Co3O4/activated carbon nanocomposites as electrocatalysts for the oxygen evolution reaction.

The Oxygen Evolution Reaction (OER) is crucial in various processes such as hydrogen production via water splitting. Several electrocatalysts, including metal oxides, have been evaluated to enhance the reaction efficiency. Zeolitic Imidazolate Framework-67 (ZIF-67) has been employed as a precursor to produce Co3O4, showing high OER activity. Additionally, the formation of composites with carbon-based materials improves the activity of these materials. Thus, this work focuses on synthesizing ZIF-67 and commercial activated carbon (AC) composites, which were used as precursors to obtain Co3O4/C electrocatalysts by calculating ZIF-67/CX (X = 10, 30, and 50, the mass percentage of AC). The obtained materials were thoroughly characterized by employing X-ray powder diffraction (XRD), confirming the cobalt oxide structure with a sphere-like morphology as observed in the TEM images. The presence of oxygen vacancies was confirmed by infrared spectroscopy and EPR measurements. The electrocatalytic performance in the OER was investigated by linear sweep voltammetry (LSV), which revealed an overpotential of 325 mV at 10 mA cm-2 and a Tafel slope value of 65.32 mV dec-1 for Co3O4/C10, superior in activity to several previously reported studies in the literature and electrochemical stability of up to 8 hours. The reduced value of charge transfer resistance, high double-layer capacitance, and the presence of Co3+ ions justify the superior performance of the Co3O4/C10 electrocatalyst.

Metal-organic frameworks as template for synthesis of Mn3+/Mn4+ mixed valence manganese cobaltites electrocatalysts for oxygen evolution reaction.

Cobalt-based oxides are among the most promising electrocatalysts for oxygen evolution reactions (OER). In this context, this work reports the synthesis of manganese-doped cobaltites using the Zeolitic-Imidazolate Frameworks 67 (ZIF-67) as template. The incorporation of manganese ions into ZIF-67 structure was evaluated in ethanol and methanol, in order to obtain the best synthetic route. Non-doped (ZIF-67C) and Mn-doped cobaltites (Mn/ZIF-67C(E) and Mn/ZIF-67C(M)) were obtained after thermal treatment at 350 °C. Structural and morphological properties were investigated and presence of Mn3+ and Mn4+ was confirmed by X-ray photoelectron spectroscopy (XPS) data and magnetization curves. The electrocatalytic activity in OER was investigated in alkaline medium for manganese cobaltites, and compared to the ZIF-67C. Overpotentials to generate a current of 10 mA cm-2 were 338 mV and 356 mV for Mn/ZIF-67C(E) and Mn/ZIF-67C(M), respectively. These results are superior to those found for similar materials in the literature. The material obtained in methanol (Mn/ZIF-67C(M)) presents lower overpotential, however, shows superior electrocatalytic performance for current density above 100 mA cm-2, therefore being an efficient electrode for commercial electrolysers.

New Composites LnBDC@AC and CB[6]@AC: From Design toward Selective Adsorption of Methylene Blue or Methyl Orange.

New porous composites LnBDC@AC (AC = Activated carbon, Ln = Eu and Gd and BDC = 1,4-benzenedicaboxylate) and CB[6]@AC (CB[6] = Cucurbit[6]uril) were obtained using hydrothermal route. The LnBDC and CB[B] are located inside the pore of the carbon materials as was observed in SEM-EDS, XRPD and FT-IR analysis. Porosimetry analysis showed values typically between AC and LnBDC material, with pore size and surface area, respectively, 29,56 Å and 353.98 m2g-1 for LnBDC@AC and 35,53 Å and 353.98 m2g-1 for CB[6]@AC. Both materials showed good absorptive capacity of metil orange (MO) and methylene blue (MB) with selectivity as a function of pH. For acid pH, both materials present selectivity by MB and alkaline pH for MO, with notable performance for CB[6]@AC. Additionally, europium luminescence was used as structural probe to investigate the coordination environment of Eu3+ ions in the EuBDC@AC composite after adsorption experiment.

New lanthanide-CB[6] coordination compounds: relationships between the crystal structure and luminescent properties.

The reaction between cucurbit[6]uril (CB[6]) and lanthanide chlorides (Eu, Sm, Tb and Tm) in acidic aqueous media led to four new structures. The compounds obtained are isostructural with general formula [Ln2(H2O)12(H2O@CB[6])]Cl6(H2O)4 (Ln = Eu(3+) (1), Sm(3+) (2), Tb(3+) (3) and Tm(3+) (4)) and crystallize in the P21/c space group. For the complexes with Eu(3+), Sm(3+) and Tb(3+), the luminescent properties in the solid state and aqueous media were explored and all spectroscopic observations are in excellent agreement with the single crystal structure data. The excitation and emission spectra show the typical f-f transitions characteristic of the trivalent lanthanide ions. The transitions (7)FJ ← (5)D1 (J = 0,1,2) in the europium compound and (7)FJ ← (5)D4 (J = 0,1,2) in the terbium compound, not yet reported in lanthanide-CB[n] compounds, were also observed.

Induction of cancer cell death by apoptosis and slow release of 5-fluoracil from metal-organic frameworks Cu-BTC.

This study aimed to evaluate the mechanism associated with cytotoxic activity displayed by the drug 5-fluorouracil incorporated in Cu-BTC MOF and its slow delivery from the Cu-BTC MOF. Structural characterization encompasses elemental analysis (CHNS), differential scanning calorimetry (DSC), thermogravimetric analysis (TG/DTG), Fournier transform infrared (FIT-IR) and X-ray diffraction (XRD) was performed to verify the process of association between the drug 5-FU and Cu-BTC MOF. Flow cytometry was done to indicate that apoptosis is the mechanism responsible for the cell death. The release profile of the drug 5-FU from Cu-BTC MOF for 48 hours was obeisant. Also, the anti-inflammatory activity was evaluated by the peritonitis testing and the production of nitric oxide and pro-inflammatory cytokines were measured. The chemical characterization of the material indicated the presence of drug associated with the coordination network in a proportion of 0.82 g 5-FU per 1.0 g of Cu-BTC MOF. The cytotoxic tests were carried out against four cell lines: NCI-H292, MCF-7, HT29 and HL60. The Cu-BTC MOF associated drug was extremely cytotoxic against the human breast cancer adenocarcinoma (MCF-7) cell line and against human acute promyelocytic leukemia cells (HL60), cancer cells were killed by apoptosis mechanisms. The drug demonstrated a slow release profile where 82% of the drug was released in 48 hours. The results indicated that the drug incorporated in Cu-BTC MOF decreased significantly the number of leukocytes in the peritoneal cavity of rodents as well as reduced levels of cytokines and nitric oxide production.