He Feng, Zhao Dongye
Environmental Engineering Program, Department of Civil Engineering, 238 Harbert Engineering Center, Auburn University, Auburn, Alabama 36849, USA.
Environ Sci Technol. 2007 Sep 1;41(17):6216-21. doi: 10.1021/es0705543.
Zerovalent iron (ZVI) nanoparticles of various sizes were synthesized by applying various types of carboxymethyl cellulose (CMC) as a stabilizer. At an initial Fe2+ concentration of 0.1 g/L and with 0.2% (w/w) of CMC (Mr = 90 000), nanoparticles with a hydrodynamic diameter of 18.6 nm were obtained. Smaller nanoparticles were obtained as the CMC/Fe2+ molar ratio was increased. When the initial Fe2+ concentration was increased to 1 g/L, only 1/4 of the CMC was needed to obtain similar nanoparticles. On an equal weight basis, CMC with a greater Mr or higher D.S. (degree of substitution) gave smaller nanoparticles, and lower the synthesizing temperature favored the formation of smaller nanoparticles. It is proposed that CMC stabilizes the nanoparticles through the accelerating nucleation of Fe atoms during the formation of ZVI nanoparticles and, subsequently, forms a bulky and negatively charged layer via sorption of CMC molecules on the ZVI nanoparticles, thereby preventing the nanoparticles from agglomeration through electrosteric stabilization. In agreement with the classical coagulation theory, the presence of high concentrations of cations (Na+ and Ca2+) promoted agglomeration of the nanoparticles. The strategy for manipulating the size of the ZVI nanoparticles may facilitate more effective applications of ZVI nanoparticles for in situ dechlorination in soils and groundwater.
通过使用各种类型的羧甲基纤维素(CMC)作为稳定剂,合成了各种尺寸的零价铁(ZVI)纳米颗粒。在初始Fe2+浓度为0.1 g/L且使用0.2%(w/w)的CMC(Mr = 90 000)时,获得了流体动力学直径为18.6 nm的纳米颗粒。随着CMC/Fe2+摩尔比的增加,获得了更小的纳米颗粒。当初始Fe2+浓度增加到1 g/L时,仅需要1/4的CMC就能获得类似的纳米颗粒。在等重量基础上,具有更大Mr或更高取代度(D.S.)的CMC产生更小的纳米颗粒,并且降低合成温度有利于形成更小的纳米颗粒。有人提出,CMC在ZVI纳米颗粒形成过程中通过加速Fe原子的成核来稳定纳米颗粒,随后通过CMC分子在ZVI纳米颗粒上的吸附形成一个庞大的带负电荷层,从而通过静电位稳定作用防止纳米颗粒团聚。与经典的凝聚理论一致,高浓度阳离子(Na+和Ca2+)的存在促进了纳米颗粒的团聚。控制ZVI纳米颗粒尺寸的策略可能有助于ZVI纳米颗粒在土壤和地下水中原位脱氯的更有效应用。