Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal
Abstract
:1. Introduction
2. Results and Discussions
2.1. Physical Characterisation of the Obtained Silica Hybrids
2.1.1. UV-Vis Spectroscopy of Sol Samples, during the Synthesis of Hybrid Materials
2.1.2. UV-Vis Spectroscopy of Solid Samples
2.1.3. Fluorescence Spectra of Solid Samples
2.1.4. The FT-IR Spectroscopy
2.1.5. Atomic Force Microscopy (AFM) Analysis
2.1.6. High Resolution Transmission Electron Microscopy (HRTEM)
2.1.7. Morphological and Textural Analyses
2.2. Silica Hybrid Materials Applied for CO2 Detection/Storage
2.3. Testing of PtTAOPP-Silica Hybrid Material and of Silica Control for Methylene Blue Removal from Wastewaters
2.3.1. Method Applied for the Adsorption of Methylene Blue (MB) from Wastewaters
2.3.2. Results of the Kinetic Studies for the Adsorption Process of MB by Silica Control and by PtTAOPP-Silica Hybrid
3. Materials and Methods
3.1. Reagents
3.2. Apparatus
3.3. In Situ Two Steps Acid/Base Catalyzed Sol-Gel Method for Obtaining Silica Hybrids
- For the obtaining of the PtTAOPP-silica hybrid, 10 mL of a solution of 2.1 × 10−6 M PtTAOPP in THF (molar ratio: TEOS:PtTAOPP = 25,000:1) was added slowly under stirring.
- For the obtaining of the PtNPs-silica hybrid, 5 mL of 4.2 × 10−6 M Pt colloidal solution was added to respect the same molar ratio regarding TEOS (TEOS:PtNPs = 25,000:1).
- For the obtaining of the (TAOPP-PtNPs)-silica hybrid, a mixture composed from 10 mL of a solution of 2.1 × 10−6 M PtTAOPP in THF and 5 mL of 4.2 × 10−6 M Pt colloidal solution was added, maintaining the same molar ratio: TEOS:PtNPs:TAOPP = 25,000:1:1.
- The control silica sample was identically synthesized, without the addition of any porphyrin derivatives or PtNPs. A transparent gel was the resulting product.
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Silica Base | Immobilized Component | Hybrid Abbreviation |
---|---|---|
Tetraethyl orthosilicate (TEOS) | Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (PtTAOPP) | PtTAOPP-silica hybrid |
TEOS | 5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (TAOPP) and Pt nanoparticles (PtNPs) | (TAOPP-PtNPs)-silica hybrid |
TEOS | Platinum nanoparticles (PtNPs) | PtNPs-silica hybrid |
TEOS | - | Silica control |
Name | Specific Surface Area [m2/g] | Pore Size Diameter [nm] | Total Pore Volume [cc/g] | Frenkel-Halsey-Hill (FHH) Fractal Dimension |
---|---|---|---|---|
PtTAOPP-silica hybrid | 593 ± 15 | 4.12 | 0.66 | 2.20 |
PtNPs-silica hybrid | 739 ± 19 | 3.73 | 0.59 | 2.45 |
(TAOPP-PtNPs)-silica hybrid | 592 ± 15 | 3.71 | 0.51 | 2.41 |
Control silica | 650 ± 17 | 3.51 | 0.49 | 2.50 |
Silica- or Porphyrin- Based Materials | Pore Size Diameter (nm) | CO2 Adsorption (mmol/g) | Range of Detection (mM) | Ref. |
---|---|---|---|---|
Mesoporous silica obtained from TEOS and a triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) impregnated with 50 wt % polyethyleneimine | 5.3 | 3.068 | - | [41] |
Circulating Fluidized Bed method with mesoporous silica having BET surface area of 250 m2/g and pore volumes of 1.7 c3/g impregnated with 40 wt % polyethyleneimine | 20 | 1.65 | - | [16] |
TEOS-based mesoporous silica impregnated with 70 wt % polyethyleneimine | - | 2.045 | - | [17] |
Silica gel from sodium silicate activated with 2-[2-(3-Trimethoxysilylpropylamino)-ethylamino] ethylamine | 6 | 4.773 | - | [42] |
Mesoporous silica gel from sodium silicate modified with propilamine | 67 | 2.3 | - | [43] |
Silica aerogels starting from TEOS, modified with (3-aminopropyl) triethoxysilane | 1.27 | 2.87 ± 0.05 | - | [44] |
TEOS-based silica matrix impregnated with 5,10,15,20-tetratolyl-21H,23H-porphyrin | 1.37–2.60 | 3.089 | 1.21–4.5 | [18] |
TEOS based silica material impregnated with 5-(4-carboxyphenyl)-5,10,15-tris(4-phenoxyphenyl)-porphyrin and Fe3O4 magnetic nanoparticles | - | - | 3 × 10−2–0.20 | [45] |
5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)-porphyrin | 200 | - | 49–306 | [8] |
Colorimetric sensor film based on phosphorescent Pt(II) meso-Tetra(pentafluorophenyl)porphine, poly(isobutyl methacrylate), α-naphtholphthalein and cetyltrimethylammonium hydroxide | - | - | 1.51–30.3 (2 to 40% in ethanol and olive oil) | [46] |
Porous crystalline framework based on 5, 10, 15, 20-tetra-(2-quinolyl)-21H, 23H-porphine (meso-tetra-2-quinolyl-porphyrin | 0.46 | 0.18 | - | [47] |
Metal-organic framework built from Rh- tetrakis(4-carboxyphenyl)porphyrin and ZrCl4 | 1.85 | 44.2 | - | [48] |
PtTAOPP-silica hybrid material | 4.12 | 25 ± 0.05 | 40–570 | This work |
PtNPs-silica hybrid material | 3.73 | 11 ± 0.06 | - | This work |
(TAOPP-PtNPs)-silica hybrid material | 3.71 | 16.3 ± 0.06 | - | This work |
TEOS-based silica control | 3.51 | 21.6 ± 0.07 | - | This work |
Equations | Parameters | Silica Control | PtTAOPP-Silica Hybrid | ||||
---|---|---|---|---|---|---|---|
0.83 g/L | 1.66 g/L | 3.33 g/L | 0.83 g/L | 1.66 g/L | 3.33 g/L | ||
Pseudo-first order | qe exp. [mg/g] | 6.921 | 3.611 | 4.803 | 7.261 | 3.656 | 4.803 |
qe calc. [mg/g] | - | - | - | 15.26 ± 1.0 | 9.603 ± 0.9 | 14.429 ± 1.2 | |
k1[min−1] | - | - | - | 0.0838 | 0.048 | 0.022 | |
Pseudo-second order | qe calc. [mg/g] | 7.001 ± 1.1 | 3.868 ± 0.3 | 5.04 ± 0.5 | 7.31 ± 0.5 | 3.709 ± 0.1 | 4.853 ± 0.2 |
k2[g × mg−1 × min−1] | 0.18 | 0.08 | 0.03 | 0.19 | 0.157 | 0.025 | |
h [mg × g−1 × min−1] | 8.622 | 1.043 | 0.69 | 10.016 | 2.099 | 0.576 |
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Anghel, D.; Lascu, A.; Epuran, C.; Fratilescu, I.; Ianasi, C.; Birdeanu, M.; Fagadar-Cosma, E. Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal. Int. J. Mol. Sci. 2020, 21, 4262. https://doi.org/10.3390/ijms21124262
Anghel D, Lascu A, Epuran C, Fratilescu I, Ianasi C, Birdeanu M, Fagadar-Cosma E. Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal. International Journal of Molecular Sciences. 2020; 21(12):4262. https://doi.org/10.3390/ijms21124262
Chicago/Turabian StyleAnghel, Diana, Anca Lascu, Camelia Epuran, Ion Fratilescu, Catalin Ianasi, Mihaela Birdeanu, and Eugenia Fagadar-Cosma. 2020. "Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal" International Journal of Molecular Sciences 21, no. 12: 4262. https://doi.org/10.3390/ijms21124262