Adsorption Behavior and Mechanism of DEAE-Modified PGMA Macro Porous Spheres Towards Pt(Ⅳ) AITranslate

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY23110029

Chinese Library Classification Number:TF84

Citation Information:

Platinum is a kind of precious metal that is highly valued due to its rarity，difficult extraction，and diverse applications. The recovery of Pt(Ⅳ) from the leachate remains challenging due to its low concentrations and the presence of different impurity metals at high concentrations. Therefore，developing efficient technologies for recovering of Pt(Ⅳ) from low-concentration and complex systems is of utmost importance. The recovery of Pt(Ⅳ) from aqueous solutions has been accomplished through various separation technologies，whereas adsorption is gaining prominence due to its high efficiency，eco-friendliness，and applicability to solutions with low concentration of Pt(Ⅳ). Therefore，this study used diethylaminoethyl (DEAE) functionalized macro porous poly(glycidyl methacrylate) (PGMA) macro porous spheres (PGMA-DEAE) as adsorbents to selectively recover Pt(Ⅳ) from simulated wastewater and systematically studied its adsorption performance and mechanism. The average particle size of PGMA-DEAE was about 34 μm. Scanning electron microscope (SEM) images showed their porous microsphere with a rough surface and good dispersibility. The results of the fully automatic nitrogen adsorption method and mercury intrusion method indicated that PGMA-DEAE has a rich macro porous structure with almost no micro porous structure. These macro porous structures could effectively improve the diffusion rate of metal ions in the adsorbent pores，increase the surface area of the adsorbent，and effectively enhance the adsorption capacity and rate of PGMA-DEAE for Pt(Ⅳ). The effect of pH，contact time，and initial concentrations of Pt(Ⅳ) was investigated. The pH of the solution had a significant impact on the adsorption performance of Pt(Ⅳ) on PGMA-DEAE within the experimental acidity range (C_HCl=2 mol·L⁻¹~pH=6). When C_HCl≥1 mol·L⁻¹，the concentration of H⁺ in the solution was very high，and the amino groups on PGMA-DEAE tended to bind with H⁺，making it difficult to coordinate with Pt(Ⅳ). At this time，the adsorption efficiency of Pt(Ⅳ) was low. Therefore，at high acidity (C_HCl≥1 mol·L⁻¹)，especially with the appropriate addition of Pt(Ⅳ) complexing agents (such as thiourea)，it was suitable for Pt(Ⅳ) to desorb from PGMA-DEAE. Within the pH range of 1~6，Pt(Ⅳ) existed as negatively charged complex anions (PtCl_x(OH)_6-x²⁻) in the solution. Therefore，at pH<4.81，on the one hand，at lower pH values，Pt(Ⅳ) in the solution was prone to exist as negatively charged complex anions in the solution，which could be adsorbed in the form of ion association with positively charged PGMA-DEAE. On the other hand，the concentration of H⁺ in the solution significantly decreased，and the coordination ability between the amino group and H⁺on PGMA-DEAE decreased，while the coordination ability with Pt(Ⅳ) rapidly increased. Pt(Ⅳ) quickly replaced the H⁺ bound to the amino group and was adsorbed by PGMA-DEAE. Therefore，in the pH range of 1~4，the adsorption rate of Pt(Ⅳ) increased with the increasing solution pH. However，after pH>4.81，with the deprotonating of ammonium ions，the surface electro positivity of PGMA-DEAE decreased continuously，and the electrostatic attraction to the negatively charged PtCl_x(OH)_6-x²⁻ decreased continuously，resulting in a slow decrease in the adsorption efficiency of Pt(Ⅳ). Therefore，at pH=4，the adsorption efficiency of Pt(Ⅳ) reached its maximum value. The adsorption of Pt(Ⅳ) by PGMA-DEAE could be described by the pseudo second order kinetic adsorption model very well，and the adsorption speed of Pt(Ⅳ) was very fast，which could reach equilibrium within 5 min. The adsorption isotherm indicated that the adsorption of Pt(Ⅳ) on PGMA-DEAE could be explained by Langmuir isotherm model very well，and the maximum adsorption capacity of Pt(Ⅳ) on PGMA-DEAE was 0.73 mmol·g⁻¹ at pH=4 and 25 ℃. After 12 cycles of adsorption desorption activation regeneration，there was no significant decrease in both adsorption and desorption rates，indicating that the PGMA-DEAE adsorbent had good stability and recyclability. PGMA-DEAE also had excellent selectivity for Pt(Ⅳ) over some base metals. At pH=1~4，PGMA-DEAE showed a high relative separation coefficient，the selectivity separation coefficients of Pt(Ⅳ) from Fe(Ⅱ)，Co(Ⅱ)，Ni(Ⅱ)，Cu(Ⅱ)，Al(Ⅲ)，and Cr(Ⅲ) were all more than 100，and the selectivity for Pt(Ⅳ) was significantly enhanced upon the addition of EDTA，broadening the pH range to 2~6 for their selective recovery. These results proved that PGMA-DEAE had excellent adsorption performance for Pt(Ⅳ) in simulated waste liquid. Based on characterization analysis such as XRD，FTIR，XPS，Zeta potential，and pH titration，it could be inferred that，on the one hand，at pH< 4.81，Pt(Ⅳ) existed in the solution as a complex anion，and the tertiary amine on PGMA-DEAE formed positively charged ammonium ions through protonation. Pt(Ⅳ) can be adsorbed in the form of ion association through electrostatic attraction at lower pH values. On the other hand，in the pH range of 1-6，the concentration of H⁺ in the solution was low，and protons in ammonium ions were easily replaced by other elements. Pt(Ⅳ) with empty orbitals coordinated with lone pair electrons on the tertiary amine N element and was adsorbed in a complex form. The adsorption mechanism of complex coordination was more conducive to the adsorption of Pt(Ⅳ).