reaction medium
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2022 ◽  
Vol 3 ◽  
Gabriela Xavier de Oliveira ◽  
Jéssica Oliveira de Brito Lira ◽  
Humberto Gracher Riella ◽  
Cíntia Soares ◽  
Natan Padoin

From the pharmaceutical industry’s point of view, photoredox catalysis has emerged as a powerful tool in the field of the synthesis of added-value compounds. With this method, it is possible to excite the catalyst by the action of light, allowing electron transfer processes to occur and, consequently, oxidation and reduction reactions. Thus, in association with photoredox catalysis, microreactor technology and continuous flow chemistry also play an important role in the development of organic synthesis processes, as this technology offers high yields, high selectivity and reduced side reactions. However, there is a lack of a more detailed understanding of the photoredox catalysis process, and computational tools based on computational fluid dynamics (CFD) can be used to deal with this and boost to reach higher levels of accuracy to continue innovating in this area. In this review, a comprehensive overview of the fundamentals of photoredox catalysis is provided, including the application of this technology for the synthesis of added-value chemicals in microreactors. Moreover, the advantages of the continuous flow system in comparison with batch systems are pointed out. It was also demonstrated how modeling and simulation using computational fluid dynamics (CFD) can be critical for the design and optimization of microreactors applied to photoredox catalysis, so as to better understand the reagent interactions and the influence of light in the reaction medium. Finally, a discussion about the future prospects of photoredox reactions considering the complexity of the process is presented.

Gels ◽  
2022 ◽  
Vol 8 (1) ◽  
pp. 54
Laura Riva ◽  
Angelo Davide Lotito ◽  
Carlo Punta ◽  
Alessandro Sacchetti

Herein we report the synthesis of cellulose-based metal-loaded nano-sponges and their application as heterogeneous catalysts in organic synthesis. First, the combination in water solution of TEMPO-oxidized cellulose nanofibers (TOCNF) with branched polyethyleneimine (bPEI) and citric acid (CA), and the thermal treatment of the resulting hydrogel, leads to the synthesis of an eco-safe micro- and nano-porous cellulose nano-sponge (CNS). Subsequently, by exploiting the metal chelation characteristics of CNS, already extensively investigated in the field of environmental decontamination, this material is successfully loaded with Cu (II) or Zn (II) metal ions. Efficiency and homogeneity of metal-loading is confirmed by scanning electron microscopy (SEM) analysis with an energy dispersive X-ray spectroscopy (EDS) detector and by inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis. The resulting materials perform superbly as heterogeneous catalysts for promoting the reaction between aromatic aldehydes and alcohols in the synthesis of aromatic acetals, which play a fundamental role as intermediates in organic synthesis. Optimized conditions allow one to obtain conversions higher than 90% and almost complete selectivity toward acetal products, minimizing, and in some cases eliminating, the formation of carboxylic acid by-products. ICP-OES analysis of the reaction medium allows one to exclude any possible metal-ion release, confirming that catalysis undergoes under heterogeneous conditions. The new metal-loaded CNS can be re-used and recycled five times without losing their catalytic activity.

Molecules ◽  
2022 ◽  
Vol 27 (2) ◽  
pp. 462
Fenghui Wu ◽  
Can Yang ◽  
Guangfei Qu ◽  
Liangliang Liu ◽  
Bangjin Chen ◽  

Phosphogypsum (PG) treatment is one of the research hotspots in the field of environmental protection. Many researchers both at home and abroad have devoted themselves to studies on harmless resource treatment of PG, but the treatment technology is unable to meet the demand of PG consumption due to the huge production and storage demands. In order to solve the problem of PG pollution, this study explored the different solidified effects of various modification formulations on the hazardous components in PG, using industrial solid waste calcium carbide slag (CCS) as an alkaline regulator; Portland cement (PC), polyaluminum chloride (PAC) and CaCl2 as the main raw materials of the solidification and stabilization formula and the water content in PG as the reaction medium. The results showed that CCS (0.5%), PC (0.4%) and PAC (0.3%) had a more significant solidified effect on phosphorus (P) and fluoride (F). PAC was added in two steps and reacted under normal temperature and pressure, and its leaching toxicity meets the requirements of relevant standards, which laid an excellent foundation for PG-based ecological restoration materials and filling materials, with low economic cost, simple process and strong feasibility. This will provide great convenience for the later mining and metallurgy.

Polymers ◽  
2022 ◽  
Vol 14 (1) ◽  
pp. 210
Vitor Vlnieska ◽  
Aline Silva Muniz ◽  
Angelo Roberto dos Santos Oliveira ◽  
Maria Aparecida Ferreira César-Oliveira ◽  
Danays Kunka

Biodiesel production from first-generation feedstock has shown a strong correlation with the increase in deforestation and the necessity of larger areas for land farming. Recent estimation from the European Federation for Transport and Environment evidenced that since the 2000s decade, an area equal to the Netherlands was deforested to supply global biodiesel demand, mainly originating from first-generation feedstock. Nevertheless, biodiesel is renewable, and it can be a greener source of energy than petroleum. A promising approach to make biodiesel independent from large areas of farming is to shift as much as possible the biodiesel production chain to second and third generations of feedstock. The second generation presents three main advantages, where it does not compete with the food industry, its commercial value is negligible, or none, and its usage as feedstock for biodiesel production reduces the overall waste disposal. In this manuscript, we present an oligomeric catalyst designed to be multi-functional for second-generation feedstock transesterification reactions, mainly focusing our efforts to optimize the conversion of tallow fat and sauteing oil to FAME and FAEE, applying our innovative catalyst. Named as Oligocat, our catalyst acts as a Brønsted-Lowry acid catalyst, providing protons to the reaction medium, and at the same time, with the course of the reaction, it sequesters glycerol molecules from the medium and changes its physical phase during the transesterification reaction. With this set of properties, Oligocat presents a pseudo-homogenous behavior, reducing the purification and separation steps of the biodiesel process production. Reaction conditions were optimized applying a 42 factorial planning. The output parameter evaluated was the conversion rate of triacylglycerol to mono alkyl esters, measured through gel permeation chromatography (GPC). After the optimization studies, a conversion yield of 96.7 (±1.9) wt% was achieved, which allows classifying the obtained mono alkyl esters as biodiesel by ASTM D6751 or EN 14214:2003. After applying the catalyst in three reaction cycles, Oligocat still presented a conversion rate above 96.5 wt% and as well an excellent recovery rate.

Catalysts ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 47
Karolina Zalewska ◽  
Małgorzata E. Zakrzewska ◽  
Luis C. Branco

Structure, and consequently properties, of ionic liquids can be easily tailored by changing cation/anion combinations and/or attaching functional groups. By grafting enantiopure moieties to the framework of ionic liquid it is possible to prepare bioinspired chiral molecules that can serve as a reaction medium, additive or even asymmetric catalyst. In this context, new chiral ionic liquids (CILs), based on biomolecules, such as aminoacids (L-cysteine derivatives), have been synthesised and tested in asymmetric aldol condensation of aldehydes and ketones. The best results were obtained for CILs composed of S-methyl-L-cysteine cation and bis(trifluoromethane)sulfonimide anion, in the reaction of 2- or 4-nitrobenzaldehyde with acetone or cyclohexanone, giving the aldol product in moderate yields 70–76% and high ee values (up to 96%).

Chemosphere ◽  
2022 ◽  
pp. 133528
Binita Dev ◽  
Arindam Bakshi ◽  
Balasubramanian Paramasivan

2022 ◽  
Vol 34 (2) ◽  
pp. 263-271
J.H. Trivedi ◽  
J.R. Jivani ◽  
K.H. Patel ◽  
H.C. Trivedi

Ceric ammonium nitrate (CAN)-initiated graft copolymerization of methyl acrylate (MA) onto sodium salt of partially carboxymethylated tamarind kernel powder (Na-PCMTKP, DS = 0.15) was studied in an aqueous medium by solution polymerization technique. The growth of the graft reaction was monitored gravimetrically. The role of various synthesis variables on the grafting yields was examined to achieve the maximum graft yields (%G = 278.27, %GE = 94.38, %Hp = 5.62) and the influence of the synthesis variables in the graft copolymerization has been discussed. The reactivity of methyl acrylate (MA) towards graft copolymerization was compared with that of acrylonitrile (AN) on the basis of the results obtained from the earlier studies and plausible explanation was furnished for the observed reactivity of both the monomers towards grafting. The evaluated optimized reaction conditions were utilized to study the effect of reaction medium on grafting and it was found that reaction medium plays an important role in graft copolymerization. In order to ascertain the grafting, characterization of the samples made by FTIR, TGA and SEM was conducted. The synthesized novel graft copolymer may find potential application to be used as metal adsorbents.

Nanomaterials ◽  
2021 ◽  
Vol 12 (1) ◽  
pp. 149
Enrico Paradisi ◽  
Roberto Rosa ◽  
Giovanni Baldi ◽  
Valentina Dami ◽  
Andrea Cioni ◽  

A new method for fast and simple synthesis of crystalline TiO2 nanoparticles with photocatalytic activity was developed by carrying out a classic sol–gel reaction directly under vacuum. The use of microwaves for fast heating of the reaction medium further reduces synthesis times. When the solvent is completely removed by vacuum, the product is obtained in the form of a powder that can be easily redispersed in water to yield a stable nanoparticle suspension, exhibiting a comparable photocatalytic activity with respect to a commercial product. The present methodology can, therefore, be considered a process intensification procedure for the production of nanotitania.

A. I. Lakhova ◽  
S. M. Petrov ◽  
N. E. Ignashev ◽  
G. G. Islamova ◽  

The article presents the results of deep processing of heavy crude oil in supercritical aqueous fluid, which makes it possible to significantly reduce the content of sulfur and resinous asphaltene compounds in products, and to increase the yield of light fuel fractions. The possibility of reducing the temperature of upgrading of heavy crude oil due to the presence of active charcoal in the reaction medium is shown. The proposed technology provides environmentally safe and residue-free processing of heavy oil and further production of high-quality hydrocarbon raw materials enriched in low-boiling fractions. Keywords: upgrading; heavy crude oil; supercritical aqueous fluid; activated charcoal.

Membranes ◽  
2021 ◽  
Vol 12 (1) ◽  
pp. 33
Marcin Tyrka ◽  
Mariusz Nowak ◽  
Dusan Misic ◽  
Tomasz Półbrat ◽  
Stanisław Koter ◽  

The study explores the grafting of cellulose acetate microfiltration membranes with an aminosilane to attain antibiofilm properties. The grafting reaction was performed in the supercritical carbon dioxide used as a transport and reaction medium. The FTIR analyses and dissolution tests confirmed the covalent bonding between the aminosilane and polymer. The membranes’ microstructure was investigated using a dual-beam SEM and ion microscopy, and no adverse effects of the processing were found. The modified membranes showed a more hydrophilic nature and larger water permeate flow rate than the neat cellulose acetate membranes. The tests in a cross-filtration unit showed that modified membranes were considerably less blocked after a week of exposure to Staphylococcus aureus and Escherichia coli than the original ones. Microbiological investigations revealed strong antibiofilm properties of the grafted membranes in experiments with Staphylococcus aureus, Listeria monocytogenes, Escherichia coli, and Salmonella Enteritidis.

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