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Characterization and Applications of Innovative Sn-doped TiO2/AC and PPy-CS/Sn-doped TiO2 Nanocomposites as Adsorbent Materials
2021
Naser, Elham | AL-Mokaram, Ali | Hussein, Fadhela
This work explores the synthesis and characterization of two novel nanocomposites that can be used in various applications, such as aqueous solution adsorption of pollutants. The first nanocomposite consists of tin (Sn)-doped titanium dioxide (TiO2) on activated carbon, while the other one consists of polypyrole (PPy), chitosan (CS), and Sn-doped TiO2. A contrast was made of their effective adsorbent materials for the removal of Cibacron Brilliant Yellow dye from aqueous solutions. Different analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX), and Fourier transform - infrared (FT-IR) were used to analysis the nanocomposite samples. SEM images show that the average particle diameter of PPy-CS/Sn-doped TiO2 NC is 75 ± 3 nm, while Sn-doped TiO2/AC particles have an average diameter of 40 ± 2 nm. The greater PPy-CS/Sn-doped TiO2 nanocoposite particle diameter indicates that the polymers cover the Sn-doped TiO2 nanoparticles, which leads to higher in the diameter of the particles. The adsorption efficiency of Sn-doped TiO2/AC was higher than that of PPy-CS/Sn-doped TiO2 sample due to its smaller particle size which resulted in a higher surface area which provides more adsorption sites. However, both samples showed remarkable adsorption capacity, where the adsorption capacity of Sn-doped TiO2/AC and PPy-CS/Sn-doped TiO2 were 104 and 103 mg/g, respectively.
Show more [+] Less [-]Molecular level study of cadmium adsorption on dithiocarbamate modified chitosan
2021
Yin, Zheng | Qiu, Dong | Zhang, Meiyi
It has been shown that chemical modification of chitosan with sulfur (S) functional groups could significantly enhance its chelating capability with heavy metals included Cd(II). However, a molecular level understanding has been lacking. Here, we carried out X-ray absorption fine structure (XAFS) and Fourier transformed infrared (FTIR) spectra studies to bridge this knowledge gap. The results indicate that both Cd–O/N and Cd–S bonds exist in the complex of Cd(II) with dithiocarbamate chitosan (DTC-CTS). S functional groups (dithiocarbamate) in DTC-CTS play the major role in complexation with Cd(II) and S content affects the adsorption mechanism. At low S content, Cd(II) is mainly adsorbed on DTC-CTS as an outer-sphere complex with two monodentate amino groups and two water molecules in tetrahedral configuration. At high S content, Cd adsorption dominantly occurs by formation of an inner-sphere complex with two bidentate mononuclear S ligands in tetrahedral configuration. This investigation provides information on the effectiveness and mechanisms of Cd(II) removal that is critical for evaluating modified chitosan applications for stabilization of Cd(II) in surface water, groundwater, soils and sediments.
Show more [+] Less [-]Mesoporous cellulose-chitosan composite hydrogel fabricated via the co-dissolution-regeneration process as biosorbent of heavy metals
2021
Yang, Shujin | Liao, Y. | Karthikeyan, K.G. | Pan, X.J.
Developing low-cost and high-performance biosorbent for water purification continues drawing more and more attention. In this study, cellulose-chitosan composite hydrogels were fabricated via a co-dissolution and regeneration process using a molten salt hydrate (a 60 wt% aqueous solution of LiBr) as a solvent. The addition of chitosan not only introduced functionality for metal adsorption but also increased the specific surface area and improved the mechanical strength of the composite hydrogel, compared to pure cellulose hydrogel. Batch adsorption experiments indicated that the composite hydrogel with 37% cellulose and 63% chitosan exhibited an adsorption capacity of 94.3 mg/g (1.49 mmol/g) toward Cu²⁺ at 23 °C, pH 5, and initial metal concentration of 1500 mg/L, which was 10 times greater than the adsorption capacity of pure cellulose hydrogel. Competitive adsorption from a mixed metals solution revealed that the cellulose-chitosan composite hydrogel exhibited selective adsorption of the metals in the order of Cu²⁺ > Zn²⁺ > Co²⁺. This study successfully demonstrated an innovative method to fabricate biosorbents from abundant and renewable natural polymers (cellulose and chitosan) for removing metal ions from water.
Show more [+] Less [-]Sustainable ferrate oxidation: Reaction chemistry, mechanisms and removal of pollutants in wastewater
2021
Dar, Afzal Ahmed | Pan, Bao | Qin, Jiani | Zhu, Qiuhui | Lichtfouse, Eric | ʻUs̲mān, Muḥammad | Wang, Chuanyi
This review is intended to evaluate the use of ferrate (Fe(VI)), being a green coagulant, sustainable and reactive oxidant, to remove micro pollutants especially pharmaceutical pollutants in contaminated water. After a brief description of advanced oxidation processes, fundamental dimensions regarding the nature, reactivity, and chemistry of this oxidant are summarized. The degradation of contaminants by Fe(VI) involves several mechanisms and reactive agents which are critically evaluated. The efficiency and chemistry of Fe(VI) oxidation differs according to the reaction conditions and activation agent, such as soluble Fe(VI) processes, which involve Fe(VI), UV light, and electro-Fe(VI) oxidation. Fe(VI) application methods (including single dose, multiple doses, chitosan coating etc), and Fe(VI) with activating agents (including sulfite, thiosulfate, and UV) are also described to degrade the micro pollutants. Besides, application of Fe(VI) to remove pharmaceuticals in wastewater are intensely studied. Electrochemical prepared Fe(VI) has more wide application than wet oxidation method. Meanwhile, we elaborated Fe(VI) performance, limitations, and proposed innovative aspects to improve its stability, such as the generation of Fe(III), synergetic effects, nanopores entrapment, and nanopores capsules. This study provides conclusive direction for synergetic oxidative technique to degrade the micro pollutants.
Show more [+] Less [-]The incorporation of lemongrass oil into chitosan-nanocellulose composite for bioaerosol reduction in indoor air
2021
Mishra, Disha | Yadav, Ranu | Pratap Singh, Raghvendra | Taneja, Ajay | Tiwari, Rahul | Khare, Puja
The bioaerosols present in indoor air play a major role in the transmission of infectious diseases to humans, therefore concern about their exposure is increased recently. In this regard, the present investigation described the preparation of lemongrass essential oil (LGEO) loaded chitosan and cellulose nanofibers composites (CH/CNF) for controlling the indoor air bioaerosol. The evaluation of the inhibitory effect of the composite system on culturable bacteria of the indoor air was done at different sites (air volume from 30 m³ to 80 m³) and in different size fractions of aerosol (<0.25 μm–2.5 μm). The composite system had high encapsulation efficiency (88–91%) and citrals content. A significant reduction in culturable bacteria of aerosol (from 6.23 log CFUm⁻³ to 2.33 log CFUm⁻³) was observed in presence of cellulose nanofibers and chitosan composites. The bacterial strains such as Staphylococcus sp., Bacillus cereus, Bacillus pseudomycoides sp., Pseudomonas otitidis, and Pseudomonas sp. Cf0-3 in bioaerosols were inhibited dominantly due to the diffusion of aroma molecules in indoor air. The results indicate that the interaction of diffused aroma molecule from the composite system with bacterial strains enhanced the production of ROS, resulting in loss of membrane integrity of bacterial cells. Among different size fractions of aerosol, the composite system was more effective in finer size fractions (<0.25 μm) of aerosol due to the interaction of smaller aroma compounds with bacterial cells. The study revealed that LGEO loaded chitosan and cellulose nanofibers composites could be a good option for controlling the culturable bacteria even in small-sized respirable bioaerosol.
Show more [+] Less [-]Enhanced electrokinetic remediation of heavy metals contaminated soil by biodegradable complexing agents
2021
Wang, Yuchen | Han, Zijian | Li, Ang | Cui, Chongwei
In this study, an electrokinetic technique for remediation of Pb²⁺, Zn²⁺ and Cu²⁺ contaminated soil was explored using sodium alginate (SA) and chitosan (CTS) as promising biodegradable complexing agents. The highest Cu²⁺ (95.69%) and Zn²⁺ (95.05%) removal rates were obtained at a 2 wt% SA dosage, which demonstrated that SA significantly improved the Cu²⁺ and Zn²⁺ removal efficiency during electrokinetic process. The abundant functional groups of SA allowed metal ions desorption from soil via ion-exchange, complexation, and electrolysis. Pb²⁺ ions were difficult to remove from soil by SA due to the higher gelation affinity with Pb²⁺ than Cu²⁺ and Zn²⁺, despite the Pb²⁺ exchangeable fraction partially transforming to the reducible and oxidizable fractions. CTS could complex metal ions and migrate into the catholyte under the electric field to form crosslinked CTS gelations. Consequently, this study proved the suitability of biodegradable complexing agents for treating soil contaminated with heavy metals using electrokinetic remediation.
Show more [+] Less [-]TiO2/CTS/ATP adsorbent modification and its application in adsorption-ultrafiltration process for dye wastewater purification
2021
Wang, Zhihong | Wu, Zekun | Zhi, Xujun | Tu, Tianfu | Nie, Jinxu | Du, Xing | Luo, Yunlong
Industrial dyeing produces highly polluting wastewater and threatens the environment. Effective treatment of dyeing wastewater is a crucial step to prevent toxic chemicals from entering receiving waters. This study aimed to assess a modified attapulgite (ATP)-based adsorbent for dyeing wastewater purification by introducing chitosan (CTS) and titanium dioxide (TiO₂) into the adsorbent material named TiO₂/CTS/ATP. It was found that after modification, the adsorbent showed a lower hydrophilicity, as demonstrated by an increase in the water contact angle from 9.1° to 42°, which could reduce the water adsorption tendency and potentially facilitate contaminants adherence. The modification also led to a significantly increased specific surface area of 79.111 m²/g from 3.791 m²/g and exhibited more uniform and smaller particle size (reduced from 3.99 to 2.52 μm). When the TiO₂/CTS/ATP adsorbent was applied to the adsorption of Congo red solution, the adsorption efficiency was observed to reach to 97.6% at the dosage of 0.5 g/L. Furthermore, the combination of adsorption and ultrafiltration was able to achieve 99% Congo red removal. Adsorption pretreatment prior to the ultrafiltration also enabled to reduce membrane fouling, increased the reversible membrane fouling, and resulted in a considerably lower transmembrane pressure as compared with the direct ultrafiltration filtration system.
Show more [+] Less [-]Development of chitosan-coated nanoemulsions of two sulfides present in onion (Allium cepa) essential oil and their nematicidal activities against the pine wood nematode, Bursaphelenchus xylophilus
2021
Yang, Eunhye | Yi, Chae-u | Chang, Pahn-Shick | Park, Il-Kwon
Pine wood nematode, Bursaphelenchus xylophilus, is a plant parasitic nematode which causes severe damage to several Pinus species. Two natural compounds, dipropyl trisulfide (DPTS) and methyl propyl trisulfide (MPTS), showed strong nematicidal activity against the pine wood nematode, presenting 4.24 and 17.81 μg/mL LC₅₀ values, respectively. However, hydrophobicity and low stability have limited their practical use in the field as nematicides. To overcome these problems, chitosan-coated nanoemulsions of DPTS and MPTS were developed. The optimum chitosan concentration for the delivery system of the two sulfides was 0.5%. Optimized chitosan-coated nanoemulsions of sulfides have a uniform size distribution (mean diameter = 203.7 and 207.7 nm, mean polydispersity index = 0.176 and 0.178) with sufficient colloidal stability (mean zeta potential = +40 and +45 mV). The LC₅₀ values of DPTS and MPTS nanoemulsions coated with 0.5% chitosan against the pine wood nematode were 5.01 and 16.60 μg/mL, respectively. In addition, chitosan coating improved the long-term storage stability and persistence of nematicidal activity of the nanoemulsions. This study indicates that the chitosan-coated nanoemulsion is a suitable formulation for sulfides as novel nematicides against the pine wood nematode for field application.
Show more [+] Less [-]Methacrylic functionalized hybrid carbon nanomaterial for the selective adsorption and detection of progesterone in wastewater
2021
Cui, Xia | Shu, Hua | Wang, Lu | Chen, Guoning | Han, Jili | Hu, Qianqian | Bashir, Kamran | Luo, Zhimin | Chang, Chun | Zhang, Jia | Fu, Qiang
Progesterone, an endocrine-disrupting chemical, has been frequently detected in wastewater for decades, posing a serious threat to ecological and human health. However, it is still a challenge to achieve the effective detection of progesterone in complex matrices water samples. In this study, a novel adsorbent CNT@CS/P(MAA) was prepared by grafting methacrylic polymers on the surface of modified carbon nanomaterials. Compared with other reported materials, the hybrid carbon nanomaterial could selectively identify the progesterone in the complex industrial pharmaceutical wastewater, and its adsorption performance is almost independent of the pH and environmental temperature. In addition, this nanomaterial could be reused with a good recovery rate. The prepared nanomaterials were characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, nitrogen adsorption and desorption experiments, and thermogravimetric analysis. The results confirmed that the methacrylic polymers and chitosan layer were successfully grafted on the surface of carbon nanotubes. Adsorption isotherms, adsorption kinetics, and selectivity tests showed that CNT@CS/P(MAA) had a high adsorption capacity (44.45 mg·g⁻¹), a fast adsorption rate and a satisfied selectivity for progesterone. Then, CNT@CS/P(MAA) was used as solid phase extraction sorbent and combined with HPLC to enrich progesterone from the wastewater samples. Under the optimum conditions, a good linearity was obtained with the correlation coefficient was 0.9998, and the limit of detection was 0.003 ng·mL⁻¹. Therefore, this method could be used for the selective and effective detection of progesterone in industrial wastewater with complex substrates and provided a new method for the detection of progesterone in other environmental waters.
Show more [+] Less [-]Enhanced phytoremediation of uranium-contaminated soils by Indian mustard (Brassica juncea L.) using slow release citric acid
2021
Wang, Guanghui | Wang, Bing | Fan, Wenzhe | Deng, Nansheng
In this study, a novel slow release carrier for the controlled release of citric acid (CA), hydroxypropyl chitosan-graft-carboxymethyl-β-cyclodextrin (HPCS-g-CMCD) was synthesized by the grafting reaction of carboxymethyl-β-cyclodextrin (CMCD) with hydroxypropyl chitosan (HPCS), and the structural characteristics of HPCS-g-CMCD were confirmed by FT-IR, TGA, and NMR. Based on HPCS-g-CMCD and CA, slow release citric acid (SRCA) was prepared by a spray drying method. HPCS-g-CMCD carrier has a better slow release performance for CA compared to HPCS and CMCD, and CA release mechanism was attributed to a Fickian diffusion. Furthermore, the release behavior of uranium in contaminated soil could be effectively controlled by SRCA. The effects of SRCA on improving the phytoremediation capacity in uranium-contaminated soil were investigated using Brassica juncea, which were grown in pots containing soil with uranium at 56 mg kg⁻¹. After 50 days of growth, 5 mmol kg⁻¹ of CA, SRCA I, SRCA II, and SRCA III was applied, respectively. The results showed that slow release citric acid could enhance the uptake of uranium in Indian mustard. Uranium concentration in the root with SRCA I treatment was increased by 80.25% compared to the control, and the uranium removal efficiency of the SRCA I treatment was 1.66-fold greater than that of the control. Simultaneously, the leaching loss of uranium in SRCA I-treated soil was decreased by 37.35% compared to CA-treated soil. As a promising remediation strategy, SRCA-assisted phytoremediation may provide a kind of feasible technology with low leaching risk for remediation of uranium-contaminated soils.
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