Kandare Everson, Hossenlopp Jeanne M
Marquette University, Department of Chemistry, P.O. Box 1881, Milwaukee, Wisconsin 53201, USA.
J Phys Chem B. 2005 May 5;109(17):8469-75. doi: 10.1021/jp0465433.
(1)H NMR spectroscopy and powder X-ray diffraction have been used to explore the details of anion exchange reactions of two layered hydroxy double salts (HDSs), zinc copper hydroxy acetate (ZCA), nickel zinc hydroxy acetate (NZA), and a related layered material, zinc hydroxy acetate (ZHA), at room temperature (21-22 degrees C). Reactions that followed Avrami-Erofe'ev kinetics with respect to temporal profiles for acetate release, ZCA with butyrate (k = 1.7 x 10(-3) s(-1)), and octanoate (k = 0.79 x 10(-3) s(-1)) anions, as well as ZHA with octanoate (k = 2.6 x 10(-3) s(-1)), demonstrate that rate constants for acetate release are influenced by the exchange anion relative size as well as by the solid precursor structure/composition. The reaction of NZA with octanoate deviated from expected Avrami-Erofe'ev behavior, with evidence for an intermediate species in the solid phase that may influence the rate of acetate release into solution. The reaction of ZCA with formate anions exhibited a unique zeroth-order kinetics release of acetate, providing the possibility of developing tunable nanostructured anion release sources by use of variations in the size of the exchange species.
（1）利用核磁共振氢谱（¹H NMR）和粉末X射线衍射技术，在室温（21 - 22摄氏度）下探究了两种层状羟基双盐（HDSs），即羟基乙酸锌铜（ZCA）、羟基乙酸镍锌（NZA）以及一种相关层状材料羟基乙酸锌（ZHA）的阴离子交换反应细节。对于乙酸根释放的时间曲线，ZCA与丁酸根（k = 1.7×10⁻³ s⁻¹）和辛酸根（k = 0.79×10⁻³ s⁻¹）阴离子的反应，以及ZHA与辛酸根（k = 2.6×10⁻³ s⁻¹）的反应，均遵循阿弗拉米 - 埃罗菲耶夫动力学，这表明乙酸根释放的速率常数受交换阴离子的相对大小以及固体前驱体结构/组成的影响。NZA与辛酸根的反应偏离了预期的阿弗拉米 - 埃罗菲耶夫行为，有证据表明在固相中存在一种中间物种，它可能会影响乙酸根释放到溶液中的速率。ZCA与甲酸根阴离子的反应呈现出独特的零级动力学乙酸根释放，这为通过改变交换物种的大小来开发可调节的纳米结构阴离子释放源提供了可能性。
