Photoreduction of Cr(VI) on B4C/AgFe2O4 composite

The present study aimed to couple boron carbide (B4C) and silver ferrite (AgFe2O4) in the composite structure for the Cr(VI) photoreduction application. B4C was synthesized through a heat treatment process of a polymer precursor, polyvinyl borate (PVB). B4C/AgFe2O4 composites were obtained by the synthesis of AgFe2O4 using a auto-combustion technique in the presence of the as-prepared B4C. Fourier-transform infrared spectroscopy and X-ray powder diffraction analyses revealed that pure B4C, pure AgFe2O4, and the B4C/AgFe2O4 composites were synthesized successfully. Field emission scanning electron microscopy and N-2 adsorption-desorption studies exhibited that the as-prepared samples had similar surface morphology. The B4C/AgFe2O4 composites can absorb a significant part of the visible light and can be used as visible-light-driven photocatalyst, shown by UV-Vis absorption spectroscopy. Coupling B4C with AgFe2O4 in the composite structure provided enhancement in the Cr(VI) photoreduction efficiency. The Cr(VI) removal rate of pure B4C increased from 65.1% to 98.0% within 120 min. of visible light irradiation. The resulting enhancement in the Cr(VI) photoreduction efficiency was attributed to the suppression of the recombination of the photoexcited charge carriers on the composites, which was shown by photoluminescence spectroscopy. Under acidic conditions, the Cr(VI) removal rate in the presence of B4C/AgFe2O4 increased to almost 99%. The Cr(VI) photoreduction efficiency decreased to 89.9% when real wastewater spiked with Cr(VI) ions was used instead of the simulated Cr(VI) solution. It was observed that the prepared composites were reusable for the Cr(VI) removal process and magnetically separable from the Cr(VI) solution.[GRAPHICS]

Design of novel well-defined organorhenium heterogeneous catalyst for unsaturated fatty acid derivatives self-metathesis

La formation des liaisons C-C est parmi les cibles les plus élevés de la science et de la technologie de la catalyse. Dans ce cadre, la réaction de métathèse catalytique a gagné une importance considérable en raison de l'efficacité du processus de transformation. Par conséquent, un grand progrès a été réalisé dans ce domaine avec le développement de plusieurs catalyseurs homogènes et hétérogènes, ainsi que les différentes approches de métathèse. Cette formule a permis une conception plus facile et plus durable de diverses stratégies de synthèse dans différents domaines, y compris la synthèse organique, la science des polymères, etc. Cependant, le développement des catalyseurs de métathèse robustes pour les applications à grande échelle est encore une tâche difficile. Tenant compte de cela, les résultats de recherche présentés dans cette thèse de doctorat se concentrent sur la synthèse d'un nouveau catalyseur hétérogène de métathèse. Par conséquent, le méthyltrioxorhénium (MTO) a été supporté sur différents matériaux à base d'alumine. La performance des catalyseurs synthétisés a été étudié par l'auto-métathèse de l'oléate de méthyle, choisi comme substrat modèle; volumineux et fonctionnalisé, afin d'évaluer la tolérance des espèces actives aux groupements fonctionnels, ainsi que d'évaluer sa diffusion à l'intérieur des canaux mésoporeux. Tout d'abord, des supports très organisés à base alumine mésoporeux organisée modifiée avec le chlorure de zinc (ZnCl2-AMO) ont été préparés avec succès grâce à un procédé sol-gel puis une imprégnation post-synthèse. Le MTO supporté sur ces supports catalytiques est très actif pour l'auto-métathèse de l'oléate de méthyle, avec des vitesses de réaction plus élevées et une meilleure sélectivité par rapport aux catalyseurs à base d'alumine classiques. Cette amélioration est attribuée à des meilleurs phénomènes de transfert de masse à l'intérieur du réseau mésoporeux organisé. Ensuite, nous avons développé une voie de synthèse efficace en une seule étape pour la préparation des matériaux ZnCl2-AMO. Cette approche a permis l'accès à des supports ZnCl2-AMO très ordonnés avec de meilleurs rendements de synthèse ainsi que de meilleures propriétés physiques et de surface. En outre, ces fonctionnalités améliorées ont permis aux catalyseurs à base de MTO supportés sur ces matériaux préparés en une seule étape de manifester une meilleure performance catalytique par rapport à celle de ZnCl2-AMO préparé par le processus en plusieurs étapes. Toutefois, des études spectroscopiques ont révélé la formation d'espèces actives semblables sur la surface pour tous les supports catalytiques préparées. Ces caractérisations nous ont guidés pour étudier et proposer un mécanisme complet pour les voies de formation des produits de métathèse, ainsi que le cycle catalytique de métathèse, démontrant l'effet d'encombrement stérique sur l'interface de catalyseurs qui contrôle la sélectivité de la réaction. La synthèse des catalyseurs de métathèse MTO/ZnCl2-AMO nous a permis d'effectuer efficacement les transformations de métathèse utilisant des matières premières renouvelables (par exemple des acides gras estérifiés provenant des huiles végétales), offrant un accès à une variété de monomères fonctionnalisés, qui pourraient éventuellement être utilisés pour d'autres transformations telles que la synthèse des bio-polymères à valeur ajoutée à base (par exemple, les bioplastiques, biosurfactants).Sustainable C-C bond forming reactions have been among the highest target of catalysis science and technology. In this scope, metathesis reaction has been gaining enormous attention due to the efficiency of the transformation process. Therefore, a great progress has been made in this area by developing several homogeneous and heterogeneous catalysts as well as distinct metathesis reaction approaches. This allows an easier and more sustainable design for various synthesis strategies in different fields including organic synthesis, polymer science, etc. However, the development of robust metathesis catalysts for large scale applications is still a challenging task. Taking this into account, this research presented in this doctoral dissertation is focusing on the synthesis of new heterogeneous metathesis catalysts. Therefore, methyltrioxorhenium (MTO) was supported on various alumina-based materials. The synthesized catalysts' performance was studied though methyl oleate self-metathesis, chosen as a model bulky functionalized substrate, in order to evaluate the active species tolerance to functional groups as well as to evaluate its diffusion inside the mesoporous channels. First, highly organized ZnCl2-modified OMA supports were successfully prepared through a sol-gel method followed by a post-synthesis modification via wet-impregnation process. MTO supported on these catalytic supports were found o be highly active for methyl oleate self-metathesis, displaying higher reaction rate and products selectivity compared to the conventional wormhole-like alumina-based catalysts. This improvement is ascribed to enhanced mass transfer phenomena inside the organized mesoporous network. Afterwards, we have developed efficient one-pot synthesis route ZnCl2-modified OMA supports. Interestingly, this approaches allowed access to numerous highly ordered ZnCl2-modified OMA supports with better synthesis yields and improved textural and surface properties. Moreover, these enhanced features allowed the MTO-based catalyst supported on these one-step prepared materials to exhibit higher metathesis reaction performance compared to ZnCl2-modified OMA supports prepared via the two-steps processes. However, spectroscopic investigations revealed the formation of similar surface active species for all the prepared catalytic supports. These characterizations guided us to study and propose a comprehensive mechanism of metathesis products formation pathways as well as the metathesis catalytic cycle, demonstrating the steric hindrance effect on the catalysts interface that governed the reaction selectivity. The synthesis of the 3 wt.% MTO/ZnCl2-OMA catalysts allowed us to efficiently perform metathesis reaction using renewable feedstock (e.g. fatty acid esters derived from vegetable oils), offering access to a variety of functionalized monomers which could be used for further transformations such as the synthesis of value-added bio-based polymers (e.g. bioplastics, biosurfactants)

The Synthesis and Application of Novel Nanostructured Carbon Materials

This study presents a comprehensive investigation on synthesis of several novel carbon materials including nitrogen-doped graphene, nitrogen-doped carbon nanotubes with encapsulated iron carbide, nitrogen-doped mesoporous carbons and Co-based nanospheres supported by carbon spheres and their applications in the catalytic oxidation of phenol solution by heterogeneous activation of peroxymonosulfate. Their structures, morphologies and relevant mechanisms were studied thoroughly. These findings would open a new avenue for the development of green catalysts in environmental remediation

Coupling of the electrochemical oxidation (EO-BDD)/photocatalysis (TiO2-Fe-N) processes for degradation of acid blue BR dye

We report on the successful preparation of Fe-N codoped Titania powders, using TiO2Degussa P25, salt of Fe (II), and Urea. Modified Titania-based materials were characterized by SEM, EDS, BET, Raman, XRD diffraction and diffuse reflectance UV–vis spectroscopy measurements. The doping of TiO2 induced a shift in the absorption threshold toward the spectral range, obtaining catalysts with a greater photoactivity than the one of pure Degussa P25. The degradation of 200 mL of a solution with 50 mg L− 1acid blue BR dye in sulfate medium at pH 3.0 has been comparatively studied by electrochemical oxidation using a boron doped diamond anode (EO-BDD), Photocatalysis TiO2-Fe-N, and coupled material of EO-BDD/Photocatalysis TiO2-Fe-N. The solution was slowly degraded by EO-BDD (25%) and single Photocatalysis TiO2-Fe-N because of the low rate of dye degradation and its colored by-products with hydroxyl radicals generated at the BDD anode and catalyst surface from water oxidation (29%), whereas the solution was more rapidly degraded using coupled material of EO-BDD/Photocatalysis TiO2-Fe-N (82%), owing to the additional generation of hydroxyl radicals from the photocatalysis of TiO2-Fe-N and BDD anode.The authors thank the PRODEP Program (PRODEP-UGTO-PTC-472 and PRODEP 2015 UGTO-PTC-457) of UGTO under the Project 007/ 2015 (Convocatoria Institucional para Fortalecer la Excelencia Académica 2015), and the Project 778/2016 (Convocatoria Institucional de Apoyo a la Investigación Científica 2016-2017) is acknowledged. Authors thank Guanajuato University-CONACYT National Laboratory for SEM-EDX analysis. Financial support from the Spanish Ministry of Economy and Competitiveness in projects CTM2015-69845- R and CTQ2015-66078-R (MINECO/FEDER, UE) is gratefully acknowledged. C. J. Escudero thanks CONACYT-CONCYTEG for the postgraduate research grant (230713/383108) from Mexico

DEVELOPMENT OF METAL MATRIX COMPOSITE GRIDLINES FOR SPACE PHOTOVOLTAICS

Space vehicles today are primarily powered by multi-junction photovoltaic cells due to their high efficiency and high radiation hardness in the space environment. While multi-junction solar cells provide high efficiency, microcracks develop in the crystalline semiconductor due to a variety of reasons, including: growth defects, film stress due to lattice constant mismatch, and external mechanical stresses introduced during shipping, installation, and operation. These microcracks have the tendency to propagate through the different layers of the semiconductor reaching the metal gridlines of the cell, resulting in electrically isolated areas from the busbar region, ultimately lowering the power output of the cell and potentially reducing the lifetime of the space mission. Pre-launch inspection are often expensive and difficult to perform, in which individual cells and entire modules must be replaced. In many cases, such microcracks are difficult to examine even with a thorough inspection. While repairs are possible pre-launch of the space vehicle, and even to some extent in low-to-earth missions, they are virtually impossible for deep space missions, therefore, efforts to mitigate the effects of these microcracks have substantial impact on the cell performance and overall success of the space mission. In this effort, we have investigated the use of multi-walled carbon nanotubes as mechanical reinforcement to the metal gridlines capable of bridging gaps generated in the underlying semiconductor while providing a redundant electrical conduction pathway. The carbon nanotubes are embedded in a silver matrix to create a metal matrix composite, which are later integrated onto commercial triple-junction solar cells

Towards scale‐up of graphene production via nonoxidizing liquid exfoliation methods

Graphene, the two‐dimensional form of carbon, has received a great deal of attention across academia and industry due to its extraordinary electrical, mechanical, thermal, chemical, and optical properties. In view of the potential impact of graphene on numerous and diverse applications in electronics, novel materials, energy, transport, and healthcare, large‐scale graphene production is a challenge that must be addressed. In the past decade, top–down production has demonstrated high potential for scale‐up. This review features the recent progress made in top–down production methods that have been proposed for the manufacturing of graphene‐based products. Fabrication methods such as liquid‐phase mechanical, chemical and electrochemical exfoliation of graphite are outlined, with a particular focus on nonoxidizing routes for graphene production. Analysis of exfoliation mechanisms, solvent considerations, key advantages and issues, and important production characteristics including production rate and yield, where applicable, are outlined. Future challenges and opportunities in graphene production are also highlighted

Advanced Oxidation Processes: Ozonation and Fenton Processes Applied to the Removal of Pharmaceuticals

This chapter aims to present the fundamentals, important variables, and pharmaceuticals removed by ozonation and Fenton, which are only two of the current existing advanced oxidation processes. Some toxicological information regarding pharmaceuticals oxidized by ozonation is also included. Some strategies to improve such processes, like adding a catalyst, light, or electrical current, are also analyzed. Thus, this chapter intends to present general but fundamental aspects of the aforementioned processes

Biomimetic route to hybrid nano-Composite scaffold for tissue engineering

Hydroxyapatite-poly(vinyl) alcohol-protein composites have been prepared by a biomimetic route at ambient conditions, aged for a fortnight at 30±2°C and given a shape in the form of blocks by thermal cycling. The structural characterizations reveal a good control over the morphology mainly the size and shape of the particles. Initial mechanical studies are very encouraging. Three biocompatibility tests, i.e., hemocompatibility, cell adhesion, and toxicity have been done from Shree Chitra Tirunal, Trivandrum and the results qualify their standards. Samples are being sent for more biocompatibility tests. Optimization of the blocks in terms of hydroxyapatite and polymer composition w.r.t the applications and its affect on the mechanical strength have been initiated. Rapid prototyping and a β-tricalcium – hydroxyapatite combination in composites are in the offing

Aluminum Anodic Oxide AAO as a Template for Formation of Metal Nanostructures

The aim of the chapter is to describe the applications of AAO as a template in metal nanostructures formation and to present the experimental results obtained by authors in this field. The basic mechanism of the process of anodic oxidation of aluminum was described. The influence of oxidation parameters on the AAO structure was discussed. The processes of electrochemical metal deposition in AAO were described. The main present as well as future applications of metal nanostructures formed were listed

From Fenton and ORR 2e−-Type Catalysts to Bifunctional Electrodes for Environmental Remediation Using the Electro-Fenton Process

Currently, the presence of emerging contaminants in water sources has raised concerns worldwide due to low rates of mineralization, and in some cases, zero levels of degradation through conventional treatment methods. For these reasons, researchers in the field are focused on the use of advanced oxidation processes (AOPs) as a powerful tool for the degradation of persistent pollutants. These AOPs are based mainly on the in-situ production of hydroxyl radicals (OH center dot) generated from an oxidizing agent (H2O2 or O-2) in the presence of a catalyst. Among the most studied AOPs, the Fenton reaction stands out due to its operational simplicity and good levels of degradation for a wide range of emerging contaminants. However, it has some limitations such as the storage and handling of H2O2. Therefore, the use of the electro-Fenton (EF) process has been proposed in which H2O2 is generated in situ by the action of the oxygen reduction reaction (ORR). However, it is important to mention that the ORR is given by two routes, by two or four electrons, which results in the products of H2O2 and H2O, respectively. For this reason, current efforts seek to increase the selectivity of ORR catalysts toward the 2e(-) route and thus improve the performance of the EF process. This work reviews catalysts for the Fenton reaction, ORR 2e(-) catalysts, and presents a short review of some proposed catalysts with bifunctional activity for ORR 2e(-) and Fenton processes. Finally, the most important factors for electro-Fenton dual catalysts to obtain high catalytic activity in both Fenton and ORR 2e(-) processes are summarized.Ministry of Science and Innovation, Spain (MICINN) Spanish Government PID2021-127803OB-I00Junta de Andalucia B.RNM.566.UGR2