Electropolymerization and Electrocatalytic Activity of Poly(4-thienylacetyl-amino-2,2,6,6-tetramethylpiperidinyl-1-yloxy)/(2,2′-bithiophene) Copolymer

Abstract

Monomer 4-thienylacetyl-amino-2,2,6,6-tetramethylpiperidinyl-1-yloxy (TATEMPO) has been synthesized. The homopolymer poly(2,2 -bithiophene) (PBTh), and poly(4-thienylacetyl-amino-2,2,6,6-tetramethylpiperidinyl-1-yloxy)/(2,2 -bithiophene) (PTATEMPO/BTh) copolymer are successfully prepared on platinum in boron trifluoride diethyl etherate solution by electrochemical polymerization. They are characterized by scanning electron microscopy. The electrochemical copolymerization of TATEMPO and BTh may be accomplished through a radical reaction process. The electrocatalytic oxidation performance of benzyl alcohol in 0.1 M NaClO 4 -CH 3 CN solution in the presence of 2,6-lutidine on PTATEMPO/BTh electrode is investigated by cyclic voltammetry and in situ FTIR. Benzyl alcohol is selectively converted to benzaldehyde on the PTATEMPO/BTh electrode, and the overoxidation to benzoic acid is suppressed.

Electropolymerized Polythiophenes Bearing Pendant Nitroxide Radicals

“…One feasible way to synthesize polythiophene-organic radical polymers is through FeCl 3 -aided oxidative polymerization; however, polymerization is uncontrolled, and the products are intractable, preventing solution processing and characterization. 31 Electropolymerization of thiophene monomers bearing pendant nitroxide radicals has been reported; 33,48,49 however, only one type of such polymer was reported due to the limited commercial availability of monomers. The physical properties of polythiophene-organic radical polymers is even less well understood and remains an intriguing topic.…”

Electrochemical Performance of ABNO for Oxidation of Secondary Alcohols in Acetonitrile Solution

“…The band at 1176 cm −1 was related to C-H in-plane bending of 2,6-lutidinium cation [58,59]. It confirmed that 2,6-lutidine got a hydrogen proton to become 2,6-lutidinium cation during the electrocatalytic process [60,61]. Meanwhile, three negative-going bands at 1685, 1360, and 1267 cm −1 were detected, which were attributed to C=O stretching vibration, C-H deformation vibration in the methyl group, and skeleton vibration of acetophenone, respectively [62].…”

Electropolymerizable Thiophene–Oligonucleotides for Electrode Functionalization

“…BTh is the dimer of the thiophene unit that can be easily electropolymerized by potentiostatic, galvanostatic, or potentiodynamic techniques . Even if potential sweep techniques require longer reaction times to obtain well-attached polymer films compared to potentiostatic or galvanostatic measurements, this method is used due to the possibility to monitor the electrochemical properties of the growing polymer, along the polymerization process, allowing a detailed study of the electropolymerization kinetics. − Hence, the electropolymerization of the monomer was carried out potentiodynamically by repetitive cycling of the electrode potential (between 0.0 and 1.2 V vs Ag/AgCl) in a solution containing 9.8 mM of the monomer and 0.1 M LiClO 4 in ACN:water (1:1 v/v), at a scan rate of 50 mV·s –1 (see SI, Figure S11). Under these conditions, an irreversible oxidation process on the surface of the ITO electrode in the ACN:water system was observed, showing in the first potentiodynamic cycle the typical trace-crossing effect observed during the electrochemical polymerization of π-conjugated systems .…”