Preparation of heteroatoms doped carboxylic acid functionalization carbon materials for efficient sorption of U(VI)
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摘要: 该文通过煅烧前驱体聚磷腈，制备了掺杂N，P和O的羧基官能化碳材料（CS-COOH）。利用TEM，SEM，XPS和FTIR技术确定了CS-COOH的结构。此外该文还研究了CS-COOH从水溶液中吸附U（VI）的情况，结果表明，吸附动力学符合准二级动力学模型，通过Langmuir模型计算得到在298 K下材料的最大吸附量为402.9 mg/g。且CS-COOH在五次吸附-解吸循环后表现出良好的吸附结果。根据XPS分析，材料较好的U（VI）吸附能力主要归因于羧基及杂原子与铀酰离子之间的强共价键结合。Abstract: In this work, carboxyl-functionalized carbonaceous material doped with N, P and O (denoted as CS-COOH) was fabricated by calcining a precursor, polyphosphazene, for adsorption applications. Employing TEM, SEM, XPS and FTIR techniques, the structure of CS-COOH was determined. The CS-COOH was also investigated for the adsorption of U(VI) from an aqueous solution. The results show that the adsorption kinetics was fitted well by the pseudo-second-order model and the maximum adsorption capacity determined by the Langmuir model at 298 K was 402.9 mg/g. In addition, the CS-COOH exhibited good adsorption results after five adsorption-desorption cycles. According to the XPS analysis, the enhanced U(VI) adsorption capacity was mainly attributed to the carboxyl groups and strong covalent bonds between heteroatoms with uranyl ions.
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Key words:
- Polyphosphazene /
- carboxyl /
- uranium /
- adsorption /
- heteroatoms
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Figure 4. (a) FTIR spectra of CS and CS-COOH; (b) high resolution XPS spectrum of CS-COOH.
Figure 5. (a) Effect of initial solution pH on the adsorption of U(VI) by CS and CS-COOH. (T = 298 K, m = 5 mg, C0 = 50 mg/L and V = 30 mL); (b) distribution of U(VI) species in aqueous solution with a total concentration of 50 mg/L and pH values ranging from 1 to 12 (calculated by using a Medusa program).
Figure 6. (a) Effect of (a) contact time (C0 = 50 mg/L) (b) initial concentration on the adsorption of U(VI) by CS and CS-COOH. (T = 298 K, m = 5 mg, V = 30 mL and pH = 6)
Figure 7. (a) Pseudo–first–order and (b) pseudo–second–order adsorption kinetics of U(VI) by CS and CS-COOH.
Figure 8. (a) Langmuir and (b) Freundlich isotherms of U(VI) adsorbed by CS and CS-COOH.
Figure 9. (a) Effect of temperature on the adsorption of U(VI) (m = 5 mg, V = 30 mL, C0 = 50 mg/L, t=180 min and pH = 6); (b) thermodynamics of U(VI) adsorption by CS and CS-COOH.
Figure 10. (a) Selective adsorption capacity of coexistent ions (C0 = 0.5 mmol/L); (b) Adsorption performance of U(VI) by CS-COOH over five cycles (C0 = 50 mg/L). (m = 5 mg, V = 30 mL, T = 298 K and pH = 6).
Figure 11. XPS survey spectra of (a) CS-COOH-U; (b) C1s; (c) O1s; (d) N1s; (e) P2p and (f) S2p.
Table 1. Kinetic parameters for adsorption of U(VI) by CS and CS-COOH.
Materials qe,exp (mg/g) Pseudo-first-order model Pseudo-second-order model q1,cal (mg/g) k1 (/min) R2 q2,cal (mg/g) k2 (g/mg·min) R2 CS 150.34 98.69 8.21×10−3 0.905 173.31 2.88×10−4 0.9764 CS-COOH 238.20 190.49 3.34×10−2 0.939 250.43 1.85×10−4 0.9957 
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Table 2. Parameters of Langmuir and Freundlich isotherms for adsorption of U(VI) by CS and CS-COOH.
Materials Langmuir isotherm Freundlich isotherm KL qm (mg·g−1) R2 KF n R2 CS 7.80 229.36 0.9976 4.05×10−3 0.31 0.9423 CS-COOH 0.018 402.90 0.9227 12.66 1.40 0.9033
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Table 3. The thermodynamic parameters for U(VI) adsorbed by CS and CS-COOH.
Materials ΔH (kJ·mol−1) ΔS (J·mol−1·
K−1)ΔG (kJ·mol−1) 288
(K)298
(K)303
(K)313
(K)318
(K)CS 49.82 216.16 −12.41 −14.57 −15.65 −17.81 −18.89 CS−COOH 7.73 91.89 −18.74 −19.66 −20.12 −21.04 −21.50
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