A Dual-Surface Mechanism of Oxidant-Free Pyrrole Polymerization in the Two-Dimensional Titanium Carbide (MXene) Interlayer Nanospace

Date

2022-01-01

Author

Yıldırım, Erol
Luo, He-Kuan
Jin, Hongmei
Wu, Gang
Tan, Teck Leong
Wong, Zicong Marvin
Xu, Jianwei.
Yang, Shuo-Wang

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

184
views

0
downloads

The influence of confinement in acidic nanotemplates on the polymerization reaction of pyrrole was previously reported. Similarly, an in situ oxidant-free polymerization of pyrrole on and in between the Ti3C2 MXene layers has been demonstrated experimentally. The newly formed PPy/MXene (PPy/polypyrrole) interface showed high electrical conductivity and supercapacitor features with excellent cycling stability. However, the polymerization mechanism remains unclear. In this study, the pyrrole polymerization mechanisms on Ti3C2 MXene surfaces and in between MXene interlayers with different terminations were investigated based on first-principles calculations. Key factors for such oxidant-free polymerization were identified, including the configuration of surface hydrogen-bonded pyrrole, surface acidity, confinement effect, and charge transfer between MXene surfaces and pyrrole monomers. By controlling these factors, one can design covalently bonded conducting organic molecules/polymers on or in between MXene interlayers for electronic applications. These findings not only uncover the mechanism for a proton-assisted pyrrole polymerization on and in between MXene interlayers but also provide a general mechanistic understanding and guideline for other possible in situ polymerizations on and in between two-dimensional MXene interlayers.

URI

https://hdl.handle.net/11511/95410

Journal

JOURNAL OF PHYSICAL CHEMISTRY C

DOI

https://doi.org/10.1021/acs.jpcc.1c08231

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

A new strategy for the synthesis of pyridines from N-propargylic beta-enaminothiones Kelgokmen, Yilmaz; Zora, Metin (Royal Society of Chemistry (RSC), 2019-03-07) A new method for the synthesis of 2,4,5-trisubstituted pyridines from N-propargylic beta-enaminothiones is reported. beta-Enaminothiones were prepared by thionation of the corresponding beta-enaminones with Lawesson's reagent. When treated with diisopropylamine in DMF at room temperature, N-propargylic beta-enaminothiones yielded 2,4,5-trisubstituted pyridines in moderate to high yields, along with small amounts of 2-methylene-2,3-dihydro-1,4-thiazepines. The reaction was found to be general for a broad ran...
A pyrolysis mass spectrometry study of polythiophene copolymers Aslan, Evren; Hacaloğlu, Jale; Toppare, Levent Kamil (2007-05-01) The thermal behaviour of copolymers of thiophene with decanedioic acid bis-(2-thiophen-3-yl-ethyl)ester (DATE) and terephthalic acid his(2-thiophen-3-yl-ethyl)ester (TATE) prepared by potentiostatic polymerization was studied via pyrolysis mass spectrometry. It was determined that the electrolytic films correspond to the related homopolymers. The increase in thermal stability of ester linkages, and evolution of characteristic degradation products of TATE and DATE together with thiophene based products above...
A soluble conducting polymer of 2,5-di(thiophen-2-yl)-1-p-tolyl-1H-pyrrole and its electrochromic device YİGİTSOY, Basak; VARİS, Serhat; Tanyeli, Cihangir; Akhmedov, Idris M.; Toppare, Levent Kamil (Elsevier BV, 2007-02-26) A monomer 2,5-di(thiophen-2-yl)-1-p-tolyl-1H-pyrrole was synthesized via reaction of 1,4-di(2-thienyl)-1,4-butanedione and p-toluidine in the presence of catalytical amount of p-toluenesulfonic acid. Chemical polymerization of the monomer yielded a soluble polymer. The average molecular weight was determined by gel permeation chromatography as number average molecular weight (Mn) 2.5 x 10(3) g/mol. The monomer was also electrochemically polymerized in the presence of LiClO4, NaClO4 (1:1) as the supporting e...
Synthesis of a new thiophene derivative and its uses as an electrochromic device component Yiğitsoy, Başak; Toppare, Levent Kamil; Department of Chemistry (2006) 2,5-Di(thiophen-2-yl)-1-p-tolyl-1H-pyrrole (DTTP) was synthesized via reaction of 1,4-di(2-thienyl)-1,4-butanedione with p-toluidine in the presence of catalytical amount of p-toluenesulfonic acid (PTSA). Homopolymer P(DTTP) was achieved both by chemical and electrochemical techniques. Chemical polymerization of the monomer yielded a soluble polymer. The average molecular weight was determined by gel permeation chromatography (GPC) as Mn: 2.5x103 g/mol. The monomer was electrochemically polymerized in the p...
A kinetic study on the decolorization of aqueous solutions of acid Red-151 by ozonation Ozbelge, TA; Erol, F; Ozbelge, O (Informa UK Limited, 2003-01-01) The ozonation kinetics of an azo dye, namely, Acid Red-151 was investigated. Effects of pH, initial ozone, and initial dye concentrations on the ozonation of the dye were studied. The reaction orders were found to be one with respect to both ozone and dye concentrations for the studied pH range of 2.5-10. The reaction rate constants were obtained as 125.8, 95.4, 87.9, and 129.9 L mmol(-1) min(-1) at the pH values of 2.5, 5, 7, and 10, respectively. The initial ozonation rate decreased with the increasing pH...

Citation Formats

E. Yıldırım et al., “A Dual-Surface Mechanism of Oxidant-Free Pyrrole Polymerization in the Two-Dimensional Titanium Carbide (MXene) Interlayer Nanospace,” JOURNAL OF PHYSICAL CHEMISTRY C, pp. 0–0, 2022, Accessed: 00, 2022. [Online]. Available: https://hdl.handle.net/11511/95410.