Revealing the Combined Effect of Active Sites and Intra-Particle Diffusion on Adsorption Mechanism of Methylene Blue on Activated Red-Pulp Pomelo Peel Biochar
Abstract
:1. Introduction
2. Results
2.1. Morphology and Textural Properties of PP and PPCs
2.2. Thermal Analysis of PP and PPCs
2.3. Surface Chemistry and Characteristics of PPCs
2.4. Adsorption Isotherms and Thermodynamics
2.4.1. Langmuir Isotherm Model
2.4.2. Freundlich Isotherm
2.4.3. Temkin Isotherm
2.5. Adsorption Thermodynamics
2.6. Adsorption Kinetics
2.6.1. Adsorption Empirical and Reaction Models
2.6.2. Adsorption Diffusion Models
3. Materials and Methods
3.1. Materials and Reagents
3.2. Preparation of Pomelo Peel Biochar
3.3. Batch Adsorption Experiments
4. Conclusions
- (1)
- The adsorption of MB on PPC-150 mainly exhibits the character of chemisorption with positive enthalpy energy of adsorption (12.3 kJ/mol), which is likely due to the formation of dipole-dipole H-bonding (N→H–O–adsorbent) and Yoshida H-bonding with electron transfer from aromatic rings (framework structure of MB) to hydroxyl groups (major surface sites of PPC-150);
- (2)
- The adsorption of MB on PPCs except for PPC-150 mainly exhibits characters of physisorption with negative enthalpy energy of adsorption (–25.0 to –32.8 kJ/mol). Desorption becomes significant at high temperatures (above 30 °C), leading to the decrease of equilibrium adsorption quantities of MB on PPCs;
- (3)
- PPC-300 and PPC-350 exhibit much higher apparent adsorption rates than either PPC-250 or PPC-200, leading to a rapid adsorption equilibrium due to synergetic contributions of surface adsorption (active sites) and pore-filling (intra-particle diffusion);
- (4)
- Especially, PPC-300 and PPC-350 exhibit intra-particle-diffusion-controlled adsorption kinetic process with low initial MB concentration (100 ppm) or at the very beginning and final stage of adsorption with high initial MB concentration (300 ppm) at 40 °C.
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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Sample Name | SBET (m2/g) | Smeso (m2/g) | Vtotal (cm3/g) | Vmicro (cm3/g) | Vmeso (cm3/g) | Mid-Value Dmicro (nm) | Average Dmeso (nm) |
---|---|---|---|---|---|---|---|
PP | 0.5503 | – | 0.00143 | – | – | – | – |
PPC-150 | 3.065 | – | 0.015 | – | – | – | – |
PPC-200 | 29.463 | 25.854 | 0.039 | – | 0.038 | – | – |
PPC-250 | 511.380 | 101.325 | 0.267 | 0.2017 | 0.101 | 0.6005 | 3.994 |
PPC-300 | 1274.577 | 646.040 | 0.927 | 0.5105 | 0.661 | 0.6444 | 4.095 |
PPC-350 | 1094.909 | 824.592 | 1.298 | 0.4559 | 1.181 | 0.6726 | 5.728 |
Isotherm Model | Temperature | Parameters | Samples | ||||
---|---|---|---|---|---|---|---|
PPC-150 | PPC-200 | PPC-250 | PPC-300 | PPC-350 | |||
Langmuir | 293 K | Qmax | 262.08 | 318.05 | 359.72 | 385.23 | 351.40 |
KL | 0.271 | 1.360 | 1.783 | 2.750 | 1.797 | ||
Adj. R2 | 0.974 | 0.968 | 0.955 | 0.946 | 0.936 | ||
313 K | Qmax | 286.57 | 304.30 | 345.06 | 356.90 | 322.68 | |
KL | 0.374 | 0.545 | 0.829 | 1.162 | 0.932 | ||
Adj. R2 | 0.967 | 0.969 | 0.946 | 0.961 | 0.958 |
Isotherm Model | Temperature | Parameters | Samples | ||||
---|---|---|---|---|---|---|---|
PPC-150 | PPC-200 | PPC-250 | PPC-300 | PPC-350 | |||
Freundlich | 293 K | KL | 104.39 | 153.46 | 171.12 | 187.50 | 163.17 |
n | 5.79 | 6.90 | 6.45 | 6.60 | 6.37 | ||
Adj. R2 | 0.951 | 0.919 | 0.947 | 0.966 | 0.935 | ||
313 K | KL | 113.15 | 131.80 | 142.33 | 155.62 | 149.56 | |
n | 5.62 | 6.19 | 5.60 | 6.04 | 6.47 | ||
Adj. R2 | 0.944 | 0.926 | 0.971 | 0.932 | 0.922 |
Isotherm Model | Temperature | Parameters | Samples | ||||
---|---|---|---|---|---|---|---|
PPC-150 | PPC-200 | PPC-250 | PPC-300 | PPC-350 | |||
Temkin | 293 K | Q | 33.29 | 32.90 | 38.68 | 38.72 | 37.10 |
Kt | 13.00 | 110.51 | 101.26 | 201.67 | 104.66 | ||
bt (kJ/mol) | 20.212 | 25.130 | 25.613 | 26.631 | 25.657 | ||
Adj. R2 | 0.992 | 0.974 | 0.986 | 0.992 | 0.968 | ||
313 K | Q | 36.11 | 35.53 | 40.94 | 39.80 | 35.84 | |
Kt | 15.50 | 30.74 | 33.76 | 55.06 | 59.52 | ||
bt (kJ/mol) | 22.704 | 24.259 | 24.821 | 25.519 | 25.318 | ||
Adj. R2 | 0.985 | 0.977 | 0.987 | 0.974 | 0.973 |
Samples | Parameters | ∆Ho (kJ/mol) | ∆So (J/mol K) | ||
---|---|---|---|---|---|
T (K) | Kc | ∆Go (kJ/mol) | |||
PPC-150 | 293 | 13,811 | −23.223 | 12.281 | 121.2 |
313 | 19,060 | −25.646 | |||
PPC-200 | 293 | 69,309 | −27.152 | −34.862 | −26.3 |
313 | 27,774 | −26.626 | |||
PPC-250 | 293 | 90,866 | −27.812 | −29.196 | −4.7 |
313 | 42,248 | −27.718 | |||
PPC-300 | 293 | 140,147 | −28.868 | −32.841 | −13.6 |
313 | 59,218 | −28.596 | |||
PPC-350 | 293 | 91,580 | −27.831 | −25.030 | 9.6 |
313 | 47,497 | −28.022 |
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Wei, F.; Jin, S.; Yao, C.; Wang, T.; Zhu, S.; Ma, Y.; Qiao, H.; Shan, L.; Wang, R.; Lian, X.; et al. Revealing the Combined Effect of Active Sites and Intra-Particle Diffusion on Adsorption Mechanism of Methylene Blue on Activated Red-Pulp Pomelo Peel Biochar. Molecules 2023, 28, 4426. https://doi.org/10.3390/molecules28114426
Wei F, Jin S, Yao C, Wang T, Zhu S, Ma Y, Qiao H, Shan L, Wang R, Lian X, et al. Revealing the Combined Effect of Active Sites and Intra-Particle Diffusion on Adsorption Mechanism of Methylene Blue on Activated Red-Pulp Pomelo Peel Biochar. Molecules. 2023; 28(11):4426. https://doi.org/10.3390/molecules28114426
Chicago/Turabian StyleWei, Fang, Shenglong Jin, Chunyi Yao, Tianhao Wang, Shengpu Zhu, Yabiao Ma, Heng Qiao, Linxi Shan, Rencong Wang, Xiaoxue Lian, and et al. 2023. "Revealing the Combined Effect of Active Sites and Intra-Particle Diffusion on Adsorption Mechanism of Methylene Blue on Activated Red-Pulp Pomelo Peel Biochar" Molecules 28, no. 11: 4426. https://doi.org/10.3390/molecules28114426