Preparation, characterization, adsorption performance and mechanism of Fe3O4@PANI-PG boron adsorbent
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摘要: 基于磁性分离原理,设计并制备了一种磁性多元醇硼吸附剂,有效解决了传统吸附剂与水相分离困难问题。首先,以苯胺为单体,采用原位聚合反应在自制的磁性Fe3O4纳米颗粒表面包裹了一层聚苯胺(PANI),然后通过缩水甘油与聚苯胺末端活性胺基开环反应,制备了一种核壳结构的多元醇硼吸附剂:丙二醇改性聚苯胺复合四氧化三铁(Fe3O4@PANI-PG);采用SEM、TEM、EDS、XRD、XPS和FTIR等表征方法对材料的微观形貌、结构、组成及官能团进行了表征。其次,通过单因素实验考察了吸附时间、硼酸初始浓度、pH等因素对其硼吸附性能的影响,在此基础上采用响应面法优化得到了吸附最佳条件:时间t=10 h,初始浓度C0=1309 mg/L,pH=9.93和相应最佳吸附量Qe=0.1181 mmol/g。此外,通过吸附动力学及吸附等温式拟合,研究发现该吸附剂对硼吸附过程符合准二级吸附动力学和Langmuir等温吸附模型。最后对其吸附机制进行探究,研究发现:该吸附剂末端邻位羟基与水相中的B(OH)4−发生络合反应形成了稳定的五元环螯合物。Abstract: In this paper, the traditional difficult problem of separation between adsorbent and water phase was effectively solved by a kind of magnetic polyols boron adsorbent, which were designed and prepared based on the principle of magnetic separation. Firstly, the polyaniline compound Fe3O4 (Fe3O4@PANI) composites with core-shell structure were prepared by the in-situ polymerization reaction at the presence of aniline and Fe3O4 nanoparticles, which were prepared by ourselves. Then propylene glycol modified polyaniline compound Fe3O4 (Fe3O4@PANI-PG) boron adsorbent was successfully prepared by the ring-opening reaction between polyaniline terminal active —NH2 and glycidyl. After that, the micro-structure, composition and functional groups were analyzed by the SEM, TEM, EDS, XRD, XPS and FTIR, respectively. The adsorption time, initial concentration of boric acid, pH and other factors of Fe3O4@PANI-PG were investigated by the single factor experiment. On this basis, the optimal adsorption conditions (time t=10 h, initial concentration C0=1309 mg/L, pH=9.93) were obtained by response surface method, and the corresponding optimal adsorption capacity up to Qe=0.1181 mmol/g. In addition, it was found that the adsorption process was in accordance with the quasi-second-order adsorption kinetics and Langmuir adsorption isotherm based on the adsorption kinetics and adsorption isotherm fitting. Finally, the adsorption mechanism of Fe3O4@PANI-PG was explored and the results indicating the complex reaction between the hydroxyl group at the end of the adsorbent and B(OH)4− in the aqueous phase formed a stable five-membered ring chelate.
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Key words:
- magnetic nanoparticles /
- boron adsorbent /
- core-shell structure /
- response surface method /
- polyaniline /
- glycidol
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图 11 各因素交互作用:(a) t和C0 (pH=9); (b) t和C0 (pH=10); (c) t和C0 (pH=11); (d) pH和t (C0=1200 mg); (e) pH和t (C0=1300 mg); (f) pH和t (C0=1400 mg); (g) pH和C0 (t=6 h); (h) pH和C0 (t=8 h); (i) pH和C0 (t=10 h)对Fe3O4@PANI-PG单位硼吸附量的影响
Figure 11. Interaction of all factors: (a) t and C0 (pH=9); (b) t and C0 (pH=10); (c) t and C0 (pH=11); (d) pH and t (C0=1200 mg); (e) pH and t (C0=1300 mg); (f) pH and t (C0=1400 mg); (g) pH and C0 (t=6 h); (h) pH and C0 (t=8 h); (I) Effects of pH and C0 (t=10 h) on Fe3O4@PANI-PG unit boron adsorption
表 1 Langmuir和Freundlich方程对Fe3O4@PANI-PG吸附等温线的拟合参数
Table 1. Fitting parameters of Langmuir and Freundlich equations to Fe3O4@PANI-PG adsorption isotherms
Model and parameter Langmuir Freundlich $\dfrac{{{C_{\text{e}}}}}{{{Q_{\text{e}}}}} = \dfrac{1}{{{Q_{\text{m}}}{K_{\text{L}}}}} + \dfrac{{{C_{\text{e}}}}}{{{Q_{\text{m}}}}}$ $\lg {Q_{\text{e}}} = \lg {K_{\text{F}}} + \dfrac{1}{n}\lg {C_{\text{e}}}$ KL Qm R2 KF n R2 Value 0.00118 0.1877 0.99241 0.00102 1.4952 0.98101 Notes: Qm—Maximum adsorption capacity; KL—Adsorption coefficient of Langmuir; KF—Adsorption coefficient of Freundlich; n—Adsorption intensity characteristic constant. 表 2 Fe3O4@PANI-PG吸附硼的动力学模型拟合参数
Table 2. Parameters of kinetic model fitting for Fe3O4@PANI-PG adsorbed boron
Model and parameter Pseudo-first-order kinetic model Pseudo-second-order kinetic model ${\text{ln}}({q_{\text{e}}} - q) = {\text{ln}}{q_{\text{e}}} - {k_{\text{1}}}t$ $\dfrac{t}{q} = \dfrac{1}{ { {k_{\text{2} } }{q_{\text{e} } }^2} } + \dfrac{t}{ { {q_{\text{e} } } }}$ k1 qe R2 k2 qe R2 Value 0.44211 0.1160 0.9802 1.7574 0.1577 0.9975 Notes: qe—Equilibrium adsorption capacity; k1—Pseudo-first order adsorption rate constant;k2—Pseudo-second order adsorption rate constant; R—Correlation coefficient. 表 3 各影响因素与水平
Table 3. Influencing factors and levels
Factor Symbol Level −1 0 1 t/h A 6 8 10 C0/(mg·L−1) B 1200 1300 1400 pH C 9 10 11 Response value/(mmol·g−1) Qe — — — Notes: Qe—Adsorption capacity; C0—Boric acid concentration. 表 4 Fe3O4@PANI-PG吸附硼酸条件的优化—Box-Behnken试验结果与分析
Table 4. Optimization of conditions for Fe3O4@PANI-PG to adsorb boric acid results and analysis of Box-Behnken test
Number A B C Qe 1 10 1300 9 0.11224 2 6 1400 10 0.10010 3 6 1300 11 0.09708 4 8 1300 10 0.11417 5 10 1300 11 0.11038 6 8 1300 10 0.11409 7 10 1200 10 0.11143 8 6 1300 9 0.09924 9 8 1400 9 0.10315 10 6 1200 10 0.09824 11 8 1400 11 0.10157 12 8 1200 11 0.09919 13 8 1300 10 0.11415 14 10 1400 10 0.11357 15 8 1200 9 0.10162 16 8 1300 10 0.11415 17 8 1300 10 0.11408 表 5 响应面试验结果方差分析
Table 5. Variance analysis of response surface test results
Source SS df MS F-value P-value Significance Modle 0.0008 9 0.0001 25359.34 <0.0001 Significant A-Time 0.0004 1 0.0004 103529.48 <0.0001 Significant B-Concentration 7.821×10–6 1 7.821×10–6 2309.52 <0.0001 Significant C-pH 8.060×10–6 1 8.060×10–6 2380.12 <0.0001 Significant AB 1.960×10–8 1 1.960×10–8 5.79 0.0471 Significant AC 2.250×10–8 1 2.250×10–8 6.64 <0.0366 Significant BC 1.806×10–7 1 1.806×10–7 53.34 0.0002 Significant A2 0.0000 1 0.0000 7587.11 <0.0001 Significant B2 0.0001 1 0.0001 42155.16 <0.0001 Significant C2 0.0002 1 0.0002 59587.03 <0.0001 Significant Residual 2.371×10–8 7 3.386×10–9 Lack of fit 1.723×10–8 3 5.742×10–9 3.54 0.1266 Not significant Pure error 6.480×10–9 4 1.620×10–9 Cor total 0.008 16 CV/%=5.44% R2=99.99% Adjust R2=99.98% Predicted R2=99.96% Notes: SS—Sum of squares; df—Degrees of freedom; MS—Mean square; F—Variance test amount; P—A parameter used to determine the hypothesis test result; CV—Ratio of the standard deviation to the average. -
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