Application of Mesoporous Silicas for Adsorption of Organic and Inorganic Pollutants from Rainwater
Abstract
:1. Introduction
2. Materials and Methods
2.1. The Subject of the Study
2.2. Analysis of Organic Micropollutants
2.3. Analysis of Physicochemical Parameters
2.4. Synthesis and Modification of MCF Materials
2.5. Adsorption Process
2.6. Characterization of Adsorbents
- The surface morphologies of the minerals studied were investigated by scanning electron microscopy (SEM/EDS). The scanning electron microscope used for the JSM 6360LA was manufactured by JEOL-Japan (Tokyo, Japan).
- The textures of the materials were also examined using transmission electron microscopy (TEM, Tecnai G2 apparatus operating at 200 kV).
- The structural properties of the adsorbents were determined by measuring the surface areas and pore size distributions using the low-temperature nitrogen adsorption and desorption technique, according to the Brunauer–Emmett–Teller (BET) method.
- The determination of functional groups and vibrational spectra was performed using FTIR spectroscopy.
2.7. Statistical Analysis of the Results
3. Results and Discussion
3.1. Characteristics of MCF
3.2. Characteristics of Rainwater
3.3. Efficiency of Adsorption of Micropollutants Using Silica
3.4. Effects of Process Time and Adsorbent Dose on the Efficiency of Zinc and Colour Adsorption Efficiency from Rainwater
3.5. Zinc Adsorption and Colour Isotherms and Kinetics for MCF-NH2
4. Conclusions
- The results of the analysis of rainwater by the applicable Polish Regulation on the quality of rainwater show that the permissible concentration of zinc was exceeded. In addition, various compounds such as alkanes, phenol derivatives, and benzothiazole were found.
- MCF-NH2 was found to be effective in the adsorption of zinc ions and colour.
- On the other hand, MCF-NH2/SH showed high colour removal efficiency, while in the case of zinc removal it was less effective than MCF-NH2. Studies confirm the effectiveness of modified MCF in the removal of organic micropollutants, especially phenolic compounds and benzothiazole. However, the alkanes were not adsorbed, probably due to their low polarity and weak intermolecular interactions.
- It was found that the adsorption of zinc and colour by MCF-NH2 can be consistent with the Langmuir and Freundlich isotherm models. Research suggests that functionalization of silica carriers may affect their ability to remove heavy metals. In conclusion, adsorption is affected by the mechanisms of both chemisorption and pore-filling, and functional groups on the surfaces of porous materials form stable compounds with heavy metals.
- It was found that the adsorption was carried out according to second-order kinetics—the model used can be used to determine the relevant kinetic parameters.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Parameter | Determination Method |
---|---|
pH | The multifunctional analyser CX-461 (Elmetron, Zabrze, Poland). |
Conductivity | |
TOC | TOC-L series analyser (Shimadzu, Kioto, Prefektura Kioto, Japan). |
COD | Test Method—UV–Vis Spectroquant® Prove 100 (Merck, Kenilworth, NJ, USA). (Measuring ranges: NO3—0.2–20 mgN-NO3/L, PO4—0.5–30 mgP-PO4/L), colour—0–2500 mgPt/L, COD—10–150 mgO2/L, Cu—0.02–6.0 mgCu/L, Ni—0.02–6.0 mgNi/L, Pb—0.01–5.0 mgPb/L, Zn—0.2–5.0 mgZn/L. |
Nitrate nitrogen | |
Phosphate phosphorus | |
Colour | |
Copper | |
Nickel | |
Zinc | |
Lead |
Sample | SBET [m2/g] | VpN2 [cm3/g] | dp [nm] | dw [nm] |
---|---|---|---|---|
MCF | 480 | 2.1 | 24 | 15 |
MCF-NH2 | 300 | 1.5 | 19.7 | 13.0 |
MCF-SH | 370 | 1.8 | 23.1 | 14.3 |
MCF-NH2/SH | 380 | 1.9 | 22.1 | 14.9 |
Parameter | Unit | Rainwater | Polish Regulation [47], Journal of Laws 2019, Item 1311 |
---|---|---|---|
pH | - | 6.7 | 6.5–9.0 |
Conductivity | mS/cm | 5.78 | - |
Colour | mgPt/L | 21 | - |
TOC | mgC/L | 2.64 | 30.0 |
COD | mgO2/L | 63 | 125.0 |
Hardness | mval/L | 3.2 | - |
N-NO3− | mg/L | 3.3 | 30 |
P-PO43− | mg/L | 0.0 | 1.0 |
Zn | mg/L | 4.7 | 2.0 |
Cu | mg/L | 0.00 | 0.5 |
Ni | mg/L | 0.07 | 0.5 |
Pb | mg/L | 0.00 | 0.5 |
Compounds | Rt [min] | CAS Number | Molar Mass [g/mol] |
---|---|---|---|
Neodecanoic acid | 14.977 | 26896-20-8 | 214.34 |
Benzothiazole | 15.058 | 95-16-9 | 135.19 |
2-Hydroxyhexadecyl butanoate | 15.346 | 145590-21-9 | 314.5 |
Hexanoic acid, 2-ethyl-, methyl ester | 15.496 | 7425-23-2 | 158.24 |
Pentanoic acid, 2-acetyl-4-methyl-, methyl ester | 16.059 | 38629-82-0 | 186.23 |
Phenol, 2,6-dimethoxy- | 18.442 | 91-17-8 | 182.21 |
(1R,2R,3S,5R)-(-)-2,3-Pinanediol | 18.573 | 4770-94-9 | 166.22 |
2-Piperidinone, N-[4-bromo-n-butyl]- | 19.043 | 27761-74-8 | 242.10 |
Benzyl oleate | 21.445 | 3687-45-4 | 316.46 |
5-tert-Butylpyrogallol | 21.814 | 96-26-4 | 214.24 |
2,4-Di-tert-butylphenol | 22.652 | 96-76-4 | 206.32 |
Hexadecane | 24.635 | 544-76-3 | 226.43 |
Dodecane, 2,6,10-trimethyl- | 24.86 | 3341-81-3 | 224.43 |
Heptacosane | 27.813 | 629-80-1 | 396.86 |
Tetradecane, 2,6,10-trimethyl- | 28.075 | 594-82-1 | 226.43 |
Octadecane | 29.289 | 593-45-3 | 254.51 |
Diisobutyl phthalate | 30.553 | 84-69-5 | 278.34 |
Dibutyl phthalate | 32.454 | 84-74-2 | 278.34 |
Adsorbent | Langmuir | Freundlich | Dubinin–Radushkevich | |||||
---|---|---|---|---|---|---|---|---|
Qm (mg/g) | KL (L/mg) | R2 (-) | KF ((mg/g) L/mg)n) | n (-) | R2 (-) | E (J/mol) | R2 (-) | |
Zinc | 52.36 | 0.06 | 0.91 | 3.03 | 0.88 | 0.93 | 1054.9 | 0.917 |
Colour | 47.62 | 0.10 | 0.64 | 2.10 | 0.34 | 0.83 | 1825.74 | 0.836 |
Adsorbate | Pseudo-First-Order Equation Parameters | Pseudo-Second-Order Equation Parameters | ||||
---|---|---|---|---|---|---|
K1 (1/min) | Qe (mg/g) | R2 | K2 (g/(mg·min)) | Qe (mg/g) | R2 | |
Zinc | 0.0205 | 13.82 | 0.989 | 0.01 | 4.89 | 0.997 |
Colour | 0.001 | 34.94 | 0.389 | 0.072 | 83.3 | 1 |
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Marszałek, A.; Puszczało, E.; Szymańska, K.; Sroka, M.; Kudlek, E.; Generowicz, A. Application of Mesoporous Silicas for Adsorption of Organic and Inorganic Pollutants from Rainwater. Materials 2024, 17, 2917. https://doi.org/10.3390/ma17122917
Marszałek A, Puszczało E, Szymańska K, Sroka M, Kudlek E, Generowicz A. Application of Mesoporous Silicas for Adsorption of Organic and Inorganic Pollutants from Rainwater. Materials. 2024; 17(12):2917. https://doi.org/10.3390/ma17122917
Chicago/Turabian StyleMarszałek, Anna, Ewa Puszczało, Katarzyna Szymańska, Marek Sroka, Edyta Kudlek, and Agnieszka Generowicz. 2024. "Application of Mesoporous Silicas for Adsorption of Organic and Inorganic Pollutants from Rainwater" Materials 17, no. 12: 2917. https://doi.org/10.3390/ma17122917