Francisco G. E. Nogueira

Immobilization of soybean peroxidase on silica-coated magnetic particles: a magnetically recoverable biocatalyst for pollutant removal

In this work we investigated the enzymatic degradation of ferulic acid, a model pollutant, by free and immobilized soybean peroxidase. With the aim of developing greener catalysts, we proposed the synthesis of a magnetic catalyst prepared via immobilization of soybean peroxidase onto a magnetic nanosupport by covalent attachment. The immobilization of soybean peroxidase was carried out using magnetite nanoparticles modified with amino groups as support. The magnetite particles were characterized before and after chemical modification by XRD, SEM and TEM analysis. The characterization data indicated that the Fe3O4–SiO2 nanoparticles were successfully synthetized. The high immobilization yield was obtained in only 1 hour of reaction (89.23%). The resulting nanobiocatalyst (enzyme load 5.25 U) was able to remove 99.67 ± 0.10% of ferulic acid in comparison to 57.67 ± 0.27% for free enzyme under the same reaction conditions. The immobilized peroxidase could easily be separated under a magnetic field and reused. On the basis of these results, we concluded that the prepared magnetic nanoparticles can be considered a high-performance nanocatalyst for environmental remediation.

Synthesis, structural characterization, and thermal properties of the poly(methylmethacrylate)/ δ -FeOOH hybrid material: an experimental and theoretical study

The δ-FeOOH/PMMA nanocomposites with 0.5 and 2.5 wt.% of δ-FeOOH were prepared by grafting 3-(trimethoxysilyl)propyl methacrylate on the surface of the iron oxyhydroxide particles. The FTIR spectra of the δ-FeOOH/PMMA nanocomposites showed that the silane monomers were covalently attached to the δ-FeOOH particles. Because of the strong interaction between the PMMA and δ-FeOOH nanoparticles, the thermal stability of the δ-FeOOH/PMMA nanocomposites was improved compared to the pure PMMA. The SEM analysis conferred the size agglomerate of particles regarding the morphology of samples. The theoretical study enabled a better understanding of the interaction of the polymer with the iron oxyhydroxide. The DFT-based calculations reinforce the radical trapping mechanism of stabilization of nanocomposites; that is, Fe3+ species might be able to accept electrons coming from the organic phase that decomposes via radical unzipping. The radical scavenge effect delays the weight loss of polymer.

Bismuth Vanadate Photoelectrodes with High Photovoltage as Photoanode and Photocathode in Photoelectrochemical Cells for Water Splitting

Using dual-photoelectrode photoelectrochemical (PEC) devices based on earth-abundant metal oxides for unbiased water splitting is an attractive means of producing green H2 fuel, but is challenging, owing to low photovoltages generated by PEC cells. This problem can be solved by coupling n-type BiVO4 with n-type Bi4 V2 O11 to create a virtual p/n junction due to the formation of a hole-inversion layer at the semiconductor interface. Thus, photoelectrodes with high photovoltage outputs were synthesized. The photoelectrodes exhibited features of p- and n-type semiconductors when illuminated under an applied bias, suggesting their use as photoanode and photocathode in a dual-photoelectrode PEC cell. This concept was proved by connecting a 1 mol % W-doped BiVO4 /Bi4 V2 O11 photoanode with an undoped BiVO4 /Bi4 V2 O11 photocathode, which produced a high photovoltage of 1.54 V, sufficient to drive stand-alone water splitting with 0.95 % efficiency.

Novel eco-friendly biocatalyst: soybean peroxidase immobilized onto activated carbon obtained from agricultural waste

The immobilization of enzymes is an excellent alternative to overcome the drawbacks of using these biocatalysts in free form. This process plays a significant role in cost-effective recovery, increased catalyst productivity and in simplifying process operations. After the soybean peroxidase (SP) extraction, a residue at high carbon and low ash content is generated. This residue was used as carbonaceous precursor for production of carbon activated (AC) with high surface area (1603 m2 g−1). The AC produced was used as support for SP immobilization. The immobilization of SP was evaluated in different time conditions, enzyme load, pH and temperature. The samples, before and after immobilization, were characterized by thermogravimetric analysis, elemental analysis composition, specific surface area, X-ray powder diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. In addition, repeated applications of immobilized biocatalyst were made in order to evaluate its operational stability and capacity to recover the reaction medium, in which was observed that after a decline in activity from the first to the second cycle, it remained constant until the tenth application. In the context, the process of material obtainment constitutes a clean route for the development of more sustainable biocatalysts capable of applications in various areas.

Soybean peroxidase immobilized on δ-FeOOH as new magnetically recyclable biocatalyst for removal of ferulic acid

A significant enhancement in the catalytic performance due to enzymes immobilization is a great way to enhance the economics of biocatalytic processes. The soybean peroxidase (SP) immobilization under ferroxyte and the ferulic acid removal by the enzyme free and immobilized were investigated. The immobilization via silica-coated ferroxyte nanoparticles was effective, and immobilization yield of 39%. The scanning electron microscopy (SEM) images showed significant changes in the materials morphology. Substantial differences were observed in the particles’ Fourier Transform Infrared (FTIR) spectra. The magnetic catalyst revealed a better performance than the free enzyme in the ferulic acid conversion, presenting a good Vmax/Km ratio when compared with the free enzyme. The reuse evaluated by ten cycles exhibited excellent recycling, remaining constant between the sixth and seventh cycles. The use of magnetic nanocatalyst becomes possible to eliminate the high operational costs, and complicated steps of the conventional enzymatic processes. Thus, a viable industrial route for the use of the enzyme as catalyst is possible.

Experimental and theoretical study on the reactivity of maghemite doped with Cu2+ in oxidation reactions: structural and thermodynamic properties towards a Fenton catalyst

In this work, a polymeric method was used to prepare undoped and Cu-doped iron oxide catalysts for the H2O2 decomposition reaction. These catalysts were characterized by powder X-ray diffractometry (XRD), scanning electronic microscopy (SEM) coupled to an energy dispersive X-ray spectrometer (EDX), and H2-Temperature Programmed Reduction (H2-TPR). The SEM images show an inhomogeneous particle cluster in both samples, tending to decrease in size with Cu-doping. EDX mapping reveals a good dispersion of Cu2+ in the iron oxide. In addition, Rietveld refinement of the XRD patterns reveals that the samples are constituted of hematite and maghemite, but only maghemite has octahedral Fe3+ ions isomorphically replaced by 2 wt% Cu2+. Cu-doping produces an active catalyst for H2O2 decomposition. Tests using phenol show the strong inhibition of H2O2 decomposition by the Cu-doped catalysts, suggesting that H2O2 may be decomposed via a radical mechanism. Furthermore, phenol degradation kinetics confirm that the doping of maghemite with Cu2+ brings about a significant improvement in catalytic activity. Theoretical calculations reveal that Cu-doping in maghemite produces low electronic density sites, favoring the interactions between the surface oxygens of H2O2 and Cu2+, thus improving the catalytic activity. This strategy can be extended to other materials to design active heterogeneous catalysts for environmental purposes.

Degradation of organic compounds in a fenton system based on chitosan/Fe0/Fe2O3 composites: a theoretical and experimental study

Chitosan is a polymer with interesting characteristics for use in catalysis, such as biocompatibility, high chemical reactivity and stability under various conditions. Seeking new applications, a new hybrid material was synthesized for use in the degradation of organic compound. A synthesis route proposed led to the formation of a material in the form of film. The characterization data indicated the presence of hematite, as well as metallic iron. In addition, a theoretical model for interaction of iron with chitosan was proposed. Molecular dynamics simulations indicate that non-Coulomb interactions modulate the adsorption process between reactive red dye and chitosan. The catalytic behavior of these hybrid materials was investigated for the H2O2 decomposition to O2 and the degradation of reactive red dye. The hybrid material showed high degradation capacity, confirming this material as an efficient heterogeneous Fenton catalysts.

Development of a reusable and sustainable biocatalyst by immobilization of soybean peroxidase onto magnetic adsorbent

In this work we synthesized an activated carbon/magnetite composite by a simple co-precipitation method. The activated carbon (AC) was synthesized from the solid waste obtained in the extraction process of the peroxidase enzyme and the magnetic composite was used as support for the immobilization of soybean peroxidase (SP). After the determination of the optimal immobilization parameters, a 100% yield was achieved under the following conditions: support:enzyme proportion of 1.0:0.05 g, equilibration time of 7 h, pH 3.0 (citrate buffer phosphate 0.1 mol L-1) and temperature of 50 °C. The determination of pH to the point of zero charge was also done to assist in the understanding of the immobilization process at different pH values. Several characterization techniques were used, such as thermogravimetric analysis, elemental analysis composition, X-ray powder diffraction, Fourier transform infrared spectroscopy and Scanning electron microscopy. The biocatalyst presented excellent operational stability and was reused for 11 consecutive cycles. The magnetic properties inserted in the AC contributed to the removal of the biocatalyst from the reaction medium without interfering in the adsorptive characteristics of the AC. Thus, the activated carbon/magnetite composite can be applied to different research fields with high performance.