A study on interfacial mechanisms and structure of poly(ethylene-co-methacrylic acid)/copper with reflection–absorption infrared spectroscopy

Bonding Mechanisms at Buried Interfaces between Carboxylic Polymers and Treated Zinc Surfaces

“…Therefore, both carbon–oxygen bonds in COO – are assumed to be equivalent in the complete resonance structure. The symmetric stretch transition moment is along the bisector of each oxygen–carbon–oxygen group, and the asymmetric stretch moment is perpendicular to the symmetric stretch moment, i.e., the transition moments for the symmetric and asymmetric stretching modes are parallel to and perpendicular to the 2-fold axis, respectively . The adsorption of the model compounds and polymer B shows that the adsorption peak of symmetric carboxylate stretching vibration ν s (COO – ) is stronger than the asymmetric carboxylate stretching vibration ν as (COO – ).…”

“…IEP can be calculated as the pH of an aqueous solution in which the solid surface exists in a state of electrical neutrality. A low IEP value indicates an acidic surface while a high value suggests a basic one . It is known that the Zn surface is hydrated in ambient air and covered with ZnO and Zn(OH) 2 components .…”

“…It is known that the COO − anion exhibits the resonance structure rather than the characteristic peak of dissociative carbonyl. 58 Therefore, both carbon−oxygen bonds in COO − are assumed to be equivalent in the complete resonance structure. The symmetric stretch transition moment is along the bisector of each oxygen−carbon−oxygen group, and the asymmetric stretch moment is perpendicular to the symmetric stretch moment, i.e., the transition moments for the symmetric and asymmetric stretching modes are parallel to and perpendicular to the 2-fold axis, respectively.…”

“…This provides the polymer more structural freedom in the interface area and helps the molecules at the interface to have a preferential conformation and reactivity with Zn adsorption sites. Li et al 58 showed that the interfacial orientation of the carboxylic functionalities is more perpendicular than those of small carboxylic acid molecules for which a configuration approximately vertical to the metal surface is proposed.…”

Further Understanding of the Adsorption Mechanism of N719 Sensitizer on Anatase TiO2 Films for DSSC Applications Using Vibrational Spectroscopy and Confocal Raman Imaging

“…Many research groups have used the carboxylate difference (Δν = ν asym (COO − ) − ν sym (COO − )) in the infrared spectra as a criterion to elucidate the type of bonding between the metal oxide surface and adsorbents, such as sensitizer, gas, and polymer molecules. − , In particular, the neat/solid (Δν salt ) state and the adsorbed state (Δν ads ) have been used to determine bond coordination in carboxylate and carboxylic acid groups. − ,, Deacon and Phillips made elaborate examinations of infrared spectra of solid acetates and trifluoracetates (carboxylates) having known crystal structures, , from which the Δν parameter was derived as a result of the COO − low symmetry. The nature of the binding mode can be inferred from the following criteria: if Δν ads > Δν salt = unidentate; if Δν ads < Δν salt = chelate or bridge; and if Δν ads << Δν salt = chelate. , In an effort to apply the Δν criterion to the type of bonding operating between the N719 dye and other reagents with similar binding groups onto TiO 2 , the Δν values from several previous studies were analyzed.…”