scholarly journals Assessment of Catalyst Selectivity in Carbon-Nanotube Silylesterification

2019 ◽  
Vol 10 (1) ◽  
pp. 109 ◽  
Author(s):  
Simon Detriche ◽  
Arvind K. Bhakta ◽  
Patrick N’Twali ◽  
Joseph Delhalle ◽  
Zineb Mekhalif

The functionalization of carbon nanotubes (CNTs) plays a key role in their solubilization and compatibility for many applications. Among the many possible ways to functionalize CNTs, the creation of an Si–O–C bond is crucial for the formation of silicone composites. Catalyst-mediated silylesterification is useful in creating Si–O–C bonds because it is cost-effective and uses a hydrosilane precursor of lower reactivity than that of chlorosilane. However, it was previously demonstrated that two important silylesterification catalysts (zinc chloride and Karstedt’s catalyst) exhibit different selectivity for oxidized functional groups that are present on the surface of CNTs after oxidative acid treatment. This report details the selective modification of CNTs with various oxygenated functional groups (aromatic and nonaromatic alcohols, carboxylic acids, ethers, and ketones) using diazonium chemistry. Modified CNTs were used to assess the specifity of zinc chloride and Karstedt’s catalyst for oxygenated functional groups during a silylesterification reaction. Karstedt’s catalyst appeared to be widely applicable, allowing for the silylesterification of all of the aforementioned oxygenated functional groups. However, it showed lower efficacy for ethers and ketones. By contrast, zinc chloride was found to be very specific for nonaromatic carboxylic acids. This study also examined the Hansen solubility parameters of modified CNTs.

2021 ◽  
Vol 19 ◽  
pp. 228080002110174
Author(s):  
Vincenzina Barbera ◽  
Giulio Torrisi ◽  
Maurizio Galimberti

In this study, carbon papers and aerogels were prepared from chitosan and graphene layers with aldehydic edge functional groups (G-CHO) able to form chemical bonds with chitosan and thus to form a crosslinked network. A high surface area graphite was edge functionalized with hydroxyl groups (G-OH) through the reaction with KOH. G-CHO, with 4.5 mmol/g of functional group, was prepared from G-OH by means of the Reimer-Tieman reaction. Characterization of the graphitic materials was performed with elemental analysis, titration, X-ray analysis, Raman spectroscopy and by estimating their Hansen solubility parameters. CS and G-CHO were mixed with mortar and pestle and carbon papers and aerogels were obtained from a stable acidic water suspension through casting and liophilization, respectively. Free standing and foldable carbon papers and monolithic aerogels based on a continuous covalent network between G-CHO and CS were prepared. G-CHO, which had about 22 stacked layers, was extensively exfoliated in the carbon paper, as confirmed by the absence of the 002 reflection of the graphitic crystallites in the XRD pattern. Carbon paper was found to be resistant to solvents and to be stable for pH ⩾ 7. Composites revealed electrical conductivity. The covalent network between the graphene layers and CS, suggested by the IR findings, accounts for these results. This work demonstrates the effectiveness of a continuous covalent network between chitosan and graphene layers edge functionalized with tailor made functional groups for the preparation of carbon papers and aerogels and paves the way for the scale up of such a type of composites.


2018 ◽  
Author(s):  
Erin Stache ◽  
Alyssa B. Ertel ◽  
Tomislav Rovis ◽  
Abigail G. Doyle

Alcohols and carboxylic acids are ubiquitous functional groups found in organic molecules that could serve as radical precursors, but C–O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen centered nucleophile. We first show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H-atom trapping to afford the deoxygenated product. Using the same method, we demonstrate access to synthetically versatile acyl radicals which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge new C–O, C–N and C–C bonds in a single step.


Burns ◽  
2021 ◽  
Author(s):  
Maryam Hosseini ◽  
Michael S. Roberts ◽  
Reza Aboofazeli ◽  
Hamid R. Moghimi

Agronomy ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 561
Author(s):  
José A. Fernández-López ◽  
Marta Doval Miñarro ◽  
José M. Angosto ◽  
Javier Fernández-Lledó ◽  
José M. Obón

The sustainable management of biomass is a key global challenge that demands compliance with fundamental requirements of social and environmental responsibility and economic effectiveness. Strategies for the valorization of waste biomass from agrifood industries must be in line with sustainable technological management and eco-industrial approaches. The efficient bioremoval of the pesticides imazalil and thiabendazole from aqueous effluents using waste biomass from typically Mediterranean agrifood industries (citrus waste, artichoke agrowaste and olive mill residue) revealed that these residues may be transformed into cost-effective biosorbents. Agrifood wastes present irregular surfaces, many different sized pores and active functional groups on their surface, and they are abundant in nature. The surface and adsorptive properties of olive mill residue, artichoke agrowaste and citrus waste were characterized with respect to elemental composition, microstructure, crystallinity, pore size, presence of active functional groups, thermal stability, and point of zero charge. Olive mill residue showed the highest values of surface area (Brunauer–Emmett–Teller method), porosity, crystallinity index, and pH of zero point of charge. Olive mill residue showed the highest efficiency with sorption capacities of 9 mg·g−1 for imazalil and 8.6 mg·g−1 for thiabendazole.


Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3091
Author(s):  
Mohammed Ghazwani ◽  
Prawez Alam ◽  
Mohammed H. Alqarni ◽  
Hasan S. Yusufoglu ◽  
Faiyaz Shakeel

This research deals with the determination of solubility, Hansen solubility parameters, dissolution properties, enthalpy–entropy compensation, and computational modeling of a naturally-derived bioactive compound trans-resveratrol (TRV) in water, methanol, ethanol, n-propanol, n-butanol, propylene glycol (PG), and various PG + water mixtures. The solubility of TRV in six different mono-solvents and various PG + water mixtures was determined at 298.2–318.2 K and 0.1 MPa. The measured experimental solubility values of TRV were regressed using six different computational/theoretical models, including van’t Hoff, Apelblat, Buchowski–Ksiazczak λh, Yalkowsly–Roseman, Jouyban–Acree, and van’t Hoff–Jouyban–Acree models, with average uncertainties of less than 3.0%. The maxima of TRV solubility in mole fraction was obtained in neat PG (2.62 × 10−2) at 318.2 K. However, the minima of TRV solubility in the mole fraction was recorded in neat water (3.12 × 10−6) at 298.2 K. Thermodynamic calculation of TRV dissolution properties suggested an endothermic and entropy-driven dissolution of TRV in all studied mono-solvents and various PG + water mixtures. Solvation behavior evaluation indicated an enthalpy-driven mechanism as the main mechanism for TRV solvation. Based on these data and observations, PG has been chosen as the best mono-solvent for TRV solubilization.


2021 ◽  
Author(s):  
KANAT ANURAKPARADORN ◽  
ALAN TAUB ◽  
ERIC MICHIELSSEN

The proliferation of wireless technology calls for the development of cost-effective Electromagnetic Interference (EMI) shielding materials that reduce the susceptibility of high-speed electronic circuits to undesired incoming radiation. Ideally, such materials offer protection over wide frequency ranges and are insensitive to the polarization or angle of incidence of the impinging fields. Here, next-generation EMI shielding materials composed of polymer composites with conductive and magnetic fillers are introduced. It is shown that careful control of the concentration and dispersion of the polymers’ conductive and magnetic constituents permits tuning of the composites’ intrinsic electrical and magnetic properties. The resulting EMI shields are lightweight, cheap and offer greater protection than traditional metal gaskets and foams. In this work, cobalt ferrite magnetic nanoparticles (CoFe2O4) decorated on graphene-based material were dispersed in polylactic acid (PLA) matrix for high EM absorption level in X-band (8-12 GHz). The decoration of the magnetic particles was performed on the as-prepared conductive graphene nanoplatelets (GNP) and reduced graphene oxide (rGO). GNP composites exhibited higher DC conductivity, and permittivity than rGO composites. This is attributed to issues associated with the reduction process, including a lack of conductivity due to the insulated oxygen functional groups and the reduction in the lateral size. Compared with rGOs, the lack of out-plane functional groups causes the cobalt ferrite nanoparticles to agglomerate and not cover the entire surface of the GNPs. These morphological differences improve the magnetization and EM absorption of the composite system. The compatibilizer (pyrene-PLA-OH) was added to the composites to enhance dispersion of the GNPs in the polymer matrix which benefits in higher absorption of the shield. The influence of the compatibilizer on parameter, the reflection loss (RL) of the composite were determined from the characterized intrinsic properties


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