Sorption Potential of Different Forms of TiO2 for the Removal of Two Anticancer Drugs from Water
Abstract
:1. Introduction
2. Materials and Methods
2.1. Chemicals and Reagents
2.2. Sorbent Preparation and Characterization
2.3. Sorbent Studies
2.4. Instrumental Procedure
2.5. Data Anaylsis
2.6. Sorption Kinetic Models
3. Results and Discussion
3.1. Kinetic Study
3.2. Modeling of Sorption Isotherms—Influence of pH
3.3. Influence of Ionic Strength
3.4. Effect of Sorbent Dosage
3.5. Sorption Thermodynamics
3.6. Statistical Analysis
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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PhAc | IMT | CRZ |
---|---|---|
| | |
Formula | C29H31N7O | C21H22Cl2FN5O |
CAS | 152459-95-5 | 877399-52-5 |
Mr | 493.6 | 450.1 |
pKa | 8.07; 3.73; 2.56; 1.52 | 5.6; 9.4 |
log Kow | 2.89 | / |
IMT | Initial Concentration, mg/L | qe,exp, μg/g | Pseudo-First-Order | Pseudo-Second-Order | ||||
---|---|---|---|---|---|---|---|---|
qe,calc, μg/g | k1, min−1 | R2 | qe,calc, μg/g | k2, g/μg min | R2 | |||
suspended TiO2 | 5 | 14.62 | 8.47 | 0.0059 | 0.9488 | 14.90 | 2.03 × 10−4 | 0.9990 |
15 | 28.40 | 8.50 | 5 × 10−5 | 0.6238 | 29.67 | 4.26 × 10−4 | 0.9981 | |
25 | 32.47 | 10.76 | 3 × 10−5 | 0.6731 | 34.25 | 3.13 × 10−4 | 0.9969 | |
TiO2-GF | 5 | 27.37 | 4.73 | 0.0002 | 0.6430 | 28.57 | 8.36 × 10−4 | 0.9989 |
15 | 118.50 | 6.52 | 0.0004 | 0.6385 | 125 | 2.96 × 10−4 | 0.9999 | |
25 | 168.25 | 8.94 | 0.0002 | 0.6516 | 174.44 | 1.67 × 10−4 | 0.9995 | |
TiO2/CNT-GF | 5 | 32.35 | 4.87 | 0.0003 | 0.5734 | 36.76 | 1.72 × 10−4 | 0.9792 |
15 | 68.18 | 8.23 | 0.0002 | 0.6100 | 85.47 | 4.20 × 10−4 | 0.8151 | |
25 | 104.65 | 10.48 | 0.0002 | 0.6309 | 161.29 | 1.05 × 10−5 | 0.5285 |
CRZ | Initial Concentration, mg/L | qe,exp, μg/g | Pseudo-First-Order | Pseudo-Second-Order | ||||
---|---|---|---|---|---|---|---|---|
qe,calc, μg/g | k1, min−1 | R2 | qe,calc, μg/g | k2, g/μg min | R2 | |||
suspended TiO2 | 5 | 15.88 | 8.00 | 0.0059 | 0.9460 | 15.77 | 9.87 × 10−3 | 0.9997 |
15 | 46.32 | 7.91 | 4 × 10−5 | 0.6230 | 46.30 | 1.13 × 10−3 | 0.9996 | |
25 | 67.39 | 10.21 | 5 × 10−5 | 0.7200 | 68.03 | 4.12 × 10−4 | 0.9989 | |
TiO2-GF | 5 | 42.39 | 2.86 | 0.0002 | 0.4222 | 42.55 | 7.15 × 10−4 | 1.000 |
15 | 120.57 | 5.72 | 0.0002 | 0.7360 | 121.95 | 5.37 × 10−4 | 0.9996 | |
25 | 207.93 | 8.99 | 0.0004 | 0.9133 | 212.77 | 7.43 × 10−4 | 0.9954 | |
TiO2/CNT-GF | 5 | 30.29 | 3.90 | 6 × 10−5 | 0.3427 | 30.40 | 7.07 × 10−3 | 1.000 |
15 | 86.52 | 7.35 | 0.0002 | 0.648 | 88.50 | 3.39 × 10−4 | 0.9996 | |
25 | 121.43 | 9.96 | 0.0002 | 0.7592 | 128.21 | 1.07 × 10−4 | 0.9954 |
Sample | c0, mg/L | Intraparticle Diffusion | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
First Stage | Second Stage | Third Stage | ||||||||
kp1, µg/g min1/2 | R2 | C1 | kp2, µg/g min1/2 | R2 | C2 | kp3, µg/g min1/2 | R2 | C3 | ||
suspended TiO2 | 5 | 2.484 | 0.9731 | 5.757 | 0.1139 | 0.8928 | 10.73 | 0.1018 | 0.9800 | 10.92 |
15 | 3.257 | 0.9751 | 8.884 | 0.5956 | 0.9853 | 12.35 | 0.2395 | 0.9997 | 19.34 | |
25 | 3.475 | 0.9577 | 9.525 | 0.4854 | 0.9901 | 15.42 | 0.4181 | 0.9788 | 17.096 | |
TiO2-GF | 5 | 0.7496 | 0.9828 | 7.675 | 1.6248 | 0.9915 | 2.012 | 0.0121 | 0.8842 | 27.19 |
15 | 12.317 | 0.9942 | 4.801 | 4.8479 | 0.9873 | 44.82 | 0.1761 | 0.9614 | 115.88 | |
25 | 12.738 | 0.9840 | 40.46 | 8.4091 | 0.9867 | 35.57 | 0.0867 | 0.9994 | 166.9 | |
TiO2/CNT-GF | 5 | 1.732 | 0.9623 | 4.491 | 2.7714 | 0.9100 | 8.461 | 0.0018 | 0.8187 | 32.33 |
15 | 5.338 | 0.9557 | 18.016 | 5.5006 | 0.9850 | 15.58 | 0.0402 | 0.9712 | 67.58 | |
25 | 5.018 | 0.9373 | 17.199 | 10.283 | 0.9694 | 51.27 | 0.1127 | 0.9920 | 102.87 |
Sample | c0, mg/L | Intraparticle Diffusion | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
First Stage | Second Stage | Third Stage | ||||||||
kp1, µg/g min1/2 | R2 | C1 | kp2, µg/g min1/2 | R2 | C2 | kp3, µg/g min1/2 | R2 | C3 | ||
suspended TiO2 | 5 | 0.4913 | 0.9539 | 11.00 | 0.0330 | 0.9046 | 14.51 | - | - | - |
15 | 2.318 | 0.9776 | 17.81 | 0.6452 | 0.9935 | 31.13 | 0.1536 | 0.9508 | 40.21 | |
25 | 2.814 | 0.9465 | 20.05 | 1.779 | 0.9395 | 27.35 | 0.3887 | 0.9971 | 52.47 | |
TiO2-GF | 5 | 1.261 | 0.9530 | 30.34 | 0.1787 | 0.8709 | 39.17 | 0.0045 | 0.9976 | 42.22 |
15 | 5.441 | 0.9524 | 60.15 | 0.6495 | 0.9812 | 98.46 | 0.0220 | 1.000 | 119.73 | |
25 | 14.914 | 0.9918 | 0.7623 | 4.138 | 0.9168 | 80.25 | 2.803 | 0.9994 | 102.09 | |
TiO2/CNT-GF | 5 | 2.009 | 0.8401 | 15.59 | 0.1506 | 0.9554 | 26.73 | 0.0210 | 0.9436 | 29.54 |
15 | 17.532 | 0.9269 | 2.124 | 1.948 | 0.9928 | 43.26 | 0.3957 | 0.9324 | 72.35 | |
25 | 10.690 | 0.9609 | 17.21 | 3.713 | 0.9979 | 31.72 | 1.048 | 0.9345 | 83.87 |
Isotherm Parameter | Suspended TiO2 | TiO2-GF | TiO2/CNT-GF | ||||||
---|---|---|---|---|---|---|---|---|---|
5 | 7 | 9 | 5 | 7 | 9 | 5 | 7 | 9 | |
Linear | |||||||||
Kd (mL/g) | 162.2 | 213.8 | 672.3 | 22.1 | 36.4 | 160.5 | 75.4 | 82.3 | 113.2 |
R2 | 0.9960 | 0.9980 | 0.9910 | 0.9930 | 0.9970 | 0.9910 | 0.9900 | 0.9900 | 0.9920 |
Langmuir | |||||||||
qm (mg/g) | 5.0 | 5.0 | 20 | 5.0 | 1.1 | 5.0 | 0.45 | 0.62 | 0.67 |
KL (mL/g) | 0.5 | 0.4 | 0.07 | 0.004 | 0.15 | 0.03 | 0.051 | 0.049 | 0.059 |
R2 | 0.8896 | 0.9199 | 0.9989 | 0.9990 | 0.9190 | 0.9900 | 0.9430 | 0.9540 | 0.9440 |
Freundlich | |||||||||
n | 3.0 | 2.6 | 1.4 | 0.95 | 1.88 | 0.91 | 0.64 | 0.68 | 0.66 |
KF (μg/g)(mL/μg)1/n | 2027.2 | 1944.5 | 1563.5 | 17.7 | 9.3 | 9.8 | 14.2 | 21.1 | 27.2 |
R2 | 0.9750 | 0.9990 | 0.9990 | 0.9980 | 0.9690 | 0.9910 | 0.9720 | 0.9770 | 0.9680 |
Isotherm Parameter | Suspended TiO2 | TiO2-GF | TiO2/CNT-GF | ||||||
---|---|---|---|---|---|---|---|---|---|
5 | 7 | 9 | 5 | 7 | 9 | 5 | 7 | 9 | |
Linear | |||||||||
Kd (mL/g) | 103.5 | 233.8 | 234.4 | 117.12 | 179.18 | 208.91 | 197.74 | 234.12 | 329.67 |
R2 | 0.9965 | 0.9970 | 0.9993 | 0.9980 | 0.9930 | 0.9922 | 0.9911 | 0.9936 | 0.9940 |
Langmuir | |||||||||
qm (mg/g) | 10.0 | 5.0 | 20.0 | 100 | 5.0 | 10.0 | 50 | 166.7 | 33.3 |
KL (mL/g) | 0.015 | 0.5 | 0.5 | 0.001 | 0.074 | 0.036 | 0.004 | 0.0013 | 0.0097 |
R2 | 0.9968 | 0.8665 | 0.9072 | 0.9980 | 0.9976 | 0.9990 | 0.9911 | 0.9994 | 0.9986 |
Freundlich | |||||||||
n | 1.2 | 2.6 | 2.7 | 0.99 | 1.3 | 1.2 | 0.99 | 0.97 | 0.98 |
KF (μg/g)(mL/μg)1/n | 174.2 | 2025.8 | 2105.7 | 116.5 | 399.9 | 382.6 | 204.2 | 208.8 | 329.7 |
R2 | 0.9982 | 0.9482 | 0.9707 | 0.9984 | 0.9974 | 0.9994 | 0.9965 | 0.9975 | 0.9967 |
Sample | Kd, mL/g | ΔG°, kJ/mol | ΔH°, kJ/mol | ΔS°, J/mol | ||||
---|---|---|---|---|---|---|---|---|
IMT | 298 K | 303 K | 308 K | 298 K | 303 K | 308 K | ||
suspended TiO2 | 213.8 | 61.9 | 49.7 | −13.3 | −10.4 | −10.0 | −57.9 | −151.0 |
TiO2-GF | 36.4 | 40.3 | 47.4 | −8.8 | −9.3 | −9.5 | 10.4 | 64.6 |
TiO2/CNT-GF | 82.3 | 82.5 | 88.7 | −10.9 | −11.1 | −1.8 | 2.9 | 46.4 |
CRZ | ||||||||
suspended TiO2 | 233.8 | 268.8 | 271.7 | −13.5 | −14.3 | −14.8 | 16.7 | 101.7 |
TiO2-GF | 179.2 | 180.9 | 197.6 | −10.1 | −11.6 | −11.9 | 3.82 | 55.8 |
TiO2/CNT-GF | 234.1 | 325.2 | 357.0 | −8.1 | −8.7 | −9.7 | 5.97 | 65.6 |
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Tolić Čop, K.; Mutavdžić Pavlović, D.; Duić, K.; Pranjić, M.; Fereža, I.; Jajčinović, I.; Brnardić, I.; Špada, V. Sorption Potential of Different Forms of TiO2 for the Removal of Two Anticancer Drugs from Water. Appl. Sci. 2022, 12, 4113. https://doi.org/10.3390/app12094113
Tolić Čop K, Mutavdžić Pavlović D, Duić K, Pranjić M, Fereža I, Jajčinović I, Brnardić I, Špada V. Sorption Potential of Different Forms of TiO2 for the Removal of Two Anticancer Drugs from Water. Applied Sciences. 2022; 12(9):4113. https://doi.org/10.3390/app12094113
Chicago/Turabian StyleTolić Čop, Kristina, Dragana Mutavdžić Pavlović, Katarina Duić, Minea Pranjić, Iva Fereža, Igor Jajčinović, Ivan Brnardić, and Vedrana Špada. 2022. "Sorption Potential of Different Forms of TiO2 for the Removal of Two Anticancer Drugs from Water" Applied Sciences 12, no. 9: 4113. https://doi.org/10.3390/app12094113