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Electrochemical analysis of the adsorption and desorption behaviors of carboxylic acid and anhydride monomers onto zinc surfaces

机译:羧酸和酸酐单体在锌表面上的吸附和解吸行为的电化学分析

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The interfacial bondings formed between succinic acid and myristic acid, as well as succinic anhydride molecules with a set of differently treated zinc substrates have been investigated using infrared reflection absorption spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The compounds were selected to model typically used carboxylic-based adhesives and coatings. Moreover, the adsorption kinetic has been evaluated by means of chronoamperometry (CA) and chronovoltammetry measurements. XPS results showed a relation between the amount of carboxylates formed by adsorption of succinic acid/myristic acid and the hydroxyl fraction presented on the surfaces as proved by a higher electron transfer in CA. On the other hand a set of oxidative/reductive interactions was detected during the adsorption of succinic anhydride, in turn proving a spontaneous ring opening and adsorption mechanism. A clear relationship between the amount of adsorbents and surface hydroxyls/carbonates was detected for the adsorption of succinic anhydride. The extent to which the formed carboxylates resisted negative potentials was also investigated by cyclic voltammetry (CV) in an aqueous solution. The coordinative bonding of a bifunctional carboxylic acid group to the oxide surface was found to be not stable in the presence of a negative potential, while a monofunctional carboxylic acid group could resist displacement by water for a prolonged period of time. On the other hand, a low double layer capacitance was obtained after the adsorption of succinic anhydride, which was related to a change in potential of zero charge (PZC) upon the adsorption.
机译:使用红外反射吸收光谱(FTIR)和X射线光电子能谱(XPS)研究了琥珀酸和肉豆蔻酸以及琥珀酸酐分子与一组经过不同处理的锌底物之间形成的界面键。选择这些化合物以模拟通常使用的基于羧基的粘合剂和涂料。此外,吸附动力学已经通过计时电流法(CA)和计时伏安法测量进行了评估。 XPS结果表明,由琥珀酸/肉豆蔻酸的吸附形成的羧酸盐的量与表面上存在的羟基部分之间的关​​系,由CA中较高的电子转移证明。另一方面,在琥珀酸酐的吸附过程中检测到一组氧化/还原相互作用,从而证明了自发的开环和吸附机理。对于琥珀酸酐的吸附,检测到吸附剂的量与表面羟基/碳酸盐之间的明确关系。还通过循环伏安法(CV)在水溶液中研究了所形成的羧酸盐抵抗负电位的程度。发现双官能羧酸基团与氧化物表面的配位键合在负电势下不稳定,而单官能羧酸基团可以长时间抵抗水的置换。另一方面,琥珀酸酐吸附后的双层电容低,这与吸附时的零电荷(PZC)的电位变化有关。

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