Isomer‐dependent properties of poly(vinyl pyridine)‐based films grown on copper surfaces

Abstract

The effect of poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) isomers on the growth of surface films on copper substrates was studied by electrochemical, spectroscopic, thermogravimentric, and microscopic methods. In acid environment (3% v/v acetic acid) and in the presence of KSCN, electrochemically generated copper cations reacted rapidly with SCN À and P2VP or P4VP, yielding coordination compounds, which deposited onto copper surfaces as films. The characteristics of such polymer-metal complexes (films) were markedly isomer-dependent. Cu(I)/ P2VP/SCN À complexes with monovalent cations and sulfur-coordinated thiocyanate were obtained in the presence of P2VP, whereas the formation of Cu(II)/P4VP/SCN À complexes with divalent cations and nitrogen-coordinated thiocyanate was observed in the presence of P4VP. Interestingly, similar physical-chemical properties (electronic structure, stoichiometry, and thermal behavior) were observed for materials synthesized by electrochemical and chemical methods. These results suggest, therefore, that control over the surface properties of copper substrates can be achieved using electrosynthesized films based on different PVP isomers. Besides acting as effective protective barriers against aggressive media and thus reducing the metal dissolution (corrosion) kinetics, these materials are potentially attractive for other applications in which surface properties are paramount, such as in catalysis.

Robust Electroreduction of CO2 at a Poly(4‐vinylpyridine)–Copper Electrode

“…Secondly, shoulders at 1025 and 1615–1620 cm −1 appear and develop with time. These shoulders are at the same positions as the ν 1 and ν 8a ring stretching modes of Cu II –P4VP complexes . The blueshift of these peaks is caused by electron polarization upon the pyridyl–copper σ coordination and correlates with the strength of the N–metal bond .…”

“…For analysis of the complex formation of interest are peaks at 993 and 1598 cm −1 , which are attributed to in‐plane symmetric and asymmetric ring deformations, labeled ν 1 and ν 8a , respectively. These modes are most sensitive to the σ‐coordination of pyridyl groups …”

Ultraporous Films with Uniform Nanochannels by Block Copolymer Micelles Assembly

“…Copper ions are known to form complex with pyridine groups. , The lone electron pair on nitrogen acts as a strong ligand for coordination with transition metals. Using copper acetate part of the acetate anions might remain complexed with copper, as confirmed for the analogous P4VP homopolymer by Belfiore and McCurdie (Scheme ), using spectroscopic methods.…”

Adsorption behavior of caffeine as a green corrosion inhibitor for copper

“…Chromate, molybdate and tetraborate have been cited as inorganic corrosion inhibitors. More recently, short-chain alkanoic acid potassium salts [9], poly(4-vinylpyridine) [10][11][12] and poly(4-vinylpyrrolidone) [13] have also been shown to be potential corrosion inhibitors for copper.…”