Lucas Tonetti Teixeira

Hydrogen has been explored as a greener alternative for greenhouse gas emissions reduction. Sodium borohydride (NaBH₄) is a favorable hydrogen carrier due to its high hydrogen content, safe handling, and rapid hydrogen release. This work presents a novel synthesis of the catalyst CoFe₂O₄/Fe₂O₃ using nanocellulose fibers (TCNF) as reactive templates for metal adsorption and subsequent calcination. The resulting material was tested for H₂ production from basic NaBH₄ aqueous solutions (10–55 °C). The catalyst’s composition is 74.8 wt% CoFe₂O₄, 25 wt% Fe₂O₃, and 0.2 wt% Fe₂(SO₄)₃ with agglomerated spheroidal particles (15–20 nm) and homogeneous Fe and Co distribution. The catalyst produced 1785 mL of H₂ in 15 min at 25 °C (50 mg catalyst, 4.0% NaBH₄, and 2.5 wt% NaOH), close to the stoichiometric maximum (2086 mL). The maximum H₂ generation rate (HGR) reached 3.55 L min⁻¹ g_cat⁻¹ at 40 °C. Activation energies were determined using empirical (38.4 ± 5.3 kJ mol⁻¹) and Langmuir–Hinshelwood (L–H) models (42.2 ± 5.8 kJ mol⁻¹), consistent with values for other Co-ferrite catalysts. Kinetic data fitted better to the L–H model, suggesting that boron complex adsorption precedes H₂ evolution.

Carboxylate (TCNF) and sulfonated (SCNC) cellulose nanofibers were synthesized and used as adsorbents for metallic cations in aqueous solutions: Na⁺ and Hg²⁺ (SCNC); Mg²⁺ and Hg²⁺ (TCNF). ICP-OES analysis of the liquid phase revealed metal removal efficiencies at room temperature of 89.3% (Hg²⁺) and 100% (Mg²⁺) for TCNF, 35.2% (Hg²⁺) and 63.3% (Na⁺) for SCNC after 3 h of contact. Interestingly, the nanofibers exhibited a distinct thermal degradation profile (characterized by two main events) compared to that of cellulose, suggesting that their nanostructured morphology and surface functionalization may enhance thermal instability. Additionally, the presence of metals at its surface notably altered the thermal degradation kinetics, as observed for mercury and magnesium in TCNF. Finally, the results for SCNC strongly suggest that the mechanism for thermal degradation can also change, as observed for mercury and sodium, expressed through the appearance of a new DTG peak located around 300 °C.

Spinel ferrites are versatile, low-cost, and abundant metal oxides with remarkable electronic and magnetic properties, which find several applications. Among them, they have been considered part of the next generation of electrochemical energy storage materials due to their variable oxidation states, low environmental toxicity, and possible synthesis through simple green chemical processing. However, most traditional procedures lead to the formation of poorly controlled materials (in terms of size, shape, composition, and/or crystalline structure). Thus, we report herein a cellulose nanofibers-mediated green procedure to prepare controlled highly porous nanocorals comprised of spinel Zn-ferrites. Then, they presented remarkable applications as electrodes in supercapacitors, which were thoroughly and critically discussed. The spinel Zn-ferrites nanocorals supercapacitor showed a much higher maximum specific capacitance (2031.81 F g⁻¹ at a current density of 1 A g⁻¹) than Fe₂O₃ and ZnO counterparts prepared by a similar approach (189.74 and 24.39 F g⁻¹ at a current density of 1 A g⁻¹). Its cyclic stability was also scrutinized via galvanostatic charging/discharging and electrochemical impedance spectroscopy, indicating excellent long-term stability. In addition, we manufactured an asymmetric supercapacitor device, which offered a high energy density value of 18.1 Wh kg⁻¹ at a power density of 2609.2 W kg⁻¹ (at 1 A g⁻¹ in 2.0 mol L⁻¹ KOH electrolyte). Based on our findings, we believe that higher performances observed for spinel Zn-ferrites nanocorals could be explained by their unique crystal structure and electronic configuration based on crystal field stabilization energy, which provides an electrostatic repulsion between the d electrons and the p orbitals of the surrounding oxygen anions, creating a level of energy that determines their final supercapacitance then evidenced, which is a very interesting property that could be explored for the production of clean energy storage devices.