Open Access Article
Hong Zhua,
Yucheng Zhoua,
Shengsen Wangab,
Xiaoge Wua,
Jianhua Houab,
Weiqin Yina,
Ke Fengab,
Xiaozhi Wang
*abc and
Jie Yangd
aCollege of Environmental Science and Engineering, Yangzhou University, Jiangsu 225127, China. E-mail: xzwang@yzu.edu.cn
bJiangsu Collaborative Innovation Center for Solid Organic Waste Resource Utilization, Nanjing 210095, China
cInstitutes of Agricultural Science and Technology Development, Yangzhou University, Yangzhou 225127, Jiangsu, China
dKey Laboratory of Crop and Livestock Integration, Ministry of Agriculture, Nanjing 210095, China
First published on 2nd August 2018
In this study, a novel magnetic nanocomposite was prepared using waste toner (WT) through high temperature decomposition, and calcination was conducted in different atmospheres (air, ammonia, and vacuum). WT calcined in ammonia (WT(NH3)), and it was then utilized as an efficient absorbent for the reduction of Cr(VI) in aqueous solutions; a batch experiment with different conditions was performed to investigate its Cr(VI) removal ability. The effects of two pH-regulating acid (HCl and H2SO4) treatments were also studied. It was found that WT(NH3) could remove about 99% Cr(VI) at pH 2 under H2SO4 treatment. The XRD and TEM results coupled with VSM results confirmed that WT(NH3) is an Fe3O4/Fe2N nanohybrid, which possesses excellent water-dispersibility and remarkable magnetic properties. XPS analysis showed the presence of Cr(VI) and Cr(III) on the surface of WT(NH3), which indicated that Cr(VI) was reduced to Cr(III). Furthermore, H2SO4 regulation also promoted the reduction of Cr(VI) by WT(NH3), and this reduction was higher than that obtained by HCl regulation.
With the increasing demand for electronic and electrical equipment (EEE) in modern society, a significant amount of EEE waste (WEEE) is produced, and the major constituents of WEEE plastics include polypropylene (PP) and high-impact polystyrene (HIPS).13 To recycle WEEE, some researchers have prepared R-PP/R-HIPS blends by adding polystyrene–poly(ethylene/propylene) (SEP) or glycidyl methacrylate (GMA) to obtain functional polymer nanocomposites.14 Also, it has been reported that near-critical water can be used to recycle printed circuit boards for the collection of copper foils and fabrics.15 The overuse of printing equipment has led to a significant increase in the number of waste toner cartridges.16 Powdery waste toner (WT) accounts for 8.0 wt% of a toner cartridge. Also, the weight of WT has reached about 36 t per year in China. Furthermore, if WT is disposed without reasonable management, its toxic components, including hazardous organic components, will be released into the environment, which can pollute the soil, underground water and air; this will be a tremendous threat to the human health.17 In fact, WT is a mixture that includes about 7.0 wt% polyacrylate, 55.0 wt% polystyrene, 3.0 wt% SiO2, and 35.0 wt% Fe3O4.18–20 In recent years, very few researchers have studied the recycling and transformation of WT. The method of vacuum-gasification-condensation was used to treat WT since the organic matter in WT can be decomposed and gasified at high temperature. Meanwhile, SiO2 and Fe3O4 in WT were transformed into nanosized Fe3O4 and nano-SiO2.19 A thermal transformation process was investigated to convert WT into 98% pure iron by using the gases collected during the thermal transformation as an in situ source of carbon.21
Recently, iron-bearing materials have been applied to various fields such as drug delivery, sensors, electromagnetic interference shielding, and adsorbents for environmental remediation.22–24 In the environmental field, iron-bearing materials such as magnetite,25,26 iron sulfides,27,28 goethite,29 and zerovalent iron30 can remediate Cr(VI). It has also been reported that fabric- and cellulose-derived magnetic carbon–iron nanomaterials possess high efficiency for Cr(VI) removal,31,32 where Cr(VI) is reduced to Cr(III) by the reductive intermediates generated from ZVI such as Fe(II). Moreover, the nanocarbon structure and different carbonization temperatures affect the Cr(VI) removal capacity.33,34 Also, Fe3O4 is a type of iron oxide, and it exhibits remarkable performance owing to its high efficiency of adsorbing Cr(VI) and reducing Cr(VI) to less toxic Cr(III).35 Furthermore, compared to traditional absorbents, this compound can be separated and recovered rapidly using an external magnetic field. It is known that Fe3O4 nanoparticles can be obtained by calcining WT. Although the calcination of WT has been previously studied, its calcination under different atmospheres and Cr(VI) uptake using the resultant nanoparticles have not been well investigated.
In this study, we attempted to develop a novel low-cost magnetic nanocomposite by recycling waste toner through high-temperature decomposition. Calcination was conducted in air, ammonia and vacuum to explore the influence of atmosphere on WT modification. Due to the unique properties of the materials, we used different acids to adjust the pH value during the experiments, and the results showed significant difference. The aim of this study is to characterize the as-prepared WTs, evaluate their applicability for Cr(VI) adsorption and reduction, and explore the mechanisms of Cr(VI) removal.
The mixture was placed on an Orbit shaker with continual mixing at 300 rpm. All experiments were carried out at the room temperature of 25 °C and were performed in duplicate. After reacting for a certain time, WTs were filtered through a 0.45 μm membrane, and the residual Cr(VI) concentration was determined using an ultraviolet visible (UV) spectrophotometer at λ = 540 nm, according to the 1,5-diphenylcarbazide colorimetric method.36 To measure total Cr concentration, the 1,5-diphenylcarbazide colorimetric method (with KMnO4) was used.37 Also, the leached iron in the solution was determined using the 1,10-phenanthroline spectrophotometry method.38
As shown in Fig. 2, compared with the result for the spectrum of original WT, the organic groups disappeared in the spectra of WT(Air), WT(Vac) and WT(NH3). The band at 578 cm−1 was related to the vibration of the Fe–O functional group, which matched well with the characteristic peak of Fe3O4.41 This finding was in accordance with the XRD patterns. The weak peaks between 1101 and 1151 cm−1 were assigned to the Si–O–Si group antisymmetric stretching vibration modes, indicating the existence of SiO2 in the material.
It can be seen from the SEM image (Fig. 3(a)) that original WT is a granular mixture with a diameter of about 5 μm. After calcination, Fe3O4 and SiO2 were retained in the residue. As shown in Fig. 3(b) and (c), WT(Vac) is found to be more aggregated than WT(NH3), which was in accordance with the TEM results (Fig. 4(b)). The Fe3O4/Fe2N nanoparticles displayed a spherical morphology with a mean diameter of 200 nm (Fig. 4(a)).
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| Fig. 4 TEM images of (a) WT(NH3) and (b) WT(Vac) and the corresponding EDX elemental mappings of iron, nitrogen, oxygen, carbon, and silicon. | ||
To further verify the distribution and structure of the material, TEM images of WT(NH3) and WT(Vac) were obtained (Fig. 4). Both samples showed few tetragonal or spherical Fe2N species, and spherical Fe3O4 species were also observed. Furthermore, WT(NH3) had more phase interfaces of Fe3O4 and Fe2N than WT(Vac). The EDS and TEM mapping analysis revealed the presence of Fe, Si, C and O in WTs and Fe, Si, C, N and O in WT(NH3). Higher amount of N (8.6 wt%) was believed to be due to N-doping from annealing in ammonia (Table 1).
| Sample | N | C | H | Fe |
|---|---|---|---|---|
| WT | 0.049 | 52.66 | 5.232 | 32.07 |
| WT(Air) | 0.012 | 0.11 | 0.420 | 56.54 |
| WT(Vac) | 0.068 | 9.66 | 0.322 | 66.41 |
| WT(NH3) | 8.641 | 7.50 | 0.357 | 69.56 |
The Brunauer–Emmett–Teller (BET) surface areas of WT(Air), WT(Vac) and WT(NH3) are shown in Table S1.† WT(NH3) has a larger surface area (42.53 m2 g−1) than WT(Vac) (11.93 m2 g−1) and WT(Air) (11.75 m2 g−1), which can improve mass transfer and increase the number of active sites.42 The pore volume is in good agreement with the surface area.
The XPS spectra of WT(NH3) depicted in Fig. 5 exhibit the presence of C, O, N, and Fe before the reaction. The C 1s spectra exhibit four peaks; the peaks at binding energies of 284.7 eV and 285.9 eV corresponded to C–H, C–C, and hydroxyl (C–OH) bonds, and the peaks at 287.5 eV (C
O, O–C–O) and 288.9 eV corresponded to the carbonyl (O–C
O) bond (Fig. 5(b)).43 Fig. 5(c) shows the high-resolution XPS spectra of the N peaks: pyrrolic-N at 400.5 eV, Fe–N at 399.3 eV, and pyridinic-N at 398.6 eV.44 Nitrogen was successfully doped into Fe3O4 and reacted with iron, which was consistent with Fe2N from XRD characterization. The XPS Fe 2p spectra of WT(NH3) showed two peaks centered at 710.9 eV and 724.1 eV, which were assigned to Fe 2p3/2 and Fe 2p1/2, respectively. For Fe 2p3/2, the peak at BE of 710.6 eV was assigned to ferrous iron in Fe3O4 (FeO·Fe2O3) and Fe2N, whereas that at 711.8 eV corresponded to Fe(III) in Fe3O4.45 Metallic iron was also observed at the binding energy of 707.5 eV based on the Fe 2p3/2 spectra. The satellite peak at 719.9 eV was much weaker, which further proved the absence of Fe3O4 rather than γ-Fe2O3.46 These results were consistent with the TEM and XRD results.
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| Fig. 5 XPS total survey (a), C 1s (b), N 1s (c), Cr-unloaded Fe 2p (d), Cr-loaded Fe 2p (e), and Cr 2p's (f) spectra. | ||
The magnetization curves of original WT and WT(NH3) were studied using a vibrating sample magnetometer (VSM) at an ambient temperature. The corresponding hysteresis loops are shown in Fig. 6, and the saturation magnetization of original WT was determined to be about 37.9 emu g−1, which decreased to 21.1 emu g−1 (WT(NH3)) after calcination in an ammonia atmosphere. This can guarantee its convenient separation from pollutants when used as an adsorbent.
As shown in Fig. 7, Cr(VI) removal efficiencies decreased in the following order: WT(NH3) > WT(Vac) > WT(Air) > original WT. The effects of two pH-regulating acid (HCl and H2SO4) treatments were investigated. Under HCl treatment, WT(NH3) removed 78.2% of Cr(VI) compared to WT(Vac) and WT(Air), which removed 29.9% and 5.3% of Cr(VI), respectively. Also, there was only a slight difference between WT(Vac) and WT(Air) under the two acid treatments. However, for WT(NH3), its Cr(VI) removal efficiency was greatly affected. Within the first 1.5 h, its Cr(VI) removal efficiencies under HCl and H2SO4 treatments were almost identical. For HCl treatment, its efficiency showed only a gradually increasing trend after 2 h; on the contrary, its efficiency increased sharply with H2SO4 treatment, which resulted in 99.9% Cr(VI) removal after 7 h.
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| Fig. 7 Removal efficiency of Cr(VI) using different systems with reaction time. Reaction conditions: 4 g L−1 as-prepared sorbents, 49.68 mg L−1 Cr(VI) concentration, and pH = 2.0. | ||
The linearized modeled isotherms are plotted in Fig. S2.† As shown, high correlation coefficients and good R2 values were obtained from the isotherm models described for the removal of Cr(VI) by WT(NH3) in both HCl and H2SO4 systems (Table S3†). The adsorption of Cr(VI) was well fitted by the Langmuir model than the Freundlich model, indicating that Cr(VI) removal by WT(NH3) is a monolayer adsorption process.
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| Fig. 8 Effect of initial pH on Cr(VI) removal efficiency by WT(NH3). Reaction conditions: 4 g L−1 WT(NH3), 49.68 mg L−1 Cr(VI) concentration, and 7 h reaction time. | ||
To investigate the surface charge of WT(NH3), we measured its zeta potential (Fig. S3†). The isoelectric point of WT(NH3) was found to be about pH 2. Below this value, the surface of WT(NH3) was positively charged, which was beneficial to bind with chromium anions through electrostatic attraction and ion exchange. At high pH values, the surface of WT(NH3) became less positively charged, which might be unfavourable for Cr(VI) adsorption.50
:
1, implying that the reaction mechanisms might be sorption together with reduction processes. In addition, the concentrations of total Cr decreased by 14% and 46% in the H2SO4 and HCl systems, respectively. All the Cr(VI) ions were almost reduced to Cr(III) in the solution; thus, the H2SO4 system can promote the reduction of Cr(VI) by WT(NH3) (Fig. S4(b)†).
As shown in Fig. 5(e), the binding energies of Fe 2p after Cr adsorption at 724.6 eV, 720.4 eV, and 711.1 eV may be assigned to Fe(III), suggesting that Fe(II) on the surface of the material was oxidized to Fe(III) during the redox process. Hence, lower pH facilitated the transformation of Fe(III) to Fe(II) during the adsorption process. The measurements of the concentration of Fe(II) were performed in acidic solution (pH = 2) during the reaction (Fig. S4(a)†). Under H2SO4 treatment, the content of Fe(II) was considerably higher than that under HCl treatment with and without Cr(VI), and the results showed that the content of Fe(II) ions reached about 108.3 mg L−1 with no Cr(VI) in the H2SO4 system. When Cr(VI) was added, the concentration of Fe(II) ions decreased to about 9.24 mg L−1 in 7 h.
These interesting findings indicate that Fe3O4/Fe2N may have high reduction activity and can release a large amount of Fe(II) under H2SO4 treatment. As shown in Fig. 7, Fe3O4 alone has no effect on activation in the H2SO4 system. Also, both Fe3O4 and Fe2N are inefficient in reducing Cr(VI) in the HCl system. Therefore, this suggests that the high efficiency of WT(NH3) is due to the active sites at the interface of the two phases of Fe2N and Fe3O4 or Fe2N itself;53 this is consistent with the TEM results, showing that WT(NH3) has much more Fe3O4 and Fe2N interfaces.
According to the above-mentioned analysis and discussion, a possible mechanism for Cr(VI) removal by WT(NH3) is proposed (Fig. 9). First, Cr(VI) was partly absorbed by WT(NH3) in both the HCl and H2SO4 systems. Second, WT(NH3) released both Fe(III) and Fe(II). Meanwhile, some Fe(III) ions were converted to Fe(II) at a very low pH value. Third, the Cr(VI) ions were reduced to Cr(III) by Fe(II) (eqn (1)),31 which explained the presence of Cr(III) species in both the aqueous solution and on the surface of WT(NH3). This was also supported by the decrease in the concentration of Fe(II) in the solution with Cr(VI). In addition, SO42− could activate Fe2N or the interface of Fe2N and Fe3O4 and thus, it could accelerate the release of ferrous ions.
| 3Fe2+ + CrO42− + 4H2O → 3Fe3+ + Cr3+ + 8OH− | (1) |
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| Fig. 9 Preparation route for magnetic WT(NH3) and its mechanism for Cr(VI) removal in the H2SO4 system. | ||
From the above-mentioned results, waste toner can be utilized to prepare functional nanomaterials under different conditions. As indicated in this study, the good sorptive and reductive capacities for CrO42− are ascribed to the active sites and Fe3O4 and Fe2N in the nanocomposites. Since functional magnetic Fe3O4 shows good affinity for many heavy metals such as lead,54 arsenic55 and copper,56 the as-prepared toner-based sorbents can be used to remove a wide spectrum of heavy metals. Besides, the sorbents can be used to remediate wastewater contaminated by pharmaceuticals and other organic pollutants because Fe2N may promote catalytic degradation of organic compounds.53,57 Thus, waste toner can be potentially used for the removal of heavy metals and organic contaminants.
Footnote |
| † Electronic supplementary information (ESI) available. See DOI: 10.1039/c8ra05291c |
| This journal is © The Royal Society of Chemistry 2018 |