Study on preparation of two-dimensional Ti3C2Tx nanomaterials modified by sulfonic acid groups and the adsorption performance of lead(II) ion
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摘要: 对二维Ti3C2Tx材料进行了磺酸基团接枝改性(Ti3C2Tx—SO3H),表征了改性前后微观结构的变化,研究了对重金属Pb2+的吸附行为与机制。XRD、FTIR及EDS表明磺酸基团在Ti3C2Tx表面成功接枝,而SEM则发现Ti3C2Tx−SO3H呈现较Ti3C2Tx更轻薄的层状结构。改性后,Ti3C2Tx—SO3H对重金属Pb2+20 min内达到吸附平衡,最大吸附量达到733.6 mg·g−1,较Ti3C2Tx吸附量提升了23%,且吸附量随着pH(2~6)的增加而逐渐增大,在Mg2+、Ca2+、Co2+、Zn2+等共存离子的干扰下,仍保持较高的吸附水平。机制分析表明,改性前后吸附过程均符合准二级动力学模型和Langmuir吸附等温线拟合模型,以单分子层化学吸附为主,但由于磺酸基团提供了更多的吸附饱和活性位点,并提高了Ti3C2Tx在水溶液中的分散性,使改性后对Pb2+吸附性能更优异。
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关键词:
- Ti3C2Tx /
- Ti3C2Tx—SO3H /
- 接枝改性 /
- Pb2+ /
- 吸附
Abstract: The two-dimensional Ti3C2Tx was modified by sulfonic acid group grafting (abbreviated as Ti3C2Tx—SO3H), and its microstructure before and after the modification was characterized. The adsorption behavior and mechanism of heavy metal Pb2+ by the Ti3C2Tx—SO3H were also investigated. XRD, FTIR and EDS analyses indicate that sulfonic acid group is successfully grafted on the surface of the Ti3C2Tx, while SEM shows that the Ti3C2Tx—SO3H has a lighter and thinner layered structure than the Ti3C2Tx. Pb2+ adsorption by the Ti3C2Tx—SO3H reaches equilibrium within 20 minutes. The maximum adsorption capacity of the Ti3C2Tx—SO3H is 733.6 mg·g−1, which is 23% higher than the Ti3C2Tx. And Pb2+ adsorption capacity by the Ti3C2Tx—SO3H gradually increases with the increase of pH (2-6). Under the interference of coexisting ions such as Mg2+, Ca2+, Co2+ and Zn2+, the Ti3C2Tx-SO3H still maintains a high level of Pb2+ adsorption. Pb2+ adsorption processes by both the Ti3C2Tx and the Ti3C2Tx—SO3H fit well the pseudo second kinetic model and Langmuir isotherm model, suggesting that the adsorption processes are monolayer chemisorption. The Ti3C2Tx—SO3H shows more excellent adsorption performance towards Pb2+ after adsorption mainly due to the more active sites provided by sulfonic acid group and the enhanced dispersion in aqueous solution.-
Key words:
- Ti3C2Tx /
- Ti3C2Tx—SO3H /
- graft modification /
- Pb2+ /
- adsorption
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图 11 Ti3C2Tx ((a1), (a2), (a3)) 和Ti3C2Tx—SO3H ((b1), (b2), (b3))吸附Pb2+的动力学模型拟合曲线((a1,b1) 准一级吸附动力学模型;(a2,b2) 准二级吸附动力学模型;(a3, b3) 颗粒内扩散模型)
Figure 11. Kinetic equation fitting curves of Pb2+ adsorbed by Ti3C2Tx ((a1), (a2), (a3)) and Ti3C2Tx—SO3H ((b1), (b2), (b3)) ((a1, b1) Pseudo-first-order adsorption kinetic model; (a2, b2) Pseudo-second-order adsorption kinetic model; (a3, b3) Intra-particle diffusion model)
表 1 不同吸附剂对Pb2+的吸附量对比表
Table 1. Comparison table of Pb2+ adsorption capacity of different adsorbents
Adsorbents qmax/(mg·g−1) pH T/℃ Ref. Amino-modified attapulgite 49.0 6.0 25 [26] CNFs/GO/Fe3O4 composite materials 126.5 6.0 25 [27] Saponified muskmelon peel 167.9 4-6.4 25 [28] Seaweed laminaria japonica 279.5 3-4.8 25 [29] Silanized red mud 361.0 6 25 [30] GO-LDH composite materials 387.7 5.2 25 [31] GO 757.6 3.0 25 [32] Ti3C2Tx 38.5 6.0 40 [16] Ti3C2Tx 594.3 6.0 25 This work Ti3C2Tx—SO3H 733.6 5.9 25 This work Notes: qmax—maximum adsorption capacity; CNFs—Cellulose nanofibrills; GO—Graphene oxide; GO-LDH—Graphene oxide-double layer magnesium & aluminum hydroxide. 表 2 25℃下二维Ti3C2Tx和Ti3C2Tx—SO3H吸附Pb2+的吸附等温式参数表
Table 2. Ti3C2Tx and Ti3C2Tx—SO3H adsorption isotherm parameters of Pb2+ at 25℃
Sample Dosage/g Langmuir Freundlich qm/(mg·g−1) KL/(L·mg−1) R2 n kF/(mg1-(1/n) ·L1/n·g−1) R2 Ti3C2Tx 0.02 793.65 0.0001 0.9604 0.0039 1.2616 0.9817 0.04 300.48 0.0229 0.9338 0.0001 1.0442 0.9694 Ti3C2Tx—SO3H 0.005 199.01 0.0073 0.9366 − − − 0.01 811.10 0.0003 0.9309 − − − Notes: qm—Maximum saturation adsorption capacity; R—Correlation coefficient; KL—Langmuir adsorption equilibrium constant; KF, n—Freundlich adsorption equilibrium constant, denotes adsorption capacity and density in adsorption, respectively. -
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