Electrochemically mediated atom transfer radical polymerization of acrylonitrile and poly(acrylonitrile-b-butyl acrylate) copolymer as a precursor for N-doped mesoporous carbons

Trevisanello, Enrico; Bon, Francesco De; Daniel, Giorgia; Lorandi, Francesca; Durante, Christian; Isse, Abdirisak Ahmed; Gennaro, Armando

doi:10.1016/j.electacta.2018.07.209

Cited by 31 publications

(39 citation statements)

References 54 publications

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“…When 50 % (v/v) of MMA was added to the solution, roughly halving the concentration of Cu(II), an increase of current intensity and a positive shift of E 1/2 to −0.58 V vs Fc + /Fc were observed. Similar positive shifts of copper catalysts in other solvents were already reported and related to a decrease of solvent polarity after monomer addition . The increase of the current is due to a decrease of solution viscosity in the presence of MMA.…”

Section: Resultssupporting

confidence: 87%

“…A 3 mm diameter glassy carbon disk or a Pt mesh (Alfa Aesar, 99.9 % metals basis) with a geometric area of approximately 6 cm 2 , was used as working electrode in cyclic voltammetry and electrolysis, respectively. The electrodes were cleaned and activated as previously reported . As a counter electrode either a Pt wire or a graphite rod was used.…”

Section: Methodsmentioning

confidence: 99%

“…Last, the reaction can be stopped and restarted on demand, by appropriately adjusting the applied potential or current. This technique was applied to several monomers in organic solvents, water (at both neutral and very acidic pH), oil‐in‐water miniemulsion and ionic liquids …”

Section: Introductionmentioning

confidence: 99%

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Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange

2019

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Electrochemically mediated atom transfer radical polymerization (eATRP) of methyl methacrylate (MMA) was studied in 1‐butyl‐3‐methylimidazolium triflate ([BMIm][OTf]) and ethanol. When 2‐bromopropionitrile and ethyl 2‐bromoisobutyrate were used as initiators, poorly controlled or uncontrolled polymerizations yielding polymers with molecular weights largely exceeding the theoretical values were obtained. Poor control was attributed to a reactivity mismatch between initiator and dormant species, which was successfully suppressed by combining eATRP with catalytic halogen exchange. Well‐defined polymers (Mn>30000 and Ð<1.2) were obtained in both solvents under optimized conditions. The possibility of using PMDETA as an inexpensive ligand in combination with ethyl α‐bromophenylacetate as initiator was also successful. Good chain‐end fidelity during eATRP was confirmed by chain extension of PMMA‐Cl macroinitiator with MMA in ethanol. Polymers prepared in both solvents were found to be mainly syndiotactic, without any solvent effect on tacticity.

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Section: Resultssupporting

confidence: 87%

Section: Methodsmentioning

confidence: 99%

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Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange

2019

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“…[16][17][18][19][20][21][22][23][24][25] ATRP is catalyzed by transition metal complexes and many metals have been tested [26] but over the years the process has been refined to use small amounts of copper complexes with polydentate amine ligands. [27] Indeed, techniques such as initiators for continuous activator regeneration (ICAR) ATRP, [28,29] activators regenerated by electron transfer (ARGET) ATRP, [30][31][32][33] supplemental activator and reducing agent (SARA) ATRP, [34][35][36][37][38][39][40] photoATRP, [41][42][43][44] electrochemically mediated ATRP (eATRP), [45][46][47][48][49][50][51][52] mechanoATRP, [53] sono-ATRP [54][55][56][57][58] allowed well-controlled polymerizations with catalyst amounts down to parts per million levels relative to the monomer. Scheme 1 illustrates the mechanism of eATRP catalyzed by Cu complexes with multidentate nitrogen-based ligands (L).…”

Section: Introductionmentioning

confidence: 99%

“…This technique was applied to several monomers in organic solvents, water, oil-inwater mini-emulsion, ionic liquids and for the ultrasensitive detection of glucose. [48,49,51,52,[64][65][66][67] Furthermore, electrochemically mediated ATRP has been successfully triggered from surfaces [68][69][70][71][72][73][74] or with iron-based catalysts [75,76] or even pseudohalides. [77] This work focuses on radical polymerization of DMAA by electrochemically mediated ATRP, highlighting on one hand the possibility of obtaining well-controlled polymers with low dispersity and, on the other hand, their low chain-end fidelity despite the controlled growth in a short time with high monomer conversion.…”

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confidence: 99%

Electrochemically Mediated Aqueous Atom Transfer Radical Polymerization of N,N‐Dimethylacrylamide

et al. 2020

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Electrochemically mediated atom transfer radical polymerization (ATRP) of N,N‐dimethylacrylamide (DMAA) catalyzed by copper complexes with polydentate amine ligands was studied systematically in water, investigating several reaction parameters such as applied potential, catalyst concentration, ligand structure, monomer and initiator concentrations. Electropolymerizations were successfully performed under both potentiostatic and galvanostatic conditions; in both eATRP modes, reactions were fast (monomer conversion >90 % in less than 1 h) and well‐controlled, providing polymers with narrow molecular weight distributions. Despite the low dispersity, chain extension attempts of the obtained polymer were not successful because of partial loss of C−Br chain‐end functionality, due to an intramolecular nucleophilic attack. This is an intrinsic drawback of ATRP of acrylamides and although the electrochemical approach allowed preparation of well‐defined polymers in a very short time (down to ca. 15 min), loss of chain‐end functionality was unavoidable.

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Nitrogen‐Doped Mesoporous Carbon Electrodes Prepared from Templating Propylamine‐Functionalized Silica

et al. 2020

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In this paper, nitrogen doped carbon materials with mesopores 4–8 nm‐wide and a high surface area of ca.1100 m2 g−1 were synthesized according to an innovative hard template method. Sucrose was used as carbon source and propylamine functionalized silica acted as both nitrogen source and templating agent. The novel doped carbons were compared with mesoporous carbons featuring similar texture properties (pore size and surface area) but obtained by the pyrolysis of sucrose or 1,10‐phenantholine and employing non‐functionalized silica as a templating agent. The interest of this investigation is to understand how doping occurs when a functionalized silica is employed, and whether the nitrogen doping remains a surface property or it is extended also to the bulk of the material, influencing the morphological and the electrical properties of the resulting carbon. X‐ray photoemission spectroscopy, elemental analysis, and EDX confirmed the doping action of the functionalized silica and the electrochemical characterization allowed to compare the different performances as supercapacitor materials.

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Electrochemically mediated atom transfer radical polymerization of acrylonitrile and poly(acrylonitrile-b-butyl acrylate) copolymer as a precursor for N-doped mesoporous carbons

Cited by 31 publications

References 54 publications

Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange

Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange

Electrochemically Mediated Aqueous Atom Transfer Radical Polymerization of N,N‐Dimethylacrylamide

Nitrogen‐Doped Mesoporous Carbon Electrodes Prepared from Templating Propylamine‐Functionalized Silica

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