Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan.
J Colloid Interface Sci. 2013 Oct 1;407:22-8. doi: 10.1016/j.jcis.2013.05.058. Epub 2013 Jun 20.
In an attempt to estimate the zeta potential of various metal oxide nanoparticles (NPs) dispersed in water, it is interesting to observe that both the magnitude and the sign of this property depend highly upon their concentration. For example, in the case of naked TiO2 at pH 6, the zeta potential increased from -6.7 to 8.2 mV as the particle concentration varied from 0.5 to 5 mg L(-1). As a result, the isoelectric points of naked TiO2, Fe3O4, Fe(OH)3, and Al2O3-coated TiO2 could deviate ca. one, one, two, and three pH units, respectively, depending upon the particle concentration. We showed that these behaviors arise mainly from that the dissolved ambient CO2 reacts with the particle surface functional groups to form M-OCO2(-), which neutralizes or even overcompensates the particle surface charge. The surface density of M-OCO2(-), M-OCO2(-) depends upon the particle concentration; if it is sufficiently high, M-OCO2(-) becomes negligible, so is its influence on the zeta potential. We concluded that the zeta potential measurements for the tested NPs are reliable only if their concentration exceeds a certain level. This also applies to other metal oxides or hydroxides, the surface of which reacts appreciably with dissolved CO2. The results gathered are of practical significance in estimating the surface properties of unknown and/or newly synthesized NPs since conventional measurements are usually made at dilute particle concentrations.
为了估计分散在水中的各种金属氧化物纳米粒子(NPs)的 ζ 电位,有趣的是观察到该性质的大小和符号高度依赖于它们的浓度。例如,在 pH 6 时的裸露 TiO2 的情况下,随着粒子浓度从 0.5 到 5 mg L(-1)的变化,ζ 电位从-6.7 增加到 8.2 mV。结果,裸露 TiO2、Fe3O4、Fe(OH)3 和 Al2O3 涂覆的 TiO2 的等电点可以分别偏离约 1、1、2 和 3 个 pH 单位,这取决于粒子浓度。我们表明,这些行为主要源于溶解的环境 CO2 与粒子表面官能团反应形成 M-OCO2(-),这中和了甚至过补偿了粒子表面电荷。M-OCO2(-)的表面密度,M-OCO2(-)取决于粒子浓度;如果它足够高,则M-OCO2(-)变得可以忽略不计,因此它对 ζ 电位的影响也可以忽略不计。我们得出结论,只有当测试的 NPs 浓度超过一定水平时,ζ 电位测量才是可靠的。这也适用于其他金属氧化物或氢氧化物,其表面与溶解的 CO2 发生明显反应。由于常规测量通常在稀释的粒子浓度下进行,因此所收集的结果对于估计未知和/或新合成的 NPs 的表面性质具有实际意义。