Synthesis, Characterization of a New Polyacrylic Acid Superabsorbent, Some Heavy Metal Ion Sorption, the Adsorption Isotherms, and Quantum Chemical Investigation
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Characterization
2.2.1. Fourier Transform Infrared (FTIR) Spectra
2.2.2. 1H NMR Spectra
2.2.3. Atomic Absorption Spectrometry (AAS)
2.2.4. Thermal Gravimetric Analysis (TGA)
2.2.5. Differential Scanning Calorimeter (DSC)
2.2.6. Scanning Electron Microscopy (SEM)
3. Synthesis
3.1. Synthesis of Kry23-DM
3.2. Synthesis of the P (AA/Kry23-DM) SAP
3.3. Computational Method
3.4. Sorption Experiments of the P (AA/Kry23-DM) SAP
3.4.1. Sorption Rate
3.4.2. Sorption Capacity
3.4.3. pH Effect on Sorption Capacity
3.4.4. Competitive Sorption
3.4.5. Distribution Ratio (log D)
3.4.6. Swelling Ratio, qv
3.4.7. Desorption
3.4.8. Freundlich and Langmuir Isotherm Applications
4. Results and Discussion
4.1. Synthesis of Kry23-DM Cross-Linker and P (AA/Kry23-DM) SAP
4.2. Characterization of Kry23-DM Cross-Linker
4.3. Characterization of P (AA/Kry23-DM) SAP
4.4. Computational Method
4.5. Sorption Experiments of the P (AA/Kry23-DM) SAP
4.5.1. Sorption Rate
4.5.2. Sorption Capacity
4.5.3. pH Effect on Sorption Capacity
4.5.4. Competitive Sorption
4.5.5. The Distribution Coefficients (log D)
4.5.6. The Swelling Ratios (qv)
4.5.7. Desorption
4.5.8. Adsorption Isotherms
5. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Calculation Parameters | Quantum Method | Cross-linker | PAA (n = 8) | PAA (n = 20) |
---|---|---|---|---|
ΔfH0(kcal mol−1) | AM1 | −6580.002 | −21,083.115 | −32,872.784 |
Estr (kcal mol−1) | MM2 | 45.465 | 110.954 | 156.202 |
AMBER | 44.434 | 162.305 | 207.171 | |
OPLS | 31.802 | 90.816 | 110.439 | |
φ (°) | MM2 | 173.038 | 175.209 | 174.394 |
AMBER | 171.574 | 168.767 | 171.372 | |
OPLS | 172.267 | 170.765 | 169.816 | |
d (Å) | MM2 | – | 1.549 | 1.547 |
AMBER | – | 1.535 | 1.544 | |
OPLS | – | 1.533 | 1.522 | |
ℓ(Å) | MM2 | – | 7.832 | 27.868 |
AMBER | – | 7.773 | 24.796 | |
OPLS | – | 7.394 | 26.2141 | |
ΔE (kcal mol−1) | MM2 | −2.376 | 75.693 | 133.363 |
AMBER | 7.8059 | 80.481 | 66.881 | |
OPLS | 6.7407 | 55.867 | 47.064 |
Time (min) | Mn2+ | Ni2+ | Cu2+ | Zn2+ | Pb2+ | Cd2+ | Cr3+ | Co3+ | Fe3+ |
---|---|---|---|---|---|---|---|---|---|
15 | 0.3598 | 0.3664 | 0.3684 | 0.1109 | 0.3674 | 0.1587 | 0.3592 | 0.3673 | 0.3668 |
30 | 0.4243 | 0.3663 | 0.4918 | 0.2593 | 0.4922 | 0.2385 | 0.4892 | 0.4932 | 0.4857 |
45 | 0.6673 | 0.7367 | 0.7395 | 0.3877 | 0.7423 | 0.3556 | 0.6990 | 0.7365 | 0.6945 |
60 | 0.8340 | 1.4297 | 1.4705 | 0.7870 | 1.4635 | 0.7692 | 1.3094 | 1.4645 | 1.4621 |
120 | 1.4545 | 1.4602 | 1.4772 | 0.7792 | 1.4737 | 0.7938 | 1.4629 | 1.4647 | 1.4539 |
240 | 1.4516 | 1.4700 | 1.4720 | 0.8156 | 1.4882 | 0.8063 | 1.4415 | 1.4817 | 1.4598 |
480 | 1.4614 | 1.4641 | 1.4730 | 0.8063 | 1.4807 | 0.7818 | 1.4472 | 1.4746 | 1.4640 |
C0 | Mn2+ | Ni2+ | Cu2+ | Zn2+ | Pb2+ | Cd2+ | Cr3+ | Co3+ | Fe3+ |
---|---|---|---|---|---|---|---|---|---|
15 | 1.4537 | 1.4623 | 1.4791 | 0.8318 | 1.4972 | 0.7928 | 1.4293 | 1.4856 | 1.4585 |
20 | 1.9031 | 1.9467 | 1.9502 | 0.9675 | 1.9549 | 0.8055 | 1.9269 | 1.9637 | 1.9327 |
25 | 2.4053 | 2.4415 | 2.4418 | 1.1907 | 2.4939 | 0.8250 | 2.1855 | 2.4606 | 2.4130 |
30 | 2.8863 | 2.9345 | 2.9332 | 1.4037 | 2.9487 | 0.9071 | 2.9190 | 2.9246 | 2.9531 |
pH | Mn2+ | Ni2+ | Cu2+ | Zn2+ | Pb2+ | Cd2+ | Cr3+ | Co3+ | Fe3+ |
---|---|---|---|---|---|---|---|---|---|
1 | 1.4005 | 0.0823 | 0.6057 | 0.3518 | 2.8651 | 0.6805 | 1.1067 | 0.6669 | 2.5167 |
3 | 2.9035 | 2.9029 | 2.9421 | 0.9627 | 2.9676 | 0.9268 | 2.8612 | 2.9476 | 2.9225 |
5 | 2.8643 | 2.9451 | 2.9342 | 0.9746 | 2.9406 | 1.0188 | 2.6955 | 2.9482 | 2.8647 |
7 | 2.8683 | 2.9454 | 2.9296 | 1.4291 | 2.9473 | 0.9390 | 2.9220 | 2.9267 | 2.9693 |
9 | 2.8236 | 2.4858 | 2.9246 | 1.5315 | 2.7092 | 0.9892 | 2.6105 | 2.8848 | 2.9339 |
pH | Cu2+ | Zn2+ | Pb2+ | Cd2+ | Fe3+ |
---|---|---|---|---|---|
1 | 1.0523 | 0.8874 | 0.8394 | 0.8577 | 0.8330 |
3 | 1.4679 | 1.1680 | 1.0931 | 1.1260 | 0.9881 |
5 | 1.4606 | 1.1771 | 0.9930 | 1.0840 | 1.0345 |
7 | 1.4745 | 1.2190 | 1.1875 | 1.1897 | 1.2479 |
9 | 1.5000 | 1.2507 | 1.1802 | 1.2149 | 1.3070 |
pH | Mn2+ | Ni2+ | Cu2+ | Zn2+ | Pb2+ | Cd2+ | Cr3+ | Co3+ | Fe3+ |
---|---|---|---|---|---|---|---|---|---|
1 | 1.9876 | 0.4915 | 1.4786 | 1.1802 | 3.3801 | 1.5166 | 1.8042 | 1.6436 | 2.7773 |
3 | 3.5392 | 3.6025 | 3.7228 | 1.8388 | 3.9824 | 1.6797 | 3.3517 | 3.7714 | 3.5849 |
5 | 3.4707 | 3.7295 | 3.6864 | 1.7468 | 3.7917 | 1.8080 | 3.0226 | 3.8087 | 3.4562 |
7 | 3.3756 | 3.7926 | 3.6236 | 2.0892 | 3.7893 | 1.6960 | 3.6030 | 3.6305 | 4.0027 |
9 | 3.2043 | 2.8147 | 3.6260 | 2.0864 | 3.0832 | 1.7333 | 2.8637 | 3.3987 | 3.6681 |
Ion | Mn2+ | Ni2+ | Cu2+ | Zn2+ | Pb2+ | Cd2+ | Cr3+ | Co3+ | Fe3+ |
---|---|---|---|---|---|---|---|---|---|
log D/pH | 0.57 | 0.48 | 0.30 | 0.54 | 0.52 | 0.24 | 0.51 | 0.54 | 0.52 |
pH | 1 | 3 | 5 | 7 | 9 |
---|---|---|---|---|---|
Swollen polymer (g) | 0.4165 | 0.4472 | 0.5373 | 0.6084 | 0.7891 |
qv | 4.74 | 5.10 | 6.16 | 7.00 | 38.98 |
Metal Ion | Desorbed Metal Ion (mg) | Sorbed Metal Ion (mg) | Desorption Ratio (%) | ID (Hydrated) (Å) | ID (Å) |
---|---|---|---|---|---|
Mn2+ | 0.1125 | 0.1524 | 73.8 | 0.86 | 1.60 |
Ni2+ | 0.1107 | 0.1687 | 65.6 | 0.72 | 1.34 |
Cu2+ | 0.0849 | 0.1144 | 74.2 | 0.62 | 1.44 |
Zn2+ | 0.0536 | 0.0738 | 72.7 | 0.74 | 1.40 |
Pb2+ | 0.0912 | 0.1066 | 85.6 | 1.20 | 2.42 |
Cd2+ | 0.1047 | 0.1325 | 79.0 | 0.96 | 1.82 |
Cr3+ | 0.0880 | 0.1261 | 69.8 | 0.65 | 1.26 |
Co3+ | 0.0748 | 0.1085 | 68.9 | 0.745 | 0.69 |
Fe3+ | 0.0341 | 0.1436 | 23.7 | 0.645 | 0.63 |
Ion | Langmuir Isotherm | Freundlich Isotherm | |||||
---|---|---|---|---|---|---|---|
Kb | As | R2 | k | n | 1/n | R2 | |
Cr3+ | 0.7583 | 0.0439 | 0.9599 | 0.0563 | 10.8342 | 0.0504 | 0.0504 |
Ni2+ | −0.4554 | −0.1425 | 0.4138 | 11.6547 | 0.8163 | 0.9448 | 0.9448 |
Mn2 | 0.4259 | 0.1101 | 0.3716 | 0.6046 | 1.5152 | 0.7922 | 0.7922 |
Zn2+ | 0.0070 | 0.0439 | 0.8257 | 0.0479 | 1.6745 | 0.9485 | 0.9485 |
Cd2+ | 0.0041 | 0.0086 | 0.9863 | 0.0093 | 9.3985 | 0.6939 | 0.6939 |
Pb2+ | 1.7774 | 0.0121 | 0.9013 | 0.0249 | 8.3542 | 0.3465 | 0.3465 |
Cu2+ | 0.6626 | 0.0737 | 0.6999 | 0.4560 | 1.8982 | 0.8698 | 0.8698 |
Co3+ | 0.9605 | 0.0663 | 0.9459 | 0.3029 | 2.41255 | 0.9285 | 0.9285 |
Fe3+ | 0.5979 | 0.0558 | 0.5211 | 0.1313 | 3.6738 | 0.0926 | 0.0926 |
Sample | TI (°C) | Tf (°C) | Tmax (°C) | Weight Loss (%) | Char Yield (%) | ||
---|---|---|---|---|---|---|---|
PAA45 | 154 | 225 | 409.0 | 6.82 | 11.16 | 17.53 | 44.59 at 542.65 °C |
323 | |||||||
PAA SAP | 156.0 | 258.1 | 417.0 | 3.90 | 19.0 | 39.90 | 14.7 at 536.70 °C |
294.1 | 34.9 |
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Savaskan Yilmaz, S.; Yildirim, N.; Misir, M.; Misirlioglu, Y.; Celik, E. Synthesis, Characterization of a New Polyacrylic Acid Superabsorbent, Some Heavy Metal Ion Sorption, the Adsorption Isotherms, and Quantum Chemical Investigation. Materials 2020, 13, 4390. https://doi.org/10.3390/ma13194390
Savaskan Yilmaz S, Yildirim N, Misir M, Misirlioglu Y, Celik E. Synthesis, Characterization of a New Polyacrylic Acid Superabsorbent, Some Heavy Metal Ion Sorption, the Adsorption Isotherms, and Quantum Chemical Investigation. Materials. 2020; 13(19):4390. https://doi.org/10.3390/ma13194390
Chicago/Turabian StyleSavaskan Yilmaz, Sevil, Nuri Yildirim, Murat Misir, Yasin Misirlioglu, and Emre Celik. 2020. "Synthesis, Characterization of a New Polyacrylic Acid Superabsorbent, Some Heavy Metal Ion Sorption, the Adsorption Isotherms, and Quantum Chemical Investigation" Materials 13, no. 19: 4390. https://doi.org/10.3390/ma13194390