Effect of surface coating of microcrystalline cellulose by imidazole molecules on proton conductivity

Smolarkiewicz, I.; Rachocki, Adam; Pogorzelec‐Glaser, Katarzyna; Ławniczak, Paweł; Pankiewicz, Radosław; Tritt‐Goc, Jadwiga

doi:10.1016/j.eurpolymj.2016.03.026

Cited by 18 publications

(10 citation statements)

References 37 publications

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“…The value of the activation energy of pure CNF (0.75 eV) is lower compared to those of the other pure cellulose materials (for example, for the CNC film it is equal to 1.07 eV, for CMF it is 1.2 eV) (Jankowska et al 2018(Jankowska et al , 2020. For 2CNF-Im nanocomposite, the activation energy (0.62 eV) is the lowest from among the values for the other composites based on pure cellulose: in 5.4CMC-Im, the activation energy is 0.82 eV; 3.5CMF-Im-0.95 eV; 1.3CNC-Im-0.78 eV (Jankowska et al 2020;Smolarkiewicz et al 2015Smolarkiewicz et al , 2016Tritt-Goc et al 2019).…”

Section: Resultsmentioning

confidence: 88%

“…At first, the samples were heated from 10 to 110°C and kept at this temperature for half an hour. To compare obtained results with other cellulose-based materials which are synthesized by our group, the annealing time is the same as in our previously published articles (Jankowska et al 2018(Jankowska et al , 2020Smolarkiewicz et al 2015Smolarkiewicz et al , 2016. Next, the materials were cooled down to 10°C and then heating up to 250°C.…”

Section: Characterization Methodsmentioning

confidence: 99%

“…Cellulose materials can be divided, among others by their structure on a dimensional scale into: microcrystalline cellulose (CMC), nanocrystalline cellulose (CNC), cellulose microfibers (CMF), and CNF. Our group synthesized several anhydrous composites based on pure celluloses (CMC, CNC, CMF) functionalized with imidazole (Im), exhibit proton conductivity above the boiling point of water (Jankowska et al 2020;Smolarkiewicz et al 2015Smolarkiewicz et al , 2016Tritt-Goc et al 2018. Previously reported results (Jankowska et al 2018) allowed us to hypothesize that the functionalization of CNF with imidazole should be more effective and result in the higher conductivity values and the lower activation energy of the proton transport process in comparison to composites based on other cellulose materials.…”

Section: Introductionmentioning

confidence: 99%

“…Compared to other cellulose materials, CNF are characterized by the higher thermal stability and the lower activation energy of the proton transport process (Jankowska et al 2018). The activation energy of the proton transport process in CMC-based composite, 5.4CMC-Im (one imidazole molecule per 5.4 glucose units) is equal to 0.82 eV (Smolarkiewicz et al 2015(Smolarkiewicz et al , 2016. In CMF-based composite (1 imidazole molecule per 3.5 glucose units), the activation energy is 0.95 eV (Jankowska et al 2020).…”

Section: Introductionmentioning

confidence: 99%

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New liquid-free proton conductive nanocomposite based on imidazole-functionalized cellulose nanofibers

et al. 2020

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The first successful attempt to synthesize a new proton conducting polymeric nanocomposite film based on pure cellulose nanofibers (CNF) as a polymer matrix functionalized on their surface with imidazole molecules (Im) as a dopant, was made. The 2CNF-Im nanomaterial contains on average one molecule of imidazole per 2 glucose units from cellulose chains. Water evaporation and thermal stability of 2CNF-Im were studied by thermogravimetric analysis (TGA and DTG) and differential scanning calorimetry (DSC). The temperature dependence of electrical conductivity was studied by the impedance spectroscopy. At 140 °C, the 2CNF-Im nanocomposite has a maximum conductivity of 7.0 × 10−3 S/m, i.e. four orders of magnitude higher than that of non-functionalized CNF matrix. The newly synthesized cellulose nanocomposite exhibits high electrical and thermal stability. In 2CNF-Im, the activation energy of the proton transport process is the lowest compared to the previously synthesized imidazole-functionalized composites based on other pure cellulose materials and equals 0.62 eV. The synthesized nanomaterial is liquid-free solid polymer electrolyte showing proton conductivity above the boiling point of water.

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Section: Resultsmentioning

confidence: 88%

Section: Characterization Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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New liquid-free proton conductive nanocomposite based on imidazole-functionalized cellulose nanofibers

et al. 2020

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“…The wide band in a region of 3500-3000 cm −1 characterizes the formation of multiple hydrogen bonds in the copolymer. It is known [24,37,38] that nitrogen-containing heterocycles are capable of forming hydrogen-bound networks. To provide fast transport, imidazole membranes are generally doped by an excess of sulfuric or phosphonic acids [38] which provide ion transport by the Grotthuss mechanism.…”

Section: (1)mentioning

confidence: 99%

Sodium p-Styrene Sulfonate–1-Vinylimidazole Copolymers for Acid–Base Proton-Exchange Membranes

Лебедева

Pozhidaev

Малахова

et al. 2020

Membr. Membr. Technol.

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Binary copolymers possessing thermal stability up to 290°C and suitable for the formation of ionexchange membranes have been obtained by free radical copolymerization of sodium p-styrene sulfonate and 1-vinylimidazole with subsequent conversion to the H-form. The composition and structure of the copolymers are confirmed by elemental analysis and IR and NMR spectroscopy. Multicomponent membranes based on the copolymers of sodium p-styrene sulfonate and 1-vinylimidazole have been obtained using poly(vinyl alcohol) crosslinked by oxalic acid as a film-forming agent. It is shown by scanning electron microscopy that the surface and cut of the membranes have a uniform structure. The specific electric conductivity of the membranes with different concentrations of styrene sulfonic acid (20 to 80 mol % in the copolymer) increases with an increase in the fraction of styrene sulfonic acid and is 29.5 to 52.0 mS cm −1 at 80°C. The activation energy of proton transport of the membranes is 12.5 to 15.5 kJ mol −1. The water uptake of the membranes decreases with the increase in the concentration of the basic (imidazole) component in them, which may be associated with the increase in the density of ionic crosslinking due to the acid-base interaction of the sulfo groups and pyridine nitrogen atoms of the imidazole cycle. The formation of acid-base pairs results in the formation of continuous proton transport channels in addition to the sulfonic acid channels, which is confirmed by the high values of specific electric conductivity even in the case of a decrease in the concentration of sulfostyrene in the composition of the membrane. Increasing the concentration of 1-vinylimidazole in the composition of the copolymer from 20 to 80 mol % leads to an increase in the relative elongation at break from 3 to 6%, an increase in the tensile strength at break from 4 to 7 MPa, a decrease in the Young modulus of the membranes from 127 to 102 MPa, and a decrease in the water uptake from 45 to 15.

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Effect of imidazole‐doped nanocrystalline cellulose on the characterization of Nafion films of fuel cells

Phong

Nhi

et al. 2021

J of Chemical Tech & Biotech

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BACKGROUND: In this study, we have fabricated a polymeric material (CNC/Im) consisting of cellulose nanocrystals (CNC) synthesized from Vietnamese rice husk biomass and imidazole (Im) dopant. Next, we propose a new approach to fabricate Nafion/CNC/imidazole (NCI) composite materials by mixing the CNC/imidazole hybrid into Nafion matrix using a very simple solution method, and then investigating the influence of CNC/Im on the properties of NCI membranes. RESULTS: Electrochemical impedance spectroscopy (EIS) analysis showed that the proton conductivity of the CNC/Im membrane depends on the linked molar ratio of Im to glucose units (denoted by the n index), and this value is higher than that of pure CNC by a factor of 6. Differential thermal analysis (DSC) showed that the value of the n index is around 1:17 with all the content ratios between CNC and Im. Next, we synthesized composite materials based on CNC/Im and Nafion 117 (NCI) and investigated the influence of CNC/Im on the properties of NCI membranes. The results demonstrated that proton conductivity of the NCI membranes changes according to the content of Nafion 117, and reaches the highest value of 6.19 × 10 −4 S m -1 with an Nafion 117/(CNC/Im) ratio of 2:1. It was observed that the CNC fiber bundles were surrounded by a polymer layer and no phase separation occurs in the scanning electron micrographs of NCI materials.CONCLUSIONS: These results indicate that the prepared NCI composites will be potential materials for eco-friendly fuel cell operating in low humidity conditions.

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Effect of surface coating of microcrystalline cellulose by imidazole molecules on proton conductivity

Cited by 18 publications

References 37 publications

New liquid-free proton conductive nanocomposite based on imidazole-functionalized cellulose nanofibers

New liquid-free proton conductive nanocomposite based on imidazole-functionalized cellulose nanofibers

Sodium p-Styrene Sulfonate–1-Vinylimidazole Copolymers for Acid–Base Proton-Exchange Membranes

Effect of imidazole‐doped nanocrystalline cellulose on the characterization of Nafion films of fuel cells

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