The influence of structure and surface chemistry of carbon materials on the decomposition of hydrogen peroxide

Carbon materials with different structural and chemical properties, namely activated carbons, carbon xerogels, carbon nanotubes, graphene oxide, graphite and glycerol-based carbon materials, were tested under different operating conditions for their ability to catalyse hydrogen peroxide (H2O2) decomposition in aqueous solutions. Activated carbons treated with concentrated sulphuric acid (ACS) are the most active catalytic materials for H2O2 decomposition in most of the conditions studied, due to the presence of sulphur containing functional groups at their surface. In addition, ACS proved to be a stable catalyst in reutilization tests for H2O2 decomposition. Methanol was used as selective scavenger of hydroxyl radicals (HO center dot), to show that activated carbons with a markedly basic character lead to the highest yield of HO center dot formed during the H2O2 decomposition process (14%, after 150 min of reaction). Overall, from the mechanistic interpretation of H2O2 decomposition, it is concluded that the presence of sulphur containing functional groups at the surface of the activated carbons improves the removal of H2O2 in aqueous solutions, but, on the other hand, the selective decomposition of H2O2 via HO center dot formation is enhanced by the presence of basic active sites on the Carbon surface

Carbon-based materials for oxidative desulfurization and denitrogenation of fuels: a review

Sulfur (S) and nitrogen (N) are elements naturally found in petroleum-based fuels. Sand N-based compounds in liquid fuels are associated with a series of health and environmental issues. Thus, legislation has become stricter worldwide regarding their content and related emissions. Traditional treatment systems (namely hydrodesulfurization and hydrodenitrogenation) fail to achieve the desired levels of S and N contents in fuels without compromising combustion parameters. Thus, oxidative treatments (oxidative desulfurization–ODS, and oxidative denitrogenation-ODN) are emerging as alternatives to producing ultra-low-sulfur and nitrogen fuels. This paper presents a thorough review of ODS and ODN processes applying carbon-based materials, either in hybrid forms or as catalysts on their own. Focus is brought to the role of the carbonaceous structure in oxidative treatments. Furthermore, a special section related to the use of amphiphilic carbon-based catalysts, which have some advantages related to a closer interaction with the oily and aqueous phases, is discussed.This work was supported by project “PLASTIC_TO_FUEL&MAT–UpcyclingWaste Plastics into Fuel and Carbon Nanomaterials” (PTDC/EQU-EQU/31439/2017), by Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 funding of LSRE-LCM-funded by national funds through FCT/MCTES (PIDDAC), and CIMO (UIDB/00690/2020) through FEDER under Program PT2020. Fernanda F. Roman acknowledges the Foundation for Science and Technology (FCT) and the European Social Fund (FSE) for the individual research grant with reference SFRH/BD/143224/2019.info:eu-repo/semantics/publishedVersio

Solar photocatalytic degradation of parabens using UiO-66-NH2

The photocatalytic degradation of methylparaben was investigated under simulated solar light using a synthesised metal–organic framework (UiO-66-NH2). For that purpose, the pollutant was spiked in different water matrices: distilled water, water from Lima River (Northwestern Portugal), and urban wastewater. Complete removal of the methylparaben in distilled water was achieved in 1 h reaction. In natural water matrices, the photocatalytic performance decreased to 70% removal after 3 h reaction, owing to the physical–chemical properties of the water samples. The UiO-66-NH2 photocatalyst revealed high stability under the continuous mode, reaching a steady state in 5 h, from which the removal percentage was kept constant for 25 h. The photocatalytic degradation of methylparaben gave five main reaction byproducts and four short-chain carboxylic acids, identified by LC/ESI-MS and UHPLC analyses, respectively. The mechanism of degradation was investigated by using selective scavengers. Photogenerated holes and superoxide radicals were found as the main species responsible for the degradation of methylparaben. The abatement of other parabens (as ethyl- and propylparaben) was also evaluated, being the conversion influenced by the length of the alkyl side chain. The results of this study give a comprehensive sight into the effective photocatalytic remediation of parabens using UiO-66-NH2Authors acknowledge Spanish State Research Agency (PID2019- 106186RBI00/AEI/10.13039/501100011033). M. Peñas-Garzón is indebted to Spanish MECD (FPU16/00576 grant) and MICIU (EST19/ 00068). M.J.S. thanks to Project POCI-01-0145-FEDER-030674 (MicroPhotOGen, PTDC/NAN-MAT/30674/2017) funded by ERDF through COMPETE2020 - Programa Operacional Competitividade e Internacionalizaçao (POCI) – and by national funds through FCT - Fundaçao para a Ciência e a Tecnologia. We would like to thank the scientific collaboration financially supported by: Base-UIDB/50020/ 2020 and Programmatic-UIDP/50020/2020 Funding of Associate Laboratory LSRE-LCM - funded by national funds through FCT/MCTES (PIDDAC). Authors thank the Research Support Services of the Universidad Autónoma de Madrid (SIdI), University of Extremadura (SAIUEx), University of Málaga (SCAI) and Universidad Complutense of Madrid (CAI

Impact of atomic layer deposited TiO2 on the photocatalytic efficiency of TiO2/w-VA-CNT nanocomposite materials

Titanium oxide (TiO2) has been widely investigated as a photocatalytic material, and the fact that its performance depends on its crystalline structure motivates further research on the relationship between preparation methods and material properties. In this work, TiO2 thin films were grown on non- functionalized wave-like patterned vertically aligned carbon nanotubes (w-VA-CNTs) via the atomic layer deposition (ALD) technique. Grazing incidence X-ray diffraction (GIXRD) analysis revealed that the structure of the TiO2/VA-CNT nanocomposites varied from amorphous to a crystalline phase with increasing deposition temperature, suggesting a “critical deposition temperature” for the anatase crystalline phase formation. On the other hand, scanning transmission electron microscopy (STEM) studies revealed that the non-functionalized carbon nanotubes were conformally and homogeneously coated with TiO2, forming a nanocomposite while preserving the morphology of the nanotubes. X-ray photoelectron spectroscopy (XPS) provided information about the surface chemistry and stoichiometry of TiO2. The photodegradation experiments under ultraviolet (UV) light on a model pollutant (Rhodamine B, RhB) revealed that the nanocomposite comprised of anatase crystalline TiO2 grown at 200 ?C (11.2 nm thickness) presented the highest degradation efficiency viz 55% with an illumination time of 240 min. Furthermore, its recyclability was also demonstrated for multiple cycles, showing good recovery and potential for practical applications.publishe

High-performance liquid chromatography as a tool to evaluate the performance of the catalytic wet peroxide oxidation of 4-nitrophenol: pre-validation of analytical methods

A high-performance liquid chromatography (HPLC) method capable to detect 4-nitrophenol (4-NP) in aqueous solutions with concentration in the range 0.0495-118.8 mg L-1 was developed and validated under the typical criteria for in -house pre-validations. Accordingly, linearity was demonstrated through the Fisher’s exact probability test. Accuracy and precision were then assessed in three concentrationlevels over the linear range. The reproducibility of the catalytic wet peroxide oxidation (CWPO) of 4-NP was evaluated together with the analytical error of 4-NP determination in independent experiments. In this case, the sum of both contributions to error never reached 3%.Two multi-component HPLC methods were also developed for the determination of possible aromatic intermediates (hydroquinone, 1,4-benzoquinone, catechol, 4-nitrocatechol and phenol) and carboxylic acids (oxalic, formic, malic, malonic, acetic and maleic acids) resulting from the 4-NP degradation. The combination of these analytical methods already led to the proposal of an oxidation/mineralization mechanism for the CWPO of 4-NP

Overview on protein extraction and purification using ionic-liquid-based processes

Proteins are one the most widely studied biomolecules with diverse functions and applications. Aiming at overcoming the current drawbacks of purification processes of proteins, the introduction of ionic liquids (ILs) has been a hot topic of research. ILs have been applied in the creation of aqueous biphasic systems (IL-based ABS), solid-phase extractions through poly(ionic liquid)s (PILs) and supported ionic-liquid phases (SILPs), and in the crystallization of proteins. In this sense, ILs have emerged as solvents, electrolytes or adjuvants, or as supported materials to tune the adsorption/affinity capacity aiming at developing an efficient, cost-effective, sustainable and green IL-based process for protein extraction. This review discusses different IL-based processes in the extraction and purification of proteins in the past years, namely IL-based aqueous biphasic systems (IL-based ABS), solid-phase extractions through PILs and SILPs, and protein crystallization. The type and structure of ILs applied and their influence in the different processes performance are also discussed.publishe

Multi-walled carbon nanotubes as a platform for Immunoglobulin G attachment

Nanomaterials have been extensively used in different applications due to their peculiar characteristics and nanoscale dimensions. Among nanoparticles, carbon-based nanomaterials are becoming highly attractive for biomedical applications such as diagnosis, tissue engineering, drug delivery, and biosensing. The conjugation of carbon-based nanomaterials with antibodies combines the properties of these materials with the specific and selective recognition ability of the antibodies to antigens. The present work proposes a process intensification approach for immunoglobulin G (IgG present in rabbit serum) attachment on multi-walled carbon nanotubes (MWCNTs) in a single step. The effect of several parameters, namely MWCNTs external diameter, rabbit serum concentration, MWCNTs functionalization and pH value, on the IgG attachment yield was evaluated. The dilution of rabbit serum decreased other protein attachment, namely rabbit serum albumin (RSA), while increasing the IgG yield to 100%. The interaction mechanisms between IgG and MWCNTs were evaluated at pH 5.0 to 8.0. The protonation of IgG amino acids indicates that N-term are the most reactive amino acids in the antibody structure. The identification of the N-term reactivity at pH 8.0 allows to indicate a possible orientation of the antibody over the MWCNTs surface, described as “end-on”. Since the amount of RSA attached to MWNT decreased with the increase in serum dilution, the IgG orientation and amine activity was not affected. This orientation demonstrates that the IgG attachment over the surface of the MWCNTs could be an effective strategy to maintain the antigen recognition by the antibody, and to be used for biomedical applications.publishe

Tuning graphitic carbon nitride (g-C3N4) electrocatalysts for efficient oxygen evolution reaction (OER)

Nowadays, energy conversion and storage technologies are essential research topics due to the necessity of more sustainable processes. Specifically, water splitting is highly affected by slow kinetics and limited knowledge of the oxygen evolution reaction (OER). This work envisages the preparation of graphitic carbon nitride (g-C3N4) electrocatalysts for efficient OER by a facile one-pot method. The impact of the preparation temperature (450–650 ◦C) of g-C3N4 was assessed for the first time on water splitting processes and explained by different characterisation techniques. The unique crystal structure, surface chemistry, and electronic properties of the material prepared at 550 ◦C lead to a remarkable OER efficiency, with an overpotential of 355 mV at 10 mA cm− 2 and a Tafel slope of 46.8 mV dec− 1. Interestingly, three major differences were observed when comparing the material prepared at 550 ◦C with those obtained at other temperatures: the reduced structural distortion, the superior composition in oxygen and the presence of terminal functional groups. Also, compared to other metalfree g-C3N4 electrocatalysts reported in the literature, we achieved lower Tafel slope values without additional post-treatments or co-catalysts. Hence, for the first time a metal-free catalyst defeats benchmark IrO2. The prepared electrodes were stable for up to 45 h, even when increasing the applied current density to 100 mA cm− 2 for 15 h. Thus, this work provides a simple route for the fabrication of highly-efficient and long-lasting electrocatalysts for a remarkable OER performance.Agencia Estatal de Investigación | Ref. PID2020-113667 GB-I00Fundação para a Ciência e a Tecnologia | Ref. UIDB/50020/2020Fundação para a Ciência e a Tecnologia | Ref. UIDP/50020/2020Xunta de Galicia | Ref. ED481D-2023/015Universidade de Vigo/CISU

Recent strategies and applications for l-asparaginase confinement

l-asparaginase (ASNase, EC 3.5.1.1) is an aminohydrolase enzyme with important uses in the therapeutic/pharmaceutical and food industries. Its main applications are as an anticancer drug, mostly for acute lymphoblastic leukaemia (ALL) treatment, and in acrylamide reduction when starch-rich foods are cooked at temperatures above 100 °C. Its use as a biosensor for asparagine in both industries has also been reported. However, there are certain challenges associated with ASNase applications. Depending on the ASNase source, the major challenges of its pharmaceutical application are the hypersensitivity reactions that it causes in ALL patients and its short half-life and fast plasma clearance in the blood system by native proteases. In addition, ASNase is generally unstable and it is a thermolabile enzyme, which also hinders its application in the food sector. These drawbacks have been overcome by the ASNase confinement in different (nano)materials through distinct techniques, such as physical adsorption, covalent attachment and entrapment. Overall, this review describes the most recent strategies reported for ASNase confinement in numerous (nano)materials, highlighting its improved properties, especially specificity, half-life enhancement and thermal and operational stability improvement, allowing its reuse, increased proteolysis resistance and immunogenicity elimination. The most recent applications of confined ASNase in nanomaterials are reviewed for the first time, simultaneously providing prospects in the described fields of application.publishe