Adsorption properties of polyethyleneimine modified magnetic yeast composites for uranium (VI)
-
摘要: 为了高效便捷地处理放射性废水,制备了聚乙烯亚胺(PEI)改性磁性酵母(MY)复合生物材料(MY@SiO2-PEI),并将其用于铀(VI)的去除。采用SEM、FTIR、Zeta电位及XPS对材料进行表征,运用Visual MINTEQ模拟不同条件下U(VI)形态分布,通过研究不同溶液pH、温度、反应时间、离子强度,阴离子(CO32−、PO43−)及不同U(VI)初始质量浓度等方面,考察不同因素对MY@SiO2-PEI吸附U(VI)的性能影响,并对MY@SiO2-PEI的循环利用能力进行研究。结果表明,MY@SiO2-PEI对U(VI)的吸附表现出强pH依赖性,离子强度对吸附效果无显著干扰,说明反应主要受表面络合作用控制。FTIR、XPS及Zeta电位分析发现促使U(VI)吸附的主要因素是材料表面不同官能团(N=C、NH(NH2)、C—N=C)与U(VI)的络合作用及静电吸引作用。MY@SiO2-PEI最大吸附量可达173.99 mg/g,且吸附在20 min就可达到吸附平衡。准二级动力学和Langmuir等温方程能很好的拟合此吸附过程,且热力学表明吸附过程是自发吸热过程。MY@SiO2-PEI材料的合成方法简便,去除效果好,再生性佳,是一种很有前途的环境污染治理中放射性核素的吸附剂。Abstract: In order to efficiently and conveniently treat radioactive wastewater, polyethyleneimine (PEI) modified magnetic yeast(MY) composite biological material(MY@SiO2-PEI) was prepared and used for the removal of uranium (VI).The material was characterized by SEM, FTIR, Zeta potential and XPS, the U(VI) morphology distribution under different conditions was simulated by Visual MINTEQ, the different solution pH, temperature, reaction time, ionic strength, anion interference(CO32−, PO43−) and different U(VI) in terms of initial mass solubility were analyzed. In addition, the influence of different factors on the adsorption performance of MY@SiO2-PEI on U(VI) was investigated, and the recycling capacity of MY@SiO2-PEI was studied. The results show that the adsorption of U(VI) by MY@SiO2-PEI shows a strong pH dependence, and the ionic strength does not significantly interfere with the adsorption effect, indicating that the reaction is mainly controlled by surface complexation. FTIR, XPS and Zeta potential analysis found that the main factor that promotes the adsorption of U(VI) is the complexation and electrostatic attraction of different functional groups (N=C, NH(NH2), C—N=C) and U(VI) on the surface of the material. The maximum adsorption capacity of MY@SiO2-PEI can reach 173.99 mg/g, and the adsorption equilibrium can be reached within 20 minutes. Quasi-second-order kinetics and Langmuir isotherm equation can fit this adsorption process well, and thermodynamics show that the adsorption process is a spontaneous endothermic process. MY@SiO2-PEI material has simple synthesis method, good removal effect and good reproducibility. It is a promising adsorbent for radionuclides in environmental pollution control.
-
Key words:
- polyethyleneimine (PEI) /
- modification /
- compositematerial /
- adsorption /
- uranium /
- water treatment /
- biological material
-
图 4 (a) U(VI)形态分布随pH的变化图: C0(U)=10 mg/L,T=303 K,PCO2=103.58 atm (1 atm=1.0×105 Pa) ;(b) 不同pH值下MY@SiO2-PEI的Zeta电位变化图
Figure 4. (a) U(VI) speciation distribution as a function of pH in equilibrium with air (PCO2=103.58 atm (1 atm=1.0×105 Pa)): (b) C0(U)=10 mg/L, T=303 K; Zeta potential of MY@SiO2-PEI in solution
图 6 (a) Na2CO3和Na3PO4·12H2O对U(VI)去除效果的影响;(b) U(VI)形态分布随pH的变化曲线 (10 mg/L Na3PO4·12H2O,C0(U)=10 mg/L,T=303 K,PCO2=103.58atm (1 atm=1.0×105 Pa))
Figure 6. (a) Influence of Na2CO3 and Na3PO4·12H2O on U(VI) removal effect;(b) U(VI) species distribution as a function of pH in equilibrium with air (PCO2=103.58 atm (1 atm=1.0×105 Pa),10 mg/L Na3PO4·12H2O,C0(U)=10 mg/L,T=303 K)
表 1 MY@SiO2-PEI对U(VI)的吸附动力学拟合参数
Table 1. Kinetic parameters of U(VI) adsorption on MY@SiO2-PEI
ρ0 qe,exp Pseudo-first order Pseudo-second-order Intra-particle diffusion $\mathit{ln}\left({q}_{{\rm{e}}}-{q}_{{\rm{t}}}\right)=ln{q}_{{\rm{e}}}-{k}_{1}t$ $\dfrac{t}{ {q}_{t} }=\dfrac{1}{\left({k}_{2}\cdot {q}_{{\rm{e}}}^{2}\right)}+\dfrac{t}{ {q}_{{\rm{e}}} }$ ${q}_{t}={k}_{ {{\rm{d}}}_{{\rm{i}}}{\rm{f}}}·{e}^{0.5}+C$ k1 qe,cal R2 k2 qe,cal R2 C Kdif R2 5 23.491 0.361 23.249 0.959 0.042 23.629 0.999 21.493 0.181 0.564 10 44.868 0.032 44.996 0.923 0.022 45.065 0.999 43.658 0.102 0.604 15 62.289 0.129 62.478 0.785 0.016 62.461 1.000 62.018 0.025 0.782 Notes: C0—Initial Cd(Ⅱ) ions concentration; qe.exp—Calculated amount of adsorption equilibrium; qe·cal—Actual amount of adsorption equilibrium; k1, k2 —First order rate constant and second order rate constant,respectively; Kdif —Particle diffusion constant. 表 2 MY@SiO2-PEI对U(VI)的吸附等温吸附模型拟合参数
Table 2. Simulation of isotherm models and corresponding parameters of U(VI) adsorption on MY@SiO2-PEI
T/K Langmuir ${q}_{{\rm{e}}}=\dfrac{b{Q}_{\mathrm{m}\mathrm{a}\mathrm{x} }{C}_{{\rm{e}}} }{1+{b}{C}_{{\rm{e}}} }$ Freundlich ${q_{\rm{e} } } = {K_{\rm{F}}}C_{\rm{e} }^{1/n}$ Qmax/(mg·g−1) b/(L·mg−1) R2 KF /(mg1-n·Ln·g−1) n R2 283 103.541±0.820 0.287±0.01 0.999 31.336±3.619 2.761±0.362 0.932 293 157.941±3.500 0.206±0.11 0.997 32.279±4.192 2.149±0.252 0.944 303 173.990±7.094 0.311±0.03 0.991 47.095±3.813 2.189±0.202 0.965 Notes: Qmax—Adsorption capacity per unit mass of the adsorbent; b—Langmuir coefficient related to the affinity of binding site; KF, n—Constants that are related to the adsorption capacity and the adsorption intensity, respectively. 表 3 MY@SiO2-PEI吸附U(VI)的热力学参数
Table 3. Thermodynamic parameterofU(VI) adsorption onMY@SiO2-PEI
ΔG0/(kJ·mol−1) ΔH0/(kJ·mol−1) ΔS0/(J·mol−1·K−1) 283 K 303 K 308 K −3.034 −3.264 −3.586 4.761 27.494 Notes: ΔG0—Standard free energy change; ΔH0—Standard enthalpy change; ΔS0—Standard entropy change. -
[1] LI L, LIAO Q, CAO C, et al. 4-sulfonylcalix[6] Arene modified Fe3O4@aspergillus niger biosorbents for effective removal of uranium(VI) from aqueous solutions[J]. Journal for Nanoscience and Nanotechnology,2019,19(11):6978-6986. doi: 10.1166/jnn.2019.16602 [2] CHEIRA M F, ATIA B M, KOURAIM M N. Uranium(VI) recovery from acidic leach liquor by ambersep 920U SO4 resin: Kinetic, equilibrium and thermodynamic studies[J]. Journal of Radiation Research and Applied Sciences,2019,10(4):307-319. [3] ZHU Z, PRANOLO Y, CHENG C Y. Uranium recovery from strong acidic solutions by solvent extraction with cyanex 923 and a modifier[J]. Minerals Engineering,2016,89:77-83. doi: 10.1016/j.mineng.2016.01.016 [4] AYDIN F A, SOYLAK M. A novel multi-element coprecipitation technique for separation and enrichment of metal ions in environmental samples[J]. Talanta,2007,73(1):134-141. doi: 10.1016/j.talanta.2007.03.007 [5] REN X, WANG S, YANG S, et al. Influence of contact time, pH, soil humic/fulvic acids, ionic strength and temperature on sorption of U(VI) onto mx-80 bentonite[J]. Journal of Radioanalytical and Nuclear Chemistry,2009,283(1):253-259. [6] KONG L, RUAN Y, ZHENG Q, et al. Uranium extraction using hydroxyapatite recovered from phosphorus containing wastewater[J]. J Hazard Mater,2020,382:120784. [7] GISI S D, LOFRANO G, GRASSI M, et al. Characteristics and adsorption capacities of low-cost sorbents for wastewater treatment: A review[J]. Sustainable Materials & Technologies,2016,9:10-40. [8] DENG S, TING Y-P. Characterization of pei-modified biomass and biosorption of Cu(II), Pb(II) and Ni(II)[J]. Water Research,2005,39(10):2167-2177. doi: 10.1016/j.watres.2005.03.033 [9] XIA Y, YAO Q, ZHANG W, et al. Comparative adsorption of methylene blue by magnetic baker's yeast and edtad-modified magnetic baker's yeast: Equilibrium and kinetic study[J]. Arabian Journal of Chemistry,2019,12(8):2448-2456. doi: 10.1016/j.arabjc.2015.03.010 [10] ZHANG Y, ZHU J, ZHANG L, et al. Synthesis of edtad-modified magnetic baker's yeast biomass for Pb2+ and Cd2+adsorption[J]. Desalination,2011,278(1-3):42-49. doi: 10.1016/j.desal.2011.05.003 [11] SUN Y, SHAO D, CHEN C, et al. Highly efficient enrichment of radionuclides on graphene oxide-supported polyaniline[J]. Environmental Science & Technology,2013,47(17):9904-9910. doi: 10.1021/es401174n [12] PANG Y, ZENG G, TANG L, et al. Pei-grafted magnetic porous powder for highly effective adsorption of heavy metal ions[J]. Desalination,2011,281:278-284. doi: 10.1016/j.desal.2011.08.001 [13] WANG J, ZHENG S, SHAO Y, et al. Amino-functionalized Fe3O4@SiO2 core–shell magnetic nanomaterial as a novel adsorbent for aqueous heavy metals removal[J]. Journal of Colloid & Interface Science,2010,349(1):293-299. [14] ZHOU Y, PING T, MAITLO I, et al. Regional selective construction of nano-au on Fe3O4@SiO2@PEI nanoparticles by photoreduction[J]. Nanotechnology,2016,27(21):215301. doi: 10.1088/0957-4484/27/21/215301 [15] OU H X, SONG Y J, LI L R, et al. Adsorption of Pb(II) by silica/yeast composites from aqueous solution: Kinetic and equilibrium studies[J]. Advanced Materials Research,2012,496:476-479. doi: 10.4028/www.scientific.net/AMR.496.476 [16] XIE C, WEI S, CHEN D, et al. Preparation of magnetic ion imprinted polymer with waste beer yeast as functional monomer for Cd(II) adsorption and detection[J]. RSC Advances,2019,9(41):23474-23483. doi: 10.1039/C9RA03859K [17] 曹春, 巨天珍, 陈兴鹏. CMC/P(AMPS-co-AA)水凝胶对Pb(II)的吸附动力学及吸附机理研究[J]. 环境化学, 2013(10):1909-1916.CAO C, JU T Z, CHEN X P. Adsorption kinetics and mechanism of Pb (Ⅱ) ion by CMC/P (AMPS-co-AA) hydrogel[J]. Environmental Chemistry,2013(10):1909-1916(in Chinese). [18] 卞维柏, 黄卫红, 欧红香, 等. MY@SiO2-PEI磁性复合生物材料对二元Ce3+/Sr2+混合离子的吸附性能研究[J]. 环境科学学报, 2014, 34(7):1716-1723.BIAN W B, HUANG W H, OU H X, et al. Adsorption of mixed Ce3+/Sr2+ in binary system onto MY@ SiO2-PEI magnetic composite biomaterial[J]. Acta Scientiae Circumstantiae,2014,34(7):1716-1723(in Chinese). [19] CAO S, LOW J, YU J, et al. Polymeric photocatalysts based on graphitic carbon nitride[J]. Advanced Materials,2015,27(13):2150-2176. doi: 10.1002/adma.201500033 [20] CHEN Y, PAN R, RNHAIYAN L I, et al. Selective removal of Cu(II) ions by using cation-exchange resin-supported polyethyleneimine (PEI) nanoclusters[J]. Environmental Science & Technology,2010,44(9):3508. [21] ZOU Y, WANG X, AI Y, et al. Correction: β-Cyclodextrin modified graphitic carbon nitride for the removal of pollutants from aqueous solution: experimental and theoretical calculation study[J]. Journal of Materials Chemistry A,2019,7:11539-11540. [22] SCHINALER M, HAWTHORNE F C, FREUND M S, et al. XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The u 4f spectrum[J]. Geochimica et Cosmochimica Acta,2009,73(9):2471-2487. doi: 10.1016/j.gca.2008.10.042 [23] A G D, C S X, A Z L, et al. Recovery of uranium (VI) from aqueous solutions by the polyethyleneimine-functionalized reduced graphene oxide/molybdenum disulfide composition aerogels[J]. Journal of the Taiwan Institute of Chemical Engineers,2020,106:198-205. doi: 10.1016/j.jtice.2019.09.029 [24] MOREAU, JOHNW, DOUGLAS, et al. Uranium mobility in organic matter-rich sediments: A review of geological and geochemical processes[J]. Earth Science Reviews,2016,159:160-185. doi: 10.1016/j.earscirev.2016.05.010 [25] FAN Q H, HAO L M, WANG C L, et al. The adsorption behavior of U(Ⅵ) on granite[J]. Environmental Science: Processes & Impacts Impacts,2014,16(3):534-541. doi: 10.1039/c3em00324h [26] ZHANG Y Z, GAO H, FAN Q, et al. Sorption of U(VI) onto a decarbonated calcareous soil[J]. Journal of Radioanalytical & Nuclear Chemistry,2011,288(2):395-404. [27] HUANG Z, LI Z, ZHENG L, et al. Interaction mechanism of uranium(VI) with three-dimensional graphene oxide-chitosan composite: Insights from batch experiments, IR, XPS, and exafs spectroscopy[J]. Chemical Engineering Journal,2017,328:1066-1074. doi: 10.1016/j.cej.2017.07.067 [28] 段升霞. 低温等离子体改性纳米材料及其对含铀废水吸附性能研究[D]. 合肥: 中国科学技术大学, 2018.DUAN S X. Nonthermal plasma modified nanomaterials and their adsorptionon uranium containing waste water[D]. Hefei: University of Science and Technology of China, 2018(in Chinese). [29] LI J, CHENCl, ZHANGR, et al. Reductive immobilization of Re(VII) by graphene modified nanoscale zero-valent iron particles using a plasma technique[J]. Science China Chemistry,2016,59(1):150-158. doi: 10.1007/s11426-015-5452-4 [30] 毕玉玺, 凌辉, 唐振平, 等. 磁性介孔TiO2/氧化石墨烯复合材料的制备及其对U(Ⅵ)的吸附[J]. 复合材料学报, 2019, 36(09):2176-2186.BI Y X, LING H, TANG Z P, et al. Preparation of magnetic mesoporous TiO2/graphene oxide composites and their adsorption for U(Ⅵ)[J]. Acta Materiae Compositae Sinica,2019,36(09):2176-2186(in Chinese). [31] WANG P, YIN L, WANG J, et al. Superior immobilization of U(VI) and 243Am(III) on polyethyleneimine modified lamellar carbon nitride composite from water environment[J]. Chemical Engineering Journal,2017,326:863-874. doi: 10.1016/j.cej.2017.06.034