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Article

Fast Removal of Naphthol Blue Black B Dye from Water Using Polyethyleneimine Functionalized Zinc, Iron, and Manganese Porphyrinic Complexes: Structural Characterization, Kinetic, and Isotherms Studies

by
Sahar Y. Rajeh
1,
Aljazi Abdullah Alrashidi
1,
Raoudha Soury
1,* and
Mahjoub Jabli
2,*
1
Chemistry Department, College of Science, University of Ha’il, Ha’il 81451, Saudi Arabia
2
Department of Chemistry, College of Science, Majmaah University, Al-Majmaah 11952, Saudi Arabia
*
Authors to whom correspondence should be addressed.
Polymers 2025, 17(11), 1494; https://doi.org/10.3390/polym17111494
Submission received: 25 April 2025 / Revised: 18 May 2025 / Accepted: 23 May 2025 / Published: 28 May 2025
(This article belongs to the Special Issue Challenges and Opportunities in Natural and Synthetic Polymers for Wastewater Treatment)
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Abstract

In the present work, meso-tetrakis(2,4,6-trimethylphenyl) porphyrinato)zinc(II): ([Zn(TMP)] (1), meso-tetrakis-(tetraphenyl)porphyrin iron(III))chloride): [Fe(TPP)Cl] (2), and meso-tetrakis(phenyl)porphyrin manganese(III) chloride): [Mn(TPP)Cl] (3) were synthesized. Then, the three prepared porphyrinic complexes (1–3) were functionalized with branched polyethyleneimine (PEI). The prepared complexes were thoroughly analyzed using several analytical techniques, including 1H NMR, FT-IR, UV-vis, XRD, XRF, TGA-DTA, SEM, and EDX. The presence of sharp main peaks at 2θ between 10° and 80°, in XRD analysis, for all studied compounds suggested the crystalline nature of the porphyrinic complexes. The morphological properties of the porphyrininc complexes were significantly affected by the chemical modification with polyethyleneimine. EDX result confirmed the complexation of zinc, iron, and manganese metals with the porphyrinic core. The increase in carbon and nitrogen contents after the addition of polyethyleneimine to the complexes (1–3) was noticeable. After thermal decomposition, the total mass loss was equal to 92.97%, 66.77%, and 26.78% for complexes (1), (2), and (3), respectively. However, for the complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI, the total mass losses were 83.12%, 81.88%, and 35.78%, respectively. The synthetic compounds were additionally utilized for the adsorption of Naphthol blue black B from water. At optimum adsorption conditions (T = 20 °C, time = 60 min, pH = 5), the highest adsorption capacities were 154 mg/g, 139 mg/g, and 119 mg/g for complex (3)-PEI, complex (2)-PEI, and complex (1)-PEI, respectively. The adsorption mechanism followed the pseudo second order, the Freundlich, and the Temkin models. The results indicated that the adsorption process is reliant on chemical interactions. It was also governed by intraparticular diffusion and other kinetic phenomena.

1. Introduction

Porphyrinic complexes are an important class due to their versatile properties and features [1,2]. Structurally, porphyrin is composed of four pyrrolic units linked in a coplanar fashion by four methane bridges that give a planar macrocyclic structure. It has an extended conjugated 18 π-electron system, which is responsible for its aromatic behavior. Indeed, the free-base porphyrin reacts with metal cations to form complexes with a variety of conformations, depending especially on the size of metal cations, the axial ligands, the size of peripheral substituents, etc. [3,4]. The properties of metalloporphyrins can be controlled by the fine-tuning of the out-of-plane distance in the porphyrin cavity. Owing to these intriguing features, porphyrins and metalloporphyrins have been widely used in several interesting fields, including theragnostic [5,6,7,8,9,10,11,12], opto-electronics [13,14,15], photocatalysis [16], and other important applications [17,18]. In particular, there is a considerable increase in the usage of metalloporphyrin-based materials for the removal of several harmful contaminants from water in order to limit toxic substance use and manufacture. In previous work, we and other researchers showed that the characteristics, and hence the application, of a metalloporphyrin complex may be altered by modifying the metal [19,20,21,22], the axial ligand(s) coupled to the metal [23,24], and the porphyrin perimeter [25,26,27]. Recently, some investigations have concentrated on the construction of new porphyrins modified with polymers formed predominantly through intermolecular coordination and hydrogen-bonding interactions [28,29].
Polyethyleneimine, which is an organic polyamine polymer, is considered one of the most important examples of cationic polymers. It is rich in amine groups. These amine groups could rapidly interact with several organic and inorganic pollutants. In the literature, some works have reported on the chemical modification of a series of compounds using polyethyleneimine. For instance, Teng et al. [30] used polyethyleneimine to modify polyvinylidene fluoride membrane. The modified membranes exhibited good ability to adsorb organic dyes and heavy metal ions from water and reject them via filtration. Lang et al. [31] fabricated a polyethyleneimine/nanocellulose/MXene/loofah composite aerogel. The aerogel was able to efficiently adsorb heavy crude oil and can selectively adsorb methylene blue, malachite green, Congo red, and methyl orange from mixed dye systems. Yan et al. [32] synthesized a composite aerogel via the lyophilization of cellulose modified with polyethyleneimine and cadmium sulfide. This composite demonstrated exceptional efficacy in degrading methyl orange and methylene blue. In our previous work, we reported the extraction and chemical functionalization of cellulose from Echinops bannaticus leaves. The extracted cellulose was functionalized with Poly (diallyldimethylammonium chloride) and branched polyethyleneimine. The modified samples demonstrated good adsorption capacities of acid blue 25, an anionic dye [33].
Herein, we report, first, the synthesis and the characterization of the following complexes (1–3); meso-tetrakis(2,4,6-trimethylphenyl) porphyrinato)zinc(II): ([Zn(TMP)] (1), meso-tetrakis-(tetraphenyl)porphyrin iron(III))chloride): [Fe(TPP)Cl] (2), meso-tetrakis(phenyl)porphyrin manganese(III) chloride): [Mn(TPP)Cl] (3). Then, the prepared porpyrinic complexes (1–3) were functionalized with branched polyethyleneimine in order to impart reactive amino groups and improve their adsorption capacities toward anionic species. All prepared materials were thoroughly analyzed using several analytical techniques, including 1H NMR, FT-IR, UV-vis, EDX, XRF, SEM, TGA-DTA, and XRD. Materials were further used for the adsorption of Naphthol blue black B from water. Factors influencing the adsorption mechanism, such as pH, time, initial Naphthol blue black B concentration, and temperature, were assessed. The adsorption results were fitted to theoretical kinetic and isotherm models in order to understand the adsorption phenomenon. The thermodynamic parameters were also calculated.

2. Experimental

2.1. Reagents, Materials, and Apparatus

Branched polyethyleneimine solution (50 wt.% in H2O, average Mw ~750,000) was purchased from Sigma Aldrich, S. Louis and Burlington, MA, USA and used for the chemical modification of the porphyrinic compounds. Naphthol blue black B (M.W = 616.5 g/mol, purity = 85%), an anionic dye, was used as the adsorbate during adsorption experiments. The pH values of the solutions were adjusted using sodium hydroxide and sulfuric acid solutions. All other used solvents or reagents were laboratory grade. An Ultrashield spectrometer, Quassim, Saudi Arabia (CDCl3 is used as solvent, and trimethylsilane is the reference) was used to record (1H)-NMR spectra. A Perkin Elmer Spectrum FT-IR (Monastir, Tunis) was used to provide FT-IR spectra. The absorption measurements were collected using a diluted sample solution in dichloromethane (Sigma Aldrich, USA, ST) The morphological characteristics of the porphyrinic compounds under study were described using a JEOL JSM-5400 SEM (Quassim, Saudi Arabia). An X-ray diffraction (XRD) pattern was obtained using PANalytical X’Pert PRO MPD equipment (Quassim, Saudi Arabia). The samples were evaluated within a 2ϴ range (10 to 90 degrees). Thermogravimetric data (TGA/DTA) were collected in an air flow with a heating rate of 10 °C per minute. Thermal events were investigated using a platinum crucible and the NE-TZSCH STA 449F3 instrument (Quassim, Saudi Arabia).

2.2. Synthesis of Complexes 1–3

The meso-tetrakis(2,4,6-trimethylphenyl) porphyrinato)zinc(II): complex (1), meso-tetrakis-(tetraphenyl) porphyrin iron(III)chloride: complex (2) and meso-tetrakis-(tetraphenyl) porphyrin manganese(III)chloride: complex (3) were synthesized following a method reported in our previous studies [34,35,36].

2.3. Synthesis of Complex (1)-PEI: Meso-Tetrakis(2,4,6-trimethylphenyl) Porphyrinato)zinc(II) Functionalized with Branched Polyethyleneimine: [Zn(TMP)]-PEI

[Zn(TMP)] (500 mg, 0.591 mmol) and excess branched PEI polymer solution were mixed in dichloromethane (10 mL) overnight at 25 °C. The hue of the solution shifted from pink to purple. The complex [Zn(TMP)]-branched polyethyleneimine was obtained as a pink powder. UV/Vis [CH2Cl2, λmax in nm (log Ɛ)]: 424 (4.85), 554(3.68), 603(3.25).

2.4. Synthesis of Complex (2)-PEI: Meso-Tetrakis-(tetraphenyl) Porphyrin Iron(III)chloride Functionalized with Branched Polyethylenemine: [Fe(TPP)Cl]-PEI

[Fe(TPP)Cl] (500 mg, 0.747 mmol) and an excess of branched PEI polymer solution were mixed in dichloromethane (10 mL) at 25 °C overnight. The color of the solution turned purple. The complex [Fe(TPP)Cl]- branched PEI was obtained as a purple powder. UV/Vis [CH2Cl2, λmax in nm (log Ɛ)]: 425 (4.98), 515(4.02).

2.5. Synthesis of the Complex (3)-PEI: Meso-Tetrakis-(tetraphenyl) Porphyrin Manganese(III)chloride Functionalized with Branched Polyethyleneimine: [Mn(TPP)Cl]-PEI

[Mn(TPP)Cl] (500 mg, 0.749 mmol) and an excess of branched PEI polymer solution were mixed for 12 h at 25 °C in dichloromethane (10 mL). The solution changed color from green to purple. The complex [Mn(TPP)Cl]-PEI was produced as a purple powder. UV/Vis [CH2Cl2, λmax in nm (log Ɛ)]: 375 (3.97), 411 (4.74), 580(4.97), and 619(5.63).

2.6. Adsorption Experiments

An Erlenmeyer flask containing a mixture of 0.001 g of non-modified or functionalized porphyrinic complexes and 10 mL of Naphthol blue black B solution was continuously stirred (125 rpm) for a period of 2 h. Then, the contents of the flasks were filtered using Whatman filter paper, Riyadh, Saudi Arabia. The absorbance of the resulting solutions was measured using a UV-Vis spectrophotometer (Riyadh, Saudi Arabia) at the maximum wavelength absorption (λmax = 610 nm). The adsorption capacities were further calculated. The studies were designed to test the effects of various contact periods (ranging from 0 to 120 min), Naphthol blue black B concentrations (ranging from 0 mg/L to 600 mg/L), and temperatures (22 °C to 53 °C).

3. Results

3.1. Sample Characterizations

3.1.1. FT-IR Spectroscopy

The FT–IR spectra of complexes (1–3) and the modified complexes are given in Figure 1. For complexes (1–3), the spectra show the presence of the main peaks of metalloporphyrins. The C-H group of the porphyrinic core is detected around 3264–3380 cm−1. The ν (C-N) peak is detected between 1430 and 1500 cm−1. The ν(C-C) peak is seen at 1590–1552 cm−1. The absorption peak for the vibration v (C-C) is around 1102–1230 cm−1. The vibration mode δ (CCH) of the porphyrin core is located at around 1008 cm−1. The absorption peak at 810 cm−1 corresponds to the v (C-C) phenyl group [37,38]. After chemical functionalization of the porphyrinic complexes (1–3) with branched polyethyleneimine, new absorption peaks appear at 1604, 1608, and 1607 cm−1 for complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI, respectively. These absorption peaks can be assigned to the amine groups of polyethyleneimine [39]. This result confirms that the prepared porphyrinic complexes chemically interact with the polymer through amine groups.

3.1.2. Optical Spectroscopy

The UV-visible spectra of the complexes (1–3) and the modified complexes were studied in dichloromethane at a concentration of ca 10−6 M. Figure 2 elucidates the spectroscopic data of complex (1–3) and the modified ones. As observed, the change in the spectral profile is due to the presence of Zn, Fe, and Mn metals. We noticed that the spectrum of complex (1) exhibits a very intense band known as the Soret band, allowing the transition of the electrons from the ground state S0 to the second excited state S2 at 422 nm. In addition, two less intense absorption bands are observed at 550 nm and 596 nm, which are known as Q-Bands corresponding to the transition of electrons from the ground state to the first excited state S1 [30,31,34]. Regarding complex (2), the UV-vis spectrum reveals the presence of a Soret band at 421 nm and one Q-band at 510 nm [35]. We observe significant changes for complex (3) compared to complex (1) and (2). This is related to the manganese metal [36]. Complex (3) contains a hypertype electronic spectrum that includes a half-vacant metal orbital with symmetry, such as [dπ:dxz and dyz] [36]. The Soret band V, or the strongest band, is identified at 471 nm. This band results from the transfer of the porphyrin’s a1u(π) and a2u(π) orbitals to manganese orbitals, such as [dπ: dxz and dyz]. The two less intense bands than the Soret band, the VI and Va bands, are detected at 372 nm and 408 nm, respectively. In addition, there are two Q-bands, the QII and QIV bands, observed at 577 nm and 615 nm, respectively. After chemical modification of the complexes (1–3) with polyethyleneimine, we observe a slight bathochromic shift in the values of λmax of the bands. This suggests the interaction of complexes (1–3) with the polyethyleneimine polymer.

3.1.3. XRD Analysis

Figure 3 shows the XRD patterns of complex (1–3) and modified complexes. As shown, the complex 1 reveals sharp peaks observed at 2θ = 12.29°, 20.05°, 26.60°, 36.75°, 43.05°, 63.40°, and 76.52°. However, the complex 2 exhibits a series of peaks observed at 2θ = 12.30°, 19.43°, 25.94°, 36.99°, 43.10°, 63.50°, and 76.60°. The complex 3 displays a series of peaks observed at 2θ = 13.35°, 16.72°, 19.75°, 29.60°, 36.84°, 42.94°, 63.41°, and 76.53°. These peaks point to the crystalline character of the porphyrinic complexes [40,41]. In addition, we find a slight displacement of the position of the principal peaks for the modified complexes (1–3) compared to the unmodified ones. This shifting suggests again the chemical interaction between the complexes (1–3) and polyethyleneimine.

3.1.4. SEM and EDX Analysis

Figure 4 gives the morphological characteristics of the complexes (1–3) and modified complexes. As observed, the chemical modification of the prepared complexes clearly affects the morphological properties of the porphyrinic complexes. In particular, the particles become more agglomerated due to the chemical interaction between polyethyleneimine and the porphyrinic complexes.
The EDX data support the complexation of zinc, iron, and manganese metals with the porphyrinic core (Figure 5). As expected, an increase in carbon and nitrogen contents after the addition of PEI polymer to the complexes (1–3) is visible. This confirms the interaction between the porphyrinic complexes and polyethyleneimine.

3.1.5. X-Ray Fluorescence Analysis

The X-ray fluorescence (XRF) data of complexes (1–3) and modified complexes, showing the relative abundance of elements, are summarized in Table 1. The results show that the metals Zn, Fe, and Mn are present in the complexes (1–3) with relative amounts of 20.63%, 52.60%, and 70.59%, respectively. Other elements, such as Cl, Na, Al, Ca, K, Ti, Nb, Mo, In, Hf, Sx, and V are also found in the prepared complexes. As observed, the relative abundance of these elements is slightly changed after chemical modification with polyethyleneimine. This result can be explained by the electron transfer pathway between the metals and the nitrogen atom in polyethyleneimine polymer [42,43].

3.1.6. Thermal Analysis

The thermal analysis of complexes (1–3) and modified complexes is shown in Figure 6. All the obtained complexes show thermal processes at temperatures below 100 °C, indicating the release of adsorbed water [44]. The total mass reduction is 72.97%, 66.77%, and 26.78% for complexes 1, 2, and 3, respectively. For the modified complexes, five occurrences are noticed in the range [50–450 °C], with total mass loss of 83.12% (complex 1-PEI), 81.88% (complex 2-PEI), and 35.78% (complex 3-PEI). The increase in the mass loss for the modified complexes confirms the chemical interaction of the porphyrinic complexes modified with polyethyleneimine. This trend also justifies the existence and degradation of the polymeric material. The thermal events indicate that the non-modified compounds are more thermostable than the functionalized ones.

3.2. Application of the Prepared Complexes in Naphthol Blue Black B Adsorption

3.2.1. Effect of the Experimental Parameters on the Adsorption Mechanism

The prepared complexes (1–3) and the modified complexes were studied for the adsorption of Naphthol blue black B from water. The effects of changing pH, dye concentration, duration, and temperature on adsorption capabilities were examined. First, it is noticed that the adsorption capacities of Naphthol blue black B using the prepared complexes (1–3) are poor. However, complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI showed high adsorption capacities. The next sections cover the adsorption of Naphthol blue black B utilizing three adsorbents: complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI. Figure 7a shows the change in the adsorbed amounts of Naphthol blue black B against pH using complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI. As observed, the adsorption capacities of Naphthol blue black B depend significantly on the pH value and it increase from 3 to 5.
At pH = 5, the three studied adsorbents reached their highest adsorption capabilities. At this pH, the negative charges of Naphthol blue black B molecules form strong electrostatic contacts with the positive charges on the surfaces of complexes (1)-PEI, (2)-PEI, and (3)-PEI. In acidic conditions, high concentrations of hydronium ions facilitate anionic dye adsorption. However, high concentrations of hydroxide ions in alkaline environments limit the adsorption capacity of anionic color molecules.
Figure 7b–d describe the change in the adsorption amounts of Naphthol blue black B using complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI. As shown, the adsorption of Naphthol blue black B increases promptly with the reaction time (from 0 to 30 min). In fact, during this stage of adsorption, the number of adsorption sites on the surface of the studied adsorbents results in high adsorption capacity. After 60 min of reaction, the adsorption level tends to stabilize due to saturation of the available adsorption sites on the surfaces of complexes (1)-PEI, (2)-PEI, and (3)-PEI.
Figure 7d–f show the effect of the change in Naphthol blue black B concentration on the adsorption capacities. At low Naphthol blue black B concentrations, dye adsorption capabilities are readily achieved. This is owing to the accessibility of multiple adsorption sites at this phase, as well as the quick dispersion of dye from the original dye solution to the surface of complexes (1)-PEI, (2)-PEI, and (3)-PEI. At optimum adsorption conditions (T = 20 °C, time = 60 min, pH = 5), the highest adsorption capacities achieve 154 mg/g, 139 mg/g, and 119 mg/g for complex (3)-PEI, complex (2)-PEI, and complex (1)-PEI, respectively. The obtained results confirm the use of the prepared compounds as efficient adsorbents of Naphthol blue black B from water. In some cases, the obtained adsorption capacities are higher compared to many adsorbents studied in the literature, and in other cases, they are comparable to some adsorbents (Table 2). In fact, the chemical modification of the metalloporphyrinic complexes with polyethyleneimine greatly improves the adsorption of Naphthol blue black B due to the existence of reactive amine groups. As also observed in Figure 7d–f, the adsorption capacities vary as a function of temperature. The adsorption abilities were reduced with rising temperatures, indicating an exothermic phenomenon. The decrease in adsorption capabilities with temperature can be attributed to the partial breakdown of the association between Naphthol blue black B molecules and the modified metalloporphyrinic complex.

3.2.2. Kinetic Investigation

The adsorption of Naphthol blue black B was evaluated using first order, second order, intra-particular dispersion, and Elovich kinetic models [48] for complexes (1)-PEI, (2)-PEI, and (3)-PEI. The computed variables are listed in Table 3. The high regression coefficients (R2 > 0.98) and correlation of measured adsorbed amounts of Naphthol blue black B with theoretically calculated amounts in the pseudo second order model imply a chemical adsorption mechanism [49,50]. The deviation from the origin in the intra-particular diffusion plots indicates that the adsorption of Naphthol blue black B is driven by both the intra-particular diffusion trend and other kinetic mechanisms [51].

3.2.3. Determination of Thermodynamic Parameters

The three isotherms of Langmuir, Freundlich, and Temkin were evaluated in attempts to analyze the adsorption process of Naphthol blue black B employing the three adsorbents complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI. Table 3 provides the fitting parameters and regression coefficients (R2). The high regression coefficients (R2 ≥ 0.97) indicate that the adsorption mechanism is consistent with the Freundlich and Temkin equations. According to these predictions, active adsorption sites may be unevenly distributed on the surfaces of complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI [52].
Figure 8 shows graphs of Ln (Kd) vs. 1/T to derive the thermodynamic parameters (entropy and enthalpy). Table 3 shows the calculated values. The computed negative enthalpy values confirm that the adsorbent complexes (1)-PEI, (2)-PEI, and (3)-PEI underwent an exothermic reaction. As the temperature rises from 20 °C to 53 °C, the amount of adsorbed Naphthol blue black B molecules decreases, supporting this finding. The entropy values are negative, indicating that the disorder in the examined adsorption system has decreased, as well as the presence of many structural alterations [53]. The positive free energy values obtained during Naphthol blue black B adsorption show that the process is not spontaneous.

4. Conclusions

In this work, meso-tetrakis(2,4,6-trimethylphenyl) porphyrinato)zinc(II): ([Zn(TMP)] (1), meso-tetrakis-(tetraphenyl)porphyrin iron(III))chloride): [Fe(TPP)Cl] (2), and meso-tetrakis(phenyl)porphyrin manganese(III) chloride): [Mn(TPP)Cl] (3) were prepared. Then, the three prepared porphyrinic complexes (1–3) were chemically modified with branched polyethyleneimine (PEI). The synthesized compounds were examined using 1H NMR, FT-IR, UV-vis, XRD, XRF, TGA-DTA, SEM, and EDX. The presence of sharp peaks at 2θ between 10° and 80°, in XRD analysis, for all studied compounds suggested the crystalline nature of the porphyrinic complexes. The morphological properties of the porphyrinic complexes were significantly affected by the chemical modification with polyethyleneimine. EDX result confirmed the complexation of zinc, iron, and manganese metals with the porphyrinic core. The increase in carbon and nitrogen contents after the addition of polyethyleneimine to the complexes 1–3 was noticeable. After thermal decomposition, the total mass losses were equal to 92.97%, 66.77%, and 26.78% for complexes 1, 2, and 3, respectively. However, for the complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI, the total mass losses were 83.12%, 81.88%, and 35.78%, respectively. The synthesized compounds were then utilized to adsorb Naphthol Blue Black B from water. At optimum adsorption conditions (T = 20 °C, time = 60 min, pH = 5), the highest adsorption capacities were 154 mg/g, 139 mg/g, and 119 mg/g for complex (3)-PEI, complex (2)-PEI, and complex (1)-PEI, respectively. The adsorption mechanism followed the pseudo second order, Freundlich, and Temkin models. The process was exothermic and non-spontaneous. Future studies will be extended for the design of other composites based porphyrinic complexes for the adsorption of other pollutants from contaminated water.

Author Contributions

Conceptualization, R.S.; Methodology, A.A.A. and M.J.; Software, S.Y.R., R.S., and M.J.; Validation, S.Y.R. and A.A.A.; Formal analysis, A.A.A.; Investigation, A.A.A. and R.S.; Resources, S.Y.R., R.S., and M.J.; Writing—review and editing, M.J. All authors have read and agreed to the published version of the manuscript.

Funding

This research has been funded by the Scientific Research Deanship at the University of Ha’il, Saudi Arabia, through project number BA-24 020.

Institutional Review Board Statement

Not applicable.

Data Availability Statement

The original contributions presented in this study are included in the article. Further inquiries can be directed to the corresponding authors.

Acknowledgments

This research has been funded by the Scientific Research Deanship at the University of Ha’il, Saudi Arabia, through project number BA-24 020.

Conflicts of Interest

The authors declare no conflict of interest.

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Polymers 17 01494 g001aPolymers 17 01494 g001b
Figure 1. FT-IR spectra of (a) complex (1) and complex (1)-PEI, (b) complex (2) and complex (2)-PEI, (c) complex (3) and complex (3)-PEI.
Figure 1. FT-IR spectra of (a) complex (1) and complex (1)-PEI, (b) complex (2) and complex (2)-PEI, (c) complex (3) and complex (3)-PEI.
Polymers 17 01494 g001aPolymers 17 01494 g001b
Polymers 17 01494 g002aPolymers 17 01494 g002b
Figure 2. Spectroscopic data of: (a); complexes (1–3) and (b); complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI in dichloromethane.
Figure 2. Spectroscopic data of: (a); complexes (1–3) and (b); complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI in dichloromethane.
Polymers 17 01494 g002aPolymers 17 01494 g002b
Polymers 17 01494 g003aPolymers 17 01494 g003b
Figure 3. XRD patterns of complexes (1–3), complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI.
Figure 3. XRD patterns of complexes (1–3), complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI.
Polymers 17 01494 g003aPolymers 17 01494 g003b
Polymers 17 01494 g004
Figure 4. SEM images of: (a) complex (1), (b) complex (2), (c) complex (3), (d) complex (1)-PEI, (e) complex (2)-PEI, and (f) complex (3)-PEI.
Figure 4. SEM images of: (a) complex (1), (b) complex (2), (c) complex (3), (d) complex (1)-PEI, (e) complex (2)-PEI, and (f) complex (3)-PEI.
Polymers 17 01494 g004
Polymers 17 01494 g005aPolymers 17 01494 g005b
Figure 5. EDX result of: (a) complex (1), (c) complex (2), (e) complex (3), (b) complex (1)-PEI, (d) complex (2)-PEI, and (f) complex (3)-PEI.
Figure 5. EDX result of: (a) complex (1), (c) complex (2), (e) complex (3), (b) complex (1)-PEI, (d) complex (2)-PEI, and (f) complex (3)-PEI.
Polymers 17 01494 g005aPolymers 17 01494 g005b
Polymers 17 01494 g006aPolymers 17 01494 g006bPolymers 17 01494 g006c
Figure 6. TGA/DTA curves of complexes (1–3) and modified complexes.
Figure 6. TGA/DTA curves of complexes (1–3) and modified complexes.
Polymers 17 01494 g006aPolymers 17 01494 g006bPolymers 17 01494 g006c
Polymers 17 01494 g007
Figure 7. Influence of some experimental conditions on the adsorption of Naphthol blue black B using complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI: (a) pH (C0 = 50 mg/L, T = 19 °C, time = 100 min), (b,c) time (C0 = 50 mg/L, C0 = 100 mg/L, pH = 5, T = 19 °C), and (d–f) temperature (data is replicated 3 times).
Figure 7. Influence of some experimental conditions on the adsorption of Naphthol blue black B using complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI: (a) pH (C0 = 50 mg/L, T = 19 °C, time = 100 min), (b,c) time (C0 = 50 mg/L, C0 = 100 mg/L, pH = 5, T = 19 °C), and (d–f) temperature (data is replicated 3 times).
Polymers 17 01494 g007
Polymers 17 01494 g008
Figure 8. Plots of Ln Kd versus 1/T for Naphthol blue black B adsorption utilizing complexes (1)-PEI, (2)-PEI, and (3)-PEI (results replicated three times).
Figure 8. Plots of Ln Kd versus 1/T for Naphthol blue black B adsorption utilizing complexes (1)-PEI, (2)-PEI, and (3)-PEI (results replicated three times).
Polymers 17 01494 g008
Table 1. Relative abundance of elements present in complexes 1–3 and modified complexes.
Table 1. Relative abundance of elements present in complexes 1–3 and modified complexes.
m/m (%)
ElementsComplex (1)Complex (1)-PEIComplex (2)Complex (2)-PEIComplex (3)Complex (3)-PEI
Na51.5248.69----
K05.1408.96----
Zn20.6319.75----
Al19.2018.59----
Ca01.7001.59----
Hf01.1401.05----
Ti00.6701.37----
Fe--52.6051.93--
Cl--40.1739.58--
Sx--06.0207.01--
V--00.6900.71--
Ni--00.4400.70--
Nb--00.0200.05--
Mo--00.1000.02--
Mn----70.5968.70
Cl----28.6027.25
Co----0.70601.14
Nb----0.04401.05
Mo----0.03501.04
In----0.01600.07
Table 2. Comparison of the adsorption capacities of Naphthol blue black B using some studied adsorbents.
Table 2. Comparison of the adsorption capacities of Naphthol blue black B using some studied adsorbents.
Q Max (mg/g)Reference
Complex (3)-PEI154This study
Complex (2)-PEI139This study
Complex (1)-PEI119This study
H3PO4 activated carbon produced from oak cupules208[45]
Immobilized Chitosan from Shrimp Shells onto Glass Plate45.5[46]
Commercial powdered activated carbon70.6[47]
Table 3. Kinetics, isotherms, and thermodynamic parameters computed during the adsorption of Naphthol blue black B employing complexes (1)-PEI, (2)-PEI, and (3)-PEI.
Table 3. Kinetics, isotherms, and thermodynamic parameters computed during the adsorption of Naphthol blue black B employing complexes (1)-PEI, (2)-PEI, and (3)-PEI.
ConstantsNaphthol Blue Black B (mg/L)IsothermsParametersTemperature (°C)
Complex (1)-PEI
First order 50100 204253
K1 (min−1)0.0290.0306qm (mg·g−1)222.22250243.90
q (mg·g−1)45.7466.99LangmuirKL (L·g−1)0.00780.00460.39
R20.980.98R20.980.850.90
Second orderK20.00170.0005Thermodynamic parametersΔH° (KJ mol−1)−6.038
q47.3960.97ΔS° (J mol−1)−27.35
R20.990.99ΔG° (KJ mol−1)8.0148.628.89
FreundlichKF (L·g−1)28.842.401.38
Elovichα (mg·g−1·min−1)32.0645.37n1.541.241.21
β (mg·g−1·min−1)0.1020.072R20.970.970.98
R20.950.95TemkinbT (J·mol−1)51.1764.3671.76
Intra-particular-DiffusionK (mg·g1·min1/2)3.364.73A (L·g−1)11.5013.3415.99
R20.880.88R20.980.970.97
Complex (2)-PEI
First orderK1 (min−1)0.0290.031 qm (mg·g−1)188.67204.08227.27
q (mg·g−1)47.8668.23LangmuirKL (L·g−1)0.00880.00420.392
R20.980.98R20.990.950.82
Second orderK20.00110.0009Thermodynamic parametersΔH° (KJ mol−1)−6.61
q44.8464.51ΔS° (J mol−1)−30.51
R20.990.99ΔG° (KJ mol−1)8.948.948.94
FreundlichKF (L·g−1)40.742.751.24
Elovichα (mg·g−1·min−1)23.4927.43n1.671.301.19
β (mg·g−1·min−1)0.0960.068R20.970.970.97
R20.950.94TemkinbT (J·mol−1)60.8655.0278.04
Intra-particular-DiffusionK (mg·g1·min1/2)3.755.47A (L·g−1)10.0868.2419.21
R20.890.87R20.970.970.97
Complex (3)-PEI
First orderK1 (min−1)0.02940.032 qm (mg·g−1)212.76285.71217.39
q (mg·g−1)45.9268.55LangmuirKL (L·g−1)0.00380.00180.37
R20.980.98R20.950.680.73
Second orderK20.00170.015Thermodynamic parametersΔH° (KJ mol−1)−7.71
q47.3972.46ΔS° (J mol−1)−35.66
R20.990.99ΔG° (KJ mol−1)10.4511.2411.59
FreundlichKF (L·g−1)6.922.5139.81
Elovichα (mg·g−1·min−1)23.4327.20n1.431.121.01
β (mg·g−1·min−1)0.0980.070R20.970.970.97
R20.940.94TemkinbT (J·mol−1)65.7371.8275.66
Intra-particular-DiffusionK (mg·g1·min1/2)4.0076.02A (L·g−1)14.1021.9829.57
R20.870.84R20.970.970.97
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Rajeh, S.Y.; Alrashidi, A.A.; Soury, R.; Jabli, M. Fast Removal of Naphthol Blue Black B Dye from Water Using Polyethyleneimine Functionalized Zinc, Iron, and Manganese Porphyrinic Complexes: Structural Characterization, Kinetic, and Isotherms Studies. Polymers 2025, 17, 1494. https://doi.org/10.3390/polym17111494

AMA Style

Rajeh SY, Alrashidi AA, Soury R, Jabli M. Fast Removal of Naphthol Blue Black B Dye from Water Using Polyethyleneimine Functionalized Zinc, Iron, and Manganese Porphyrinic Complexes: Structural Characterization, Kinetic, and Isotherms Studies. Polymers. 2025; 17(11):1494. https://doi.org/10.3390/polym17111494

Chicago/Turabian Style

Rajeh, Sahar Y., Aljazi Abdullah Alrashidi, Raoudha Soury, and Mahjoub Jabli. 2025. "Fast Removal of Naphthol Blue Black B Dye from Water Using Polyethyleneimine Functionalized Zinc, Iron, and Manganese Porphyrinic Complexes: Structural Characterization, Kinetic, and Isotherms Studies" Polymers 17, no. 11: 1494. https://doi.org/10.3390/polym17111494

APA Style

Rajeh, S. Y., Alrashidi, A. A., Soury, R., & Jabli, M. (2025). Fast Removal of Naphthol Blue Black B Dye from Water Using Polyethyleneimine Functionalized Zinc, Iron, and Manganese Porphyrinic Complexes: Structural Characterization, Kinetic, and Isotherms Studies. Polymers, 17(11), 1494. https://doi.org/10.3390/polym17111494

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