have been investigated, with the aim to obtain a quality enhanced liquid product. In the framework of this collaboration, I participated in a Round Robin study organized by VTT technical research centre of Finland, for the standardization of analytical methods for plastic-derived pyrolysis oil characterisation.
- Throughout the year, as regards to the thesis: Methane cracking: a kinetic and experimental study, the research activity focused on the experimental and modeling analysis of methane pyrolysis in molten tin for the sustainable production of hydrogen and solid carbon. Experiments were conducted in a quartz bubble reactor by varying the temperature (980–1070 °C), methane flow rate (20–40 mL/min), and the diameter of the injection capillary (0.25 and 0.32 mm). The gaseous products (CH4, H2, C2H4, C2H2, and C2H6) were analyzed by mass spectrometry, while the carbon deposits were characterized using scanning electron microscopy (SEM/EDS) and Raman spectroscopy. The results show that methane conversion increases significantly with temperature, reaching values between 1–6% at 980 °C and 25–38% at 1070 °C. The C2 intermediates (ethane, ethylene, acetylene) account for fractions between 1–2.6%, confirming their key role in the pyrolysis mechanism. Kinetic analysis enabled the determination of Arrhenius parameters for the four sequential dehydrogenation steps (CH4 → C2H6 → C2H4 → C2H2 → C(s) + H2). Characterization of the produced carbon reveals lamellar structures with an increasing degree of structural order correlated to operation time. Significant tin contamination was also observed. To optimize carbon purity, purification treatments with HCl (8–12 M) were conducted, which effectively reduced the average diameter of incorporated tin particles from 0.86 μm to 0.36 μm and the surface mass of tin from 68 μg/cm2 to less than 16 μg/cm2. Overall, the work has provided global kinetic parameters for mthane conversion and C2 intermediate formation, which can be used for future implementation in process simulators, as well as effective strategies for solid product purification through acid treatments.
- During the third year of the thesis: “Calcium batteries: a “New challenge”, activties were focused on the investigation of Ca–Zn and Ca–Sn alloys as anode materials for calcium-based batteries. In the first part of the year, the set-up for ex-situ post-cycling characterizations (FTIR, XPS) was prepared, and a paper on CaB12H12 as a promising electrolyte salt was published. Ca–Zn alloys were synthesized and analyzed by XRD, SEM, and ICP-OES, evaluating the influence of different milling methods on their morphological and electrochemical properties. Various cathodes were explored, including conversion-type (Cu–S) and organic (PAQs) materials, along with reference electrodes based on gold and lithium. In the second part of the year, asymmetric cell tests with organic cathodes confirmed a dual-ion electrochemical mechanism. In parallel, Ca–Sn alloys with different stoichiometries were synthesized and characterized, while the writing and submission of the doctoral thesis were completed.
- During the third year of the thesis: “Chemical-physical and biological remediation processes combined with hydraulic manipulation systems of the aquifer”, the research activities have continued the work initiated in previous years, developing along two main lines: on one hand, the development of remediation processes at the laboratory scale, and on the other, the design and management of innovative on-site remediation projects, from pilot to full scale in collaboration with the company co-funding the PhD scholarship, IEG Technologie GmbH. Regarding the study of laboratory processes, the distribution process for an injectable Permeable Reactive Barrier (IPRB) based on biochar (BC) adsorbent stabilized with sodium carboxymethylcellulose (CMC) was refined. The work focused particularly on optimizing the distribution in simulated aquifers in column experiments. This was achieved through pre-filtration processes of the BC-CMC suspension to remove the coarsest aggregates and ensure homogeneous retention in the packed column. The columns, loaded with the BC following the BC-CMC suspension distribution process, were subsequently fed with aqueous solutions of chlorinated solvents and petroleum hydrocarbons. This simulated the interception of a contamination plume and validated the entire process. Concerning the activities carried out for on-site remediation interventions, monitoring and data analysis work was performed to optimize the treatment systems' degradation performance and maximize the mass of contaminant mobilized by the Groundwater Circulation Wells (GCWs). A part of the research was devoted to the development and design of a pilot-scale intervention for an Italian site with high hydrogeological complexity, impacted by severe historical contamination from chlorinated solvents in Bussi sul Tirino (AQ).
- During third year of the thesis: “Valorization of phosphogypsum containing rare earths by hydrometallurgical processes, process optimization at laboratory scale and validation at pilot scale”, the research focused on completing the experimental work and expanding the study toward process simulation and economic evaluation. The phosphogypsum samples obtained from OCP Morocco were carefully analyzed to understand their physical and mineralogical properties. The material characterization was performed using scanning electron microscopy combined with energy dispersive spectroscopy to study the surface morphology and elemental composition, X ray diffraction to identify the crystalline phases, and laser diffraction to determine the particle size distribution. These analyses helped to understand the internal structure of phosphogypsum and its relation with the recovery behavior of rare earth elements.
After the characterization, a series of leaching experiments were carried out using sulfuric acid to optimize the recovery of rare earth elements from phosphogypsum. The effect of important parameters such as acid concentration, solid to liquid ratio, reaction time, and temperature were studied to identify the most efficient operating conditions. In addition, resin in leach tests were performed using a strong acid cation exchange resin to study the direct adsorption of rare earths from the leach solution.
The experimental data collected during these tests were then used to build process simulations at both pilot and industrial scale using SuperPro Designer software. The simulation allowed the selection of the required equipment, estimation of material and energy balance, and calculation of capital and operating costs. Based on these results, a complete techno economic feasibility study was performed to evaluate the industrial potential of the process for large scale phosphogypsum valorization and recovery of rare earth elements.
- During the third year of the thesis “Polymeric cryogels and extrusion-based 3D bioprinting”, During the third year of the PhD, the research activity developed along two different lines. The first continued the experimental work of previous years aimed at the characterization of cryogel-type polymer systems. Specifically, cell adhesion and proliferation tests were carried out on hybrid systems obtained from metracrylic derivatives of dextran and methacrylated gelatin, and swelling tests were carried out on systems based on dextran methacrylate. The latter were used for the construction of a mechano-diffusion model necessary for the description of swelling phenomena in cryogel matrices. The second line of research focused on the analysis of dispersion phenomena in periodic ordered structures, consisting of TPMS unit cells (triply periodic minimal surfaces). Impermeable, surface retentive and mesoporous stationary phases were investigated.
- As regards to the thesis: A study of an innovative process for the valorization of cellulose from agro-food waste”, during the first semester of the third year, Ithe work focused on the techno-economic analysis of various protein extraction methods from algae, based on literature data. Additionally, a review of existing research on protein extraction techniques for different seaweed species and initiated preliminary experiments on cellulose extraction from various biomasses was carried out. Three Design of Experiments (DOE) optimizations were performed for protein extraction using the pH-shifting method on Ulva, Gracilaria, and Furcellaria lumbricalis residues. In the second semester, the most promising residues for continued studies on cellulose extraction using Natural Deep Eutectic Solvents (NaDES) and enzymatic treatments was identified. Analysis of FTIR and XRD data, including the development of MATLAB scripts for spectral and crystalline profile interpretation, were also carried out.
- During the third year of the PhD project on: “Stochastic modeling of intracellular biochemical processes with applications to lipid nanoparticles' transport and reaction”, the following activities were carried out: (i) Study and extension of the hydromechanical approach to complex diffusion: explanation of the phenomenon of Fickian yet non-Gaussian diffusion in a homogeneous fluid; introduction of a global effective fluctuation–dissipation relation; comparative analysis of fluid–particle interaction in complex systems. (ii) Analysis of the experimental results on diffusion in hydrogels collected during the second year.
- For the PhD project, aimed at the preparation of the final dissertation entitled “Efficient Production of Polyhydroxyalkanoates with Mixed Microbial Cultures: Combining Process Engineering, Modeling Tools and Downstream Strategies”, the following activities were carried out: Development of a kinetic model representing, from a mechanistic point of view, a continuous process for the production of polyhydroxyalkanoates (PHAs) by mixed microbial cultures. This activity was conducted during the research stay abroad at the University of Santiago de Compostela (September 2024 - May 2025) and involved several stages, including literature review, learning to use coding software (MATLAB), and finally, the setup, calibration, and validation of the model. Data processing for the preparation of the final PhD dissertation, which mainly focused on the experimental work carried out in previous years, including: optimization of process parameters for the aforementioned continuous process, and recovery tests of PHA using alternative strategies that avoided the use of solvents hazardous to human health and the environment. Setup of preliminary tests for CO₂ upgrading into biopolymers through bioelectrochemical systems. A bacterial strain (Cupriavidus necator) capable of accumulating polyhydroxybutyrate (PHB) from hydrogen (H₂) and carbon dioxide (CO₂) was purchased. Preliminary tests were then conducted in bioelectrochemical systems, whose main goal was the production of PHB from externally supplied CO₂ and H₂ generated electrochemically directly within the system.
In the year 2024-25, students participated in seminars, conferences and workshops on topics related to their research activity, obtaining the training credits according to their training plan.
All PhD students also participated in the training activities proposed by the Board in the academic year. 2024-25, as it follows:
Seminars for students 38, 39 and 40th cycle:
- Professor Nuno Domingues from ISEL Engineering Polytechnic University of Lisbon December 4 and 6, 2024 “Energy system, Practical aspects of RES projects, RES calculus”
- Prof. Henri Elzakhem del Department of Chemical Engineering University of Balamand, Lebanon, April 9, 2025 "Stimulation of the Fermentation Activity by Pulsed Electric Field: Case of Saccharomyces cerevisiae"
- Prof. Aleksandar Matic, Chalmers University of Technology, Sweden, September 30, 2025 “Looking into next generation batteries with operando X-ray imaging”
Courses 39th cycle
- Experimental Techniques for the Evaluation of Battery Performance and Aging (Brutti)
- Methane Cracking for Hydrogen and Carbon Production: Research Challenges and Industrial Perspectives (De Filippis - de Caprariis)
- Hydrogen Safety for Energy Application (Russo)
- Scaling up of bioelectrochemical processes for Waste Valorization and Site Remediation (Petrangeli Papini)
- Experimental Design and data analysis (Pagnanelli)
- Experimental Research Planning and Model Development (Zuorro – Lavecchia)
Students also attended the internal Workshop held in June 5, 2025
Courses 40th cycle
- Nanotechnology based advanced processes for wastewater treatment (Di Palma)
- Hydrogen production processes and their integration with solar concentrating technologies (Murmura – Turchetti)
- Kinetic models of aggregation: application to liposomes and nanoparticles (Giona - Pagnanelli – Palocci)
- Chemical and Biochemical Approaches to Biopolymers Synthesis and Degradation (Palocci)
- Nonlinear dynamics of chemical processes (Altimari – Brasiello)
- Experimental Research Planning and Model Development (Zuorro – Lavecchia)
Students also attended the internal Workshop held in June 6, 2025.
Training abroad
Five students of the 38th cycle and two students of the 39th cycle attended a stage near foreign institutions in the AY 2024-25.
Publications
Regarding publications, doctoral students enrolled in the degree program in Chemical Processes for Industry and the Environment have published a total of 50 articles in international journals in the academic year 2024-25.