Sol-gel and Pechini niobium modified: synthesis, characterization and application in the 2,4-D herbicide degradation.

In this work, a comparison was made between the synthesis of niobium-based materials (Nb2O5), both in terms of material characterization and catalytic performance. The methods used were chemical mixtures: modified sol-gel and Pechini. The materials were calcined at different temperatures (753, 873 and 993K) and characterized by the following techniques: photoacousticspectroscopy (PAS), zero charge point (pHPZC), scanning electron microscopy (SEM/EDS), thermogravimetric analysis (TGA/DTG) and X-ray diffraction (XRD). The photocatalytic process was carried out to evaluate the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) under UV radiation (250 W mercury vapor lamp) and different experimental conditions. In addition, to better understand the influence of parameters such as pH, catalyst concentration (0.2, 0.5 and 0.8 g L-1) and calcination temperature, a Design of Experiments (DoE) was used. The results indicated that despite having similar structures and phases in the XRD analysis, the morphology presents two distinct surfaces, due to the preparation method. Differences in the synthesis method affected the catalytic activity in the parameters studied. Although the zero charge point values are close (6.18-6.36), we observed differences in the band gap depending on the calcination temperature. In the optimal condition studied, the catalyst prepared by the sol-gel method obtained the best results.

Enzymatic post-consumer poly(ethylene terephthalate) (PET) depolymerization using commercial enzymes.

Poly(ethylene terephthalate) (PET) is a synthetic polymer widely used globally. The high PET resistance to biotic degradation and its improper destination result in the accumulation of this plastic in the environment, largely affecting terrestrial and aquatic animals. This work investigated post-consumer PET (PC-PET) degradation using five commercial hydrolase enzymes (Novozym 51032, CalB, Palatase, Eversa, Lipozyme TL). Humicola insolens cutinase (HiC, Novozym 51032) was the most active among the enzymes studied. Several important reaction parameters (enzyme type, dual enzyme system, enzyme concentration, temperature, ultrasound treatment) were evaluated in PC-PET hydrolysis using HiC. The concentration and the proportion (molar ratio) of hydrolysis products, terephthalic acid (TPA), mono(2-hydroxyethyl) terephthalate (MHET), and bis(2-hydroxyethyl) terephthalate (BHET), were significantly changed depending on the reaction temperature. The TPA released at 70 °C was 3.65-fold higher than at 50 °C. At higher temperatures, the conversion of MHET into TPA was favored. The enzymatic PET hydrolysis by HiC was very sensitive to the enzyme concentration, indicating that it strongly adsorbs on the polymer surface. The concentration of TPA, MHET, and BHET increased as the enzyme concentration increased, and a maximum was achieved using 40-50 vol % of HiC. The presented results add relevant data to optimizing enzyme-based PET recycling technologies.

Pharmaceutical compounds photolysis: pH influence.

The operating parameters of photolytic and photocatalytic reaction processes directly affect the efficiency in the degradation of compounds. In particular, pH is a variable that needs to be considered as it exerts great influence on adsorption, absorption, solubility, among others. This study describes the application of the photolytic process, at different pHs, in the degradation of different pharmaceutical compounds. Photolytic reactions were performed with the following contaminants: acetylsalicylic acid (ASA), ibuprofen (IBP) and paracetamol (PAR). In addition, a comparison was performed using the commercial catalyst P25. The results indicated a great influence of the pH in the kinetic constant of the photodegradation and in the UV absorbance of the species. In particular, the degradation of ASA and PAR were favored with the reduction of pH, while the degradation of IBU and SA were favored by increasing. Also, the chromatograms indicated that pH may affect the by-products formed. In comparison, the photocatalysis process in the presence of P25 proved to be much more effective, but it was not possible to achieve complete mineralization of the compounds.

Cu/Nb2O5, Fe/Nb2O5 and Cu-Fe/Nb2O5 applied in salicylic acid degradation: Parameters studies and photocatalytic activity.

This study describes the synthesis of Cu/Nb2O5, Fe/Nb2O5, and Cu-Fe/Nb2O5 catalysts obtained by incorporating copper and/or iron metals into niobium pentoxide (Nb2O5). The new materials were characterized by the following techniques: Thermogravimetric Analysis (TA), surface and pore analysis, X-ray diffractometry (XRD), and Fourier Transform Infrared Spectroscopy (FT-IR). The catalyst was applied in the photocatalytic degradation of salicylic acid (SA). The influence of different parameters (calcined temperature, pH, and metal addition) on the photocatalytic reaction was evaluated. The results indicated that catalysts containing copper were more active and pH influenced the SA degradation process. SA removal results indicated that Cu/Nb2O5 photocatalyst presented a 1.5 fold higher degradation after 120 min in comparison to Cu-Fe/Nb2O5 and 4.6 fold higher than Fe/Nb2O5 catalyst, all them calcined at 400 °C. In tests carried out in the presence of formic acid, increasing the pH from about 3 to 7 allowed an almost 3.4-fold increase in SA degradation for the Cu-Fe/Nb2O5 catalyst calcined at 400 °C.

Paraquat degradation by photocatalysis: experimental desing and optimization.

This study describes the experimental design and optimization of application TiO2 catalysts doped with 0.5, 1, 1.5, 2.0% of Fe. The catalysts were prepared using the impregnation method applied in Paraquat herbicide degradation. The catalysts were characterized by the following techniques: specific surface area and volume, mean pore diameter (BET method), scanning electron microscopy and photoacoustic spectroscopy. The characterization presented results indicating that both calcination temperature and the increase nominal metallic load affected by the structure of catalysts, changing the textural properties, as well as the band gap. The catalyst that presented the best herbicide removal percentage was TiO2 calcined at 773 K with removal of 90.2%. However, according to the experimental design and optimization, both variables (calcination temperature and Fe percentage) are significant in the process. In addition, a positive effect was found in the interaction between the two variables. The values show that a third order kinetic model better described the Paraquat photocatalytic degradation.

Corn Straw Residue: a Strategy for Lipase Immobilization.

This work aims to study the immobilization of Candida rugosa lipase (CRL) onto corn straw residue. For this purpose, chemical, morphological, and textural characteristics of the corn straw; immobilization process by adsorption; and immobilized enzyme activity and storage stability were evaluated. The corn straw presented isoelectric point of 7.0, surface with hydroxyl bands being favorable to the immobilization process. An irregular surface was also observed with fibers and pores, which are mesoporous and macroporous, characteristics that demonstrate efficiency in mass transfer mechanisms. Upon immobilization, it was observed that adsorption velocity is proportional to the square of the available adsorption sites (pseudo-second-order), and that the immobilization occurs in monolayers (Langmuir isotherm). The adsorption process was favorable and considered as a chemical adsorption mechanism. After immobilization, the optimum temperature increased, the optimum pH reduced, and the affinity of the biocatalyst for the substrate decreased. Corn straw derivative demonstrated good thermal stability. Regarding storage stability, there was approximately 12% loss of activity after 60 days of storage at 4 °C. Considering that no treatment was applied to the corn straw, this result is satisfactory and shows good affinity between this support and CRL.