Fumihiko
Ogata
a,
Kazuki
Sugimura
a,
Noriaki
Nagai
a,
Chalermpong
Saenjum
bc,
Keiji
Nishiwaki
a and
Naohito
Kawasaki
*ad
aFaculty of Pharmacy, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan. E-mail: kawasaki@phar.kindai.ac.jp
bFaculty of Pharmacy, Chiang Mai University, Suthep Road, Muang District, Chiang Mai, 50200, Thailand
cCenter of Excellence for Innovation in Analytical Science and Technology for Biodiversity-based Economic and Society (I-ANALY-S-T_B.BES-CMU), Chiang Mai University, Chiang Mai, 50200, Thailand
dAntiaging Center, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan
First published on 4th December 2023
This research aims to evaluate waste cotton and polyester as effective potential adsorbents for the removal of crystal violet (CV) from aqueous phases. Carbonaceous materials (VCP1000 or VC1000) from waste cotton and polyester were prepared at different calcination temperatures, and their characteristics were assessed using scanning electron microscopy, pHpzc, surface functional groups, and specific surface areas. The values of the parameters of VCP1000 or VC1000 were greater than those of other adsorbents. Additionally, adsorption experiments were performed in batch mode, and various parameters, including initial concentration, adsorption temperature, contact time, and pH, were demonstrated in this study. The amount of CV adsorbed onto VCP1000 and/or VC1000 was higher than those onto other VCP and/or VC adsorbents. The adsorption equilibrium of CV was achieved within 24 h. These data were fitted to the pseudo-second-order model (correlation coefficient: 0.991–0.995). The adsorption capacity increased with increasing adsorption temperatures (7 °C < 25 °C < 45 °C). The adsorption isotherm data were fitted to both the Langmuir and Freundlich models as well. The adsorption of CV using VCP1000 or VC1000 was significantly influenced by pH under our experimental conditions. Finally, elemental distribution and binding energy analyses were conducted to elucidate the adsorption mechanisms of CV. The obtained results indicate that the adsorbed CV was presented onto the VCP1000 and/or VC1000 surface. Collectively, these obtained results show that VCP1000 or VC1000 holds promise for the removal of CV from aqueous phases.
Sustainability spotlightGoal 12, specifically focused on responsible consumption and production, aims to foster the development of innovative recycling technologies for reducing waste worldwide. In this study, we focus on textile products. The most produced fibers, such as cotton and polyester, were produced at 26 and 55 million tons, respectively. Interwoven cotton and polyester blends are extremely difficult to recycle and/or handle to reproduce new yarns. Hence, the development of value-added products, such as novel adsorbents derived from waste cotton and polyester for the purpose of removing CV from aqueous solutions, has the potential to make a substantial contribution to the realization of the SDGs and the purification of wastewater containing CV. |
Dyes possess intricate molecular structures and exhibit resilience against aerobic decomposition, remaining stable when exposed to light, heat, and oxidizing agents.7 Dyes can be categorized into three different classes: cationic, anionic, and nonionic dyes. In particular, cationic dyes are more dangerous than the other types. Crystal violet (CV) is a widely recognized triarylmethane dye among the different types of cationic dyes. CV accumulation can reportedly cause harmful effects because of its carcinogenic and mutagenic nature.9,10 Therefore, CV must be removed from aqueous phases.
Many researchers have reported several treatment processes for removing harmful materials, including dyes (CV), over the last few decades. Such technologies include physical, chemical, and physicochemical treatments (e.g., adsorption, membrane filtration, ion exchange, electrochemical techniques, coagulation, flocculation, reverse osmosis, ozonation, chemical oxidation, activated sludge, and bacterial action).11–13 Among these methods, adsorption stands out as a prominent technique in green chemistry for removing pollutants from aqueous phases. This is primarily due to its cost-effectiveness, adaptability with minimal sludge generation, straightforwardness, effectiveness, and rapidity.13,14 Furthermore, it typically does not generate by-products with substantial environmental hazard risks.15–17
Previous research has focused on assessing affordable, readily available, sustainable waste biomass-based adsorbents with high adsorption capacities. This approach was prompted by the drawbacks associated with the widely used adsorbent, activated carbon, which is renowned for its costly production and the need for regeneration during the adsorption process.18,19
In 2015, all United Nations member states adopted the Sustainable Development Goals (SDGs) to establish a sustainable society. Goal 12, specifically focused on responsible consumption and production, aims to foster the development of innovative recycling technologies for reducing waste worldwide. Therefore, numerous researchers have directed their attention towards renewable materials, including agricultural waste and residues, to assess their potential for converting these discarded resources into value-added products. Preparing adsorbents based on waste biomass is one of the most useful recycling technologies to achieve the SDGs.
In this study, we focus on textile products. The most produced fibers, such as cotton and polyester, were produced at 26 and 55 million tons, respectively.20 According to a previous report, the yearly fiber production for consumer clothing was approximately 53 million tons, with a significant portion of 73% being discarded in landfills or waste incinerators.21 Additionally, interwoven cotton and polyester blends are extremely difficult to recycle and/or handle to reproduce new yarns.22–24 Hence, the development of value-added products, such as novel adsorbents derived from waste cotton and polyester for the purpose of removing CV from aqueous solutions, has the potential to make a substantial contribution to the realization of the SDGs and the purification of wastewater containing CV.
Therefore, this study aims to prepare an adsorbent produced from waste cotton and/or polyester treated with calcination, and its characteristics, including morphology, specific surface area, surface functional group, and pHpzc, were evaluated. Furthermore, this paper presents a demonstration of the adsorption capacity of CV using the prepared adsorbent. The effect of factors, including contact time, initial concentration, temperature, and pH level, on the adsorption of CV was also evaluated. Furthermore, kinetics and equilibrium modeling, elemental distribution, and binding energy assessment were conducted to gain a comprehensive understanding of the adsorption mechanism of CV onto the chosen adsorbents. Finally, the purpose of this study is to transform waste cotton/polyester into useful adsorbents for purification of wastewater including CV.
The concentration of CV was measured through the following procedures. The equilibrium concentration of CV in the filtered sample solution after the adsorption reaction was determined using an ultraviolet-visible spectrophotometer UV-1280 (Shimadzu, Japan). The maximum absorption wavelength was 590 nm. The calibration curve was prepared over the range of 0.1–5.0 mg L−1 and the correlation coefficient was determined to be over 0.999. Furthermore, the adsorbed CV was quantified by comparing concentrations before and after adsorption at various levels. All data are expressed as mean ± standard error (n = 3–4).
Additionally, we could observe that VCP was clearly thermally decomposed at approximately 250 °C in this study (Fig. 2). These data supported the changes of the SEM image with calcination temperature.
In Table 1, the physicochemical properties of the adsorbents are presented. The value of pHpzc increased with increasing calcination temperature. Additionally, the basic functional groups and specific surface areas also increased with increasing calcination temperature. Conversely, acidic functional groups exhibited different changes in the prepared adsorbents compared with other properties. FT-IR spectra of VCPs and VCs are shown in Fig. 3. O–H stretching vibration (3200–3550 cm−1), O–H bending (850–1140 cm−1), and C–O stretching vibration (1700–1720 cm−1) were found in VCP and VC, whereas no characteristic peaks were found in calcined VCP and VC samples. In this study, the specific functional groups were not determined by FT-IR spectra. Therefore, further studies are necessary for determining the specific functional groups of carbonaceous materials prepared from waste cotton in detail.
Adsorbents | pHpzc | Basic functional groups (mmol g−1) | Acidic functional groups (mmol g−1) | Specific surface area (m2 g−1) |
---|---|---|---|---|
VCP | 6.72 | 0.00 | 0.03 | N.D. |
VCP600 | 6.60 | 0.08 | 0.26 | 583 |
VCP800 | 7.29 | 0.29 | 0.28 | 634 |
VCP1000 | 7.25 | 0.30 | 0.30 | 823 |
VC | 6.42 | 0.00 | 0.11 | N.D. |
VC600 | 7.04 | 0.26 | 0.31 | 508 |
VC800 | 7.78 | 0.63 | 0.23 | 639 |
VC1000 | 9.89 | 0.82 | 0.17 | 660 |
Fig. 4 The amount of CV adsorbed onto adsorbents. Initial concentration: 50 mg L−1, sample volume: 50 mL, adsorbent: 0.02 g, temperature: 25 °C, contact time: 24 h, 100 rpm. |
Pseudo-first-order32 and pseudo-second-order models33 are commonly applied to predict adsorption mechanisms. These models demonstrate the relationship between the amount of CV adsorbed as a function of time.32 We applied these models to analyze the data acquired from adsorption experiments, enabling us to establish kinetic parameters.
ln(qe − qt) = ln(qe) − k1t | (1) |
(2) |
The data obtained for kinetic models are shown in Table 2. The correlation coefficient of the pseudo-second-order-model (0.991–0.995) was higher than that of the pseudo-first-order-model (0.941–0.963). Furthermore, the values of qe (VCP1000, 99.4 mg g−1; VC1000, 114.8 mg g−1) estimated from experimental data also strongly align with the pseudo-second-order model (VCP1000, 103.5 mg g−1; VC1000, 117.8 mg g−1) compared with the pseudo-first-order model (VCP1000, 75.1 mg g−1; VC1000, 70.4 mg g−1). According to the results, CV adsorption onto VCP1000 or VC1000 may have occurred chemically.
Adsorbents | q e,exp (mg g−1) | Pseudo-first-order model | Pseudo-second-order model | ||||
---|---|---|---|---|---|---|---|
q e,cal (mg g−1) | k 1 (h−1) | r | q e,cal (mg g−1) | k 2 (mg g−1 h−1) | r | ||
VCP1000 | 99.4 | 75.1 | 0.103 | 0.963 | 103.5 | 3.2 × 10−3 | 0.991 |
VC1000 | 114.8 | 70.4 | 0.087 | 0.941 | 117.8 | 6.2 × 10−3 | 0.995 |
Fig. 6 presents the adsorption isotherms of CV onto VCP1000 or VC1000. The amount of CV adsorbed increased with increasing adsorption temperatures (7 °C < 25 °C or 45 °C). The amount adsorbed at 45 °C slightly increased or did not significantly change compared with that at 25 °C. These patterns indicate that the saturated adsorption capacity of CV occurred within the temperature range of 25 °C to 45 °C.
The Langmuir and Freundlich isotherm models also provide valuable insights into adsorption mechanisms by estimating the adsorption of an adsorbate as a function of equilibrium concentration.34 The Langmuir isotherm model assumes that adsorption takes place at specific homogeneous adsorption sites.35 Meanwhile, at the same time, the Freundlich isotherm model is applicable for characterizing adsorption on heterogeneous surfaces.36
(3) |
(4) |
The Langmuir and Freundlich constants for the adsorption of CV are presented in Table 3. Under our experimental conditions, the Langmuir correlation coefficient (r = 0.954–0.996) and Freundlich correlation coefficient (r = 0.940–0.993) were found to be suitable for fitting the data. The value of qmax using both VCP1000 and VC1000 increased with increasing adsorption temperatures. In addition, the value of KF increased as the adsorption temperature increased, which indicated that the permeability of CV onto the adsorbent was enhanced by the greater contribution of kinetic energy at higher adsorption temperatures.11
Adsorbents | Temperature (°C) | Langmuir isotherm model | Freundlich isotherm model | ||||
---|---|---|---|---|---|---|---|
q max (mg g−1) | K L (L mg−1) | r | 1/n | logKF | r | ||
VCP1000 | 7 | 43.9 | 0.17 | 0.996 | 0.31 | 1.08 | 0.961 |
25 | 74.8 | 0.60 | 0.959 | 0.36 | 1.39 | 0.993 | |
45 | 76.6 | 2.75 | 0.960 | 0.23 | 1.61 | 0.944 | |
VC1000 | 7 | 44.7 | 0.34 | 0.954 | 0.28 | 1.19 | 0.969 |
25 | 97.2 | 3.83 | 0.957 | 0.15 | 1.81 | 0.981 | |
45 | 117.6 | 1.62 | 0.983 | 0.28 | 1.73 | 0.940 |
These observed trends were similar to the adsorption isotherm data presented in Fig. 6.
Furthermore, the occurrence of CV adsorption was readily observed when the 1/n value varied within the range of 0.1 to 0.5.35 In this study, the value of the 1/n range was from 0.15 to 0.36, which indicated that CV was easily adsorbed onto VCP1000 or VC1000. In conclusion, the adsorption of CV onto the prepared adsorbents was controlled by multiple processes that involved both physical and chemical adsorption.37
A previous study reported that the hydrogen bonding, electrostatic interaction, and π–π interactions were related to the adsorption mechanism of 4-nitroaniline onto MCM-48,37 which indicates that the relationship between adsorbent surface roughness and contact angle is important to elucidate the adsorption mechanism in detail. In this study, the obtained results suggest that the properties of the VCP1000 and/or VC1000 surface significantly affect the adsorption mechanism of CV from aqueous phases. As a result, we evaluated the binding energy and elemental distribution analysis both before and after the adsorption of CV (Fig. 7–9). The morphology of the VCP1000 and/or VC1000 surface slightly changed before and after adsorption (Fig. 7). Therefore, the CV was presented onto the adsorbent surface following the adsorption process.
Fig. 7 The SEM images of VCP1000 and VC1000 before and after adsorption. Initial concentration, 100 mg L−1; sample volume, 50 mL; adsorbent, 0.02 g; temperature, 25 °C; contact time, 24 h, 100 rpm. |
Subsequently, carbon (C) and nitrogen (N) distribution intensities were measured. As shown in Fig. 8, the intensities of C and N, which were component elements of the CV structure, slightly increased after adsorption compared with those before adsorption (the warm and cold colors indicate high and low concentrations of CV, respectively). Additionally, the binding energies of C and N, which were slightly or not detected before adsorption, were clearly detected after the adsorption of CV in this study (Fig. 9). Collectively, the physicochemical characteristics of the adsorbent surface exhibited a notable correlation with CV adsorption.
Fig. 10 shows the effect of pH on the adsorption of CV onto VCP1000 or VC1000, the amount of adsorbed CV using VCP1000 slightly decreased or did not change. Meanwhile, a quite opposite trend was observed when using VC1000 under our experimental conditions. As mentioned, CV adsorption is possibly related to the physicochemical characteristics of the adsorbent surface. The interaction of CV with the prepared adsorbents depended on the solution pH. The adsorption capacity of CV changed with the changing surface charges of the prepared adsorbents from positive to negative.1 For VCP1000, the values of pHpzc, basic functional groups, acidic functional groups, and specific surface area were 7.25, 0.30 mmol g−1, 0.30 mmol g−1, and 823 m2 g−1, respectively, as shown in Table 1. According to our theory, alcoholic/phenolic hydroxyl groups (–OH) predominated among the functional groups in the adsorbent surface, with the remaining carbonyl groups (–COO) coming from polyester and cellulose (derived from cotton). pHpzc generally strongly affects the adsorption capacity of VC.11 However, the observed trend in adsorption capacity was not different from those previously reported in other studies.1,7 In other words, the adsorption capacity of CV was not significantly changed between pH 2 and pH 8. Therefore, physical properties, including the specific surface area, significantly affect the adsorption capacity of CV compared with other parameters in this study. However, further study is required to clarify the mechanisms by which VCP1000 adsorbs CV. In the case of VC1000, the pHpzc, basic functional groups, acidic functional groups, and specific surface area were 9.89, 0.82 mmol g−1, 0.17 mmol g−1, and 660 m2 g−1, respectively (Table 1). In particular, the number of basic functional groups was approximately five times greater compared with the number of acidic functional groups. The value of pHpzc was less than 9.89, implying that VC1000 was acidic and easily protonated. Additionally, the occurrence of excessive H+ (H3O+) ions might have slightly caused the repulsion between the positively charged VC1000 and CV in the aqueous phase. Meanwhile, at high alkaline pH, the increase in HO− ions caused deprotonation, which led to a gradually negative charge of VC1000 under our experimental conditions.1,11 Therefore, the amount of CV adsorbed increased with increasing solution pH.
Samples | Adsorption capability (mg g−1) | pH | Temperature (°C) | Initial concentration (mg L−1) | Contact time (h) | Adsorbent (g L−1) | References |
---|---|---|---|---|---|---|---|
Charred rice husks | 62.85 | — | r.t. | 50 | 24 | 1.0 | Homagai et al., 2022 |
Nascent rice husk | 24.4781 | — | 25 | 500 | 24 | 16.7 | Quansah et al., 2020 |
Mango stone biocomposite | 352.79 | 8.0 | 33 | 500 | 1 | 0.5 | Shoukat et al., 2017 |
Coconut husk | 454.54 | 5.0 | r.t. | 400 | 3 | 1.0 | Sultana et al., 2022 |
Saw dust | 37.83 | — | 23 | 100 | 5 | 4.0 | Parab et al., 2009 |
Coniferous pine bark | 32.78 | 8.0 | 30 | 50 | 2 | 2.0 | Ahmad, 2009 |
FCMFs | 872 | 7.0 | 25 | 350 | 1 | 0.2 | Baghdadi et al., 2016 |
VCP1000 | 74.8 | ∼5.0 | 25 | 100 | 24 | 0.4 | This study |
VC1000 | 92.8 | ∼5.0 | 25 | 100 | 24 | 0.4 | This study |
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