A portable electrochemical sensor was developed to determine xylazine in spiked beverages by adsorptive stripping voltammetry (AdSV). The sensor was based on a graphene nanoplatelets-modified screen-printed carbon electrode (GNPs/SPCE). The electrochemical behavior of xylazine at the GNPs/SPCE was an adsorption-controlled irreversible oxidation reaction. The loading of graphene nanoplatelets (GNPs) on the modified SPCE, electrolyte pH, and AdSV accumulation potential and time were optimized. Under optimal conditions, the GNPs/SPCE provided high sensitivity, linear ranges of 0.4-6.0 mg L-1 (r = 0.997) and 6.0-80.0 mg L-1 (r = 0.998) with a detection limit of 0.1 mg L-1 and a quantitation limit of 0.4 mg L-1. Repeatability was good. The accuracy of the proposed sensor was investigated by spiking six beverage samples at 1.0, 5.0, and 10.0 mg L-1. The recoveries from this method ranged from 80.8 ± 0.2-108.1 ± 0.3 %, indicating the good accuracy of the developed sensor. This portable electrochemical sensor can be used to screen for xylazine in beverage samples as evidence in cases of sexual assault or robbery.
Improving the stability of cuprous oxide (Cu2 O) is imperative to its practical applications in artificial photosynthesis. In this work, Cu2 O nanowires are encapsulated by metal-organic frameworks (MOFs) of Cu3 (BTC)2 (BTC=1,3,5-benzene tricarboxylate) using a surfactant-free method. Such MOFs not only suppress the water vapor-induced corrosion of Cu2 O but also facilitate charge separation and CO2 uptake, thus resulting in a nanocomposite representing 1.9 times improved activity and stability for selective photocatalytic CO2 reduction into CH4 under mild reaction conditions. Furthermore, direct transfer of photogenerated electrons from the conduction band of Cu2 O to the LUMO level of non-excited Cu3 (BTC)2 has been evidenced by time-resolved photoluminescence. This work proposes an effective strategy for CO2 conversion by a synergy of charge separation and CO2 adsorption, leading to the enhanced photocatalytic reaction when MOFs are integrated with metal oxide photocatalyst.
Chitosan-deep eutectic solvent (DES) beads were prepared from chitosan and DESs. The DESs used were choline chloride-urea (DES A) and choline chloride-glycerol (DES B). Both chitosan-DES beads were used to remove malachite green (MG) dye from an aqueous solution. The optimum pH for chitosan-DES A was recorded at pH 8.0 while optimum pH for chitosan-DES B was pH 9.0. The maximum adsorption capacity obtained for chitosan-DES A and chitosan-DES B were 6.54 mg/g and 8.64 mg/g, respectively. The optimum conditions for both chitosan-DES beads to remove MG were 0.08 g of adsorbent and 20 min of agitation time. Five kinetic models were applied to analyse the data and the results showed that the pseudo-second-order and intraparticle diffusion model fitted best with R2 > 0.999. For the adsorption capacity, results show that the Freundlich and Langmuir adsorption isotherms fitted well with chitosan-DES A and chitosan-DES B, respectively. The maximum adsorption capacities (qmax) obtained from chitosan-DES A and chitosan-DES B were 1.43 mg/g and 17.86 mg/g, respectively. Desorption indicated good performance in practical applications.
In current research work, chitosan (Chi) was subjected to subsequent physical and chemical modifications by incorporating kaolin clay (KA) into its polymeric structure, and crosslinking process with a covalent cross-linker namely epichlorohydrin (ECH) respectively. The final product of crosslinked chitosan-epichlorohydrin/kaolin (Chi-ECH/KA) composite was successfully applied for color removal and chemical oxygen demand (COD) reduction of textile dye namely reactive blue 19 dye (RB19) from aqueous environment. The influence of pertinent parameters, i.e. A: Chi-ECH/KA dose (0.02-0.1 g), B: pH (4-10), and C: time (5-30 min) on the RB19 color removal and COD reduction were statistically optimized by using response surface methodology with Box-Behnken design (RSM-BBD). The experimental data of the adsorption kinetic and the adsorption isotherm demonstrated a better fitness to pseudo-second order model and Langmuir isotherm model respectively. Excellent absorption ability of 560.9 mg/g was recorded for Chi-ECH/KA composite. The calculated thermodynamic functions clarified that the RB19 adsorption process was endothermic and spontaneous in nature. The mechanism of RB19 adsorption onto the Chi-ECH/KA may include electrostatic interactions, hydrogen bonding, Yoshida H-bonding, and n-π interactions. This study introduces Chi-ECH/KA composite as an eco-friendly, potential and multi-function composite bio adsorbent for removal of textile dye and COD reduction from aqueous environment.
Indoor air pollution with toxic volatile organic compounds (VOCs) and fine particulate matter (PM2.5) is a threat to human health, causing cancer, leukemia, fetal malformation, and abortion. Therefore, the development of technologies to mitigate indoor air pollution is important to avoid adverse effects. Adsorption and photocatalytic oxidation are the current approaches for the removal of VOCs and PM2.5 with high efficiency. In this review we focus on the recent development of indoor air pollution mitigation materials based on adsorption and photocatalytic decomposition. First, we review on the primary indoor air pollutants including formaldehyde, benzene compounds, PM2.5, flame retardants, and plasticizer: Next, the recent advances in the use of adsorption materials including traditional biochar and MOF (metal-organic frameworks) as the new emerging porous materials for VOCs absorption is reviewed. We review the mechanism for mitigation of VOCs using biochar (noncarbonized organic matter partition and adsorption) and MOF together with parameters that affect indoor air pollution removal efficiency based on current mitigation approaches including the mitigation of VOCs using photocatalytic oxidation. Finally, we bring forward perspectives and directions for the development of indoor air mitigation technologies.
The recent implication of circular economy in Australia spurred the demand for waste material utilization for value-added product generations on a commercial scale. Therefore, this experimental study emphasized on agricultural waste biomass, rice husk (RH) as potential feedstock to produce valuable products. Rice husk biochar (RB) was obtained at temperature: 180 °C, pressure: 70 bar, reaction time: 20 min with water via hydrothermal carbonization (HTC), and the obtained biochar yield was 57.9%. Enhancement of zeta potential value from - 30.1 to - 10.6 mV in RB presented the higher suspension stability, and improvement of surface area and porosity in RB demonstrated the wastewater adsorption capacity. Along with that, an increase of crystallinity in RB, 60.5%, also indicates the enhancement of the catalytic performance of the material significantly more favorable to improve the adsorption efficiency of transitional compounds. In contrast, an increase of the atomic O/C ratio in RB, 0.51 delineated high breakdown of the cellulosic component, which is favorable for biofuel purpose. 13.98% SiO2 reduction in RB confirmed ash content minimization and better quality of fuel properties. Therefore, the rice husk biochar through HTC can be considered a suitable material for further application to treat wastewater and generate bioenergy.
Cellulose with ample hydroxyl groups is considered as a promising supportive biopolymer for fabricating cellulose supported promising magnetic sorbents (CMS) for magnetic solid-phase extraction (MSPE). The easy recovery via external magnetic field, and recyclability of CMS, associated with different types and surface modifications of cellulose has made them a promising sorbent in the field of solid-phase extraction. CMS based sorbent can offer improved adsorption and absorption capabilities due to its high specific surface area, porous structure, and magnetic attraction feature. This review mainly focuses on the fabrication strategies of CMS using magnetic nanoparticles (MNPs) and various forms of cellulose as a heterogeneous and homogeneous solution either in alkaline mediated urea or Ionic liquids (ILs). Moreover, CMS will be elaborated based on their structures, synthesis, physical performance, and chemical attraction of MNPs and their MSPE in details. The advantages, challenges, and prospects of CMS in future applications are also presented.
The process parameters of microwave-induced hydrothermal carbonization (MIHTC) play an important role on the hydrothermal chars (hydrochar) yield. The effect of reaction temperature, reaction time, particle size and biomass to water ratio was optimized for hydrochar yield by modeling using the central composite design (CCD). Further, the rice straw and hydrochar at optimum conditions have been characterized for energy, chemical, structural and thermal properties. The optimum condition for hydrochar synthesis was found to be at a 180 °C reaction temperature, a 20 min reaction time, a 1:15 weight per volume (w/v) biomass to water ratio and a 3 mm particle size, yielding 57.9% of hydrochar. The higher heating value (HHV), carbon content and fixed carbon values increased from 12.3 MJ/kg, 37.19% and 14.37% for rice straw to 17.6 MJ/kg, 48.8% and 35.4% for hydrochar. The porosity, crystallinity and thermal stability of the hydrochar were improved remarkably compared to rice straw after MIHTC. Two characteristic peaks from XRD were observed at 2θ of 15° and 26°, whereas DTG peaks were observed at 50⁻150 °C and 300⁻350 °C for both the materials. Based on the results, it can be suggested that the hydrochar could be potentially used for adsorption, carbon sequestration, energy and agriculture applications.
Cephalexin (CFX) antibiotic, a potent pharmaceutical water pollutant, was efficiently removed by activated carbon (AC) derived from a single-step pyrolysis of phosphoric acid-activated chitin. Experimental conditions such as temperature, CFX initial concentration, and solution pH were screened in batch adsorption. Phosphoric acid activation of chitin and subsequent pyrolysis tailored the Brunauer-Emmett-Teller surface area, total pore volume, and average pore diameter to 1199.02 m2/g, 0.641 cm3/g, and 21.37 Å, respectively. The Langmuir isotherm adequately described the equilibrium data for CFX adsorption on chitin-AC, with an R2 of 0.99 and a monolayer capacity of 245.19 mg/g at 50 °C. Chitin-AC showed higher adsorption capacity compared with other ACs derived from industrial and agricultural precursors. When activated by phosphoric acid, chitin-AC featured functional multi-sites for vast antibiotic adsorption treatment. Overall, chitin-AC could be a promising adsorbent for removal of CFX.
The aim of this study was ultrasound assisted removal of Ceftriaxone sodium (CS) based on CCD model. Using sonochemical synthesized Bi2WO6 implanted on graphitic carbon nitride/Multiwall carbon nanotube (g-C3N4/MWCNT/Bi2WO6). For this purpose g-C3N4/MWCNT/Bi2WO6 was synthesized and characterized using diverse approaches including XRD, FE-SEM, XPS, EDS, HRTEM, FT-IR. Then, the contribution of conventional variables including pH, CS concentration, adsorbent dosage and ultrasound contact time were studied by central composite design (CCD) under response surface methodology (RSM). ANOVA was employed to the variable factors, and the most desirable operational conditions mass provided. Drug adsorption yield of 98.85% obtained under these defined conditions. Through conducting five experiments, the proper prediction of the optimum point were examined. The respective results showed that RSD% was lower than 5% while the t-test confirmed the high quality of fitting. Langmuir isotherm equation fits the experimental data best and the removal followed pseudo-second order kinetics. The estimation of the experimentally obtained maximum adsorption capacities was 19.57 mg.g- of g-C3N4/MWCNT/Bi2WO6 for CS. Boundary layer diffusion explained the mechanism of removal via intraparticle diffusion.
Over the past decade, science has experienced a growing rise in nanotechnology with ground-breaking contributions. Through various laborious technologies, nanomaterials with different architectures from 0 D to 3 D have been synthesized. However, the 3 D flower-like organic-inorganic hybrid nanomaterial with the most direct one-pot green synthesis method has attracted widespread attention and instantly become research hotspot since its first allusion in 2012. Mild synthesis procedure, high surface-to-volume ratio, enhanced enzymatic activity and stability are the main factor for its rapid development. However, its lower mechanical strength, difficulties in recovery from the reaction system, lower loading capacity, poor reusability and accessibility of enzymes are fatal, which hinders its wide application in industry. This review first discusses the selection of non-enzymatic biomolecules for the synthesis of hybrid nanoflowers followed by the innovative advancements made in organic-inorganic hybrid nanoflowers to overcome aforementioned issues and to enhance their extensive downstream applications in transduction technologies. Besides, the role of hybrid nanoflower has been successfully utilized in many fields including, water remediation, biocatalyst, pollutant adsorption and decolourization, nanoreactor, biosensing, cellular uptake and others, accompanied with several quantification technologies, such as ELISA, electrochemical, surface plasmon resonance (SPR), colorimetric, and fluorescence were comprehensively reviewed.
The influence of an anionic surfactant, a cationic surfactant, and salinity on adsorbed methane (CH4) in shale was assessed and modeled in a series of systematically designed experiments. Two cases were investigated. In case 1, the crushed Marcellus shale samples were allowed to react with anionic sodium dodecyl sulfate (SDS) and brine. In case 2, another set of crushed Marcellus shale samples were treated with cetyltrimethylammonium bromide (CTAB) and brine. The surfactant concentration and salinity of brine were varied following the Box-Behnken experimental design. CH4 adsorption was then assessed volumetrically in the treated shale at varying pressures (1-50 bar) and a constant temperature of 30 °C using a pressure equilibrium cell. Mathematical analysis of the experimental data yielded two separate models, which expressed the amount of adsorbed CH4 as a function of SDS/CTAB concentration, salinity, and pressure. In case 1, the highest amount of adsorbed CH4 was about 1 mmol/g. Such an amount was achieved at 50 bar, provided that the SDS concentration is kept close to its critical micelle concentration (CMC), which is 0.2 wt %, and salinity is in the range of 0.1-20 ppt. However, in case 2, the maximum amount of adsorbed CH4 was just 0.3 mmol/g. This value was obtained at 50 bar and high salinity (∼75 ppt) when the CTAB concentration was above the CMC (>0.029 wt %). The findings provide researchers with insights that can help in optimizing the ratio of salinity and surfactant concentration used in shale gas fracturing fluid.
We investigate the dynamic adsorption of anionic surfactant C14 - 16 alpha olefin sulfonate on Berea sandstone cores with different surface wettability and redox states under high temperature that represents reservoir conditions. Surfactant adsorption levels are determined by analyzing the effluent history data with a dynamic adsorption model assuming Langmuir isotherm. A variety of analyses, including surface chemistry, ionic composition, and chromatography, is performed. It is found that the surfactant breakthrough in the neutral-wet core is delayed more compared to that in the water-wet core because the deposited crude oil components on the rock surface increase the surfactant adsorption via hydrophobic interactions. As the surfactant adsorption is satisfied, the crude oil components are solubilized by surfactant micelles and some of the adsorbed surfactants are released from the rock surface. The released surfactant dissolves in the flowing surfactant solution, thereby resulting in an overshoot of the produced surfactant concentration with respect to the injection value. Furthermore, under water-wet conditions, changing the surface redox potential from an oxidized to a reduced state decreases the surfactant adsorption level by 40%. We find that the decrease in surfactant adsorption is caused not only by removing the iron oxide but also by changing the calcium concentration after the core restoration process (calcite dissolution and ion exchange as a result of using EDTA). Findings from this study suggest that laboratory surfactant adsorption tests need to be conducted by considering the wettability and redox state of the rock surface while recognizing how core restoration methods could significantly alter the ionic composition during surfactant flooding.
Since the turn of the 21st century, water pollution has been a major issue, and most of the pollution is generated by dyes. Adsorption is one of the most commonly used dye-removal methods from aqueous solution. Magnetic-particle integration in the water-treatment industry is gaining considerable attention because of its outstanding physical and chemical properties. Magnetic-particle adsorption technology shows promising and effective outcomes for wastewater treatment owing to the presence of magnetic material in the adsorbents that can facilitate separation through the application of an external magnetic field. Meanwhile, the introduction of activated carbon (AC) derived from various materials into a magnetic material can lead to efficient organic-dye removal. Therefore, this combination can provide an economical, efficient, and environmentally friendly water-purification process. Although activated carbon from low-cost and abundant materials has considerable potential in the water-treatment industry, the widespread applications of adsorption technology are limited by adsorbent recovery and separation after treatment. This work specifically and comprehensively describes the use of a combination of a magnetic material and an activated carbon material for dye adsorption in wastewater treatment. The literature survey in this mini-review provides evidence of the potential use of these magnetic adsorbents, as well as their magnetic separation and recovery. Future directions and challenges of magnetic activated carbon in wastewater treatment are also discussed in this paper.
In this research, an attempt to develop zwitterion composite adsorbent is conducted by modifying chitosan (CHS) with a covalent cross-linker (epichlorohydrin, ECH) and an aluminosilicate mineral (zeolite, ZL). The zwitterion composite adsorbent of chitosan-epichlorohydrin/zeolite (CHS-ECH/ZL) is performed multifunctional tasks by removing two structurally different cationic (methylene blue dye, MB), and anionic (reactive red 120 dye, RR120) dyes from aqueous solutions. The surface property, crystallinity, morphology, functionality, and charge of the CHS-ECH/ZL are analyzed using BET, XRD, SEM, FTIR, and pHpzc, analyses, respectively. The influence of pertinent parameters namely CHS-ECH/ZL dosage (0.02-0.5 g), solution pH (4-10), temperature (303-323K), initial dye concentration (30-400 mg/L), and contact time (0-600 min) on the MB and RR120 removal are tested. The research findings revealed that the adsorption isotherm at equilibrium well explained in according to the Freundlich isotherm model, and the recorded adsorption capacities of CHS-ECH/ZL are 156.1 and 284.2 mg/g for MB and RR120 respectively at 30 °C. The mechanism of MB and RR120 adsorption onto the CHS-ECH/ZL indicates various types of interactions namely, electrostatic interaction, hydrogen bonding, and Yoshida H-bonding in addition to n-π interaction. Overall, this research introduces CHS-ECH/ZL composite as an eco-friendly zwitterion adsorbent with good applicability towards the two structurally different cationic and anionic dyes from aqueous environment.
Carbon nanotubes (CNTs) have received enormous attention due to their fascinating properties to be used in various applications including electronics, sensing, energy storage and conversion. The first principles calculations within density functional theory (DFT) have been carried out in order to investigate the structural, electronic and optical properties of un-doped and doped CNT nanostructures. O2, CO2, and CH3OH have been chosen as gas molecules to study the adsorption properties based on zigzag (8,0) SWCNTs. The results demonstrate that the adsorption of O2, CO2, and CH3OH gas molecules on pristine, Si-doped and B-doped SWCNTs are either physisorption or chemisorption. Moreover, the electronic properties indicating SWCNT shows significant improvement toward gas adsorption which provides the impact of selecting the best gas sensor materials towards detecting gas molecule. Therefore, these pristine, Si-, and B-doped SWCNTs can be considered to be very good potential candidates for sensing application.
The development of wearable artificial kidney demands an efficient dialysate recovery, which relies upon the adsorption process. This study proposes a solution to solve the problem of competitive adsorption between the uremic toxins by employing two adsorptive components in a membrane separation process. Dual-layer hollow fiber (DLHF) membranes, which are composed of a polysulfone (PSf)/activated carbon (AC) inner layer and a PSf/poly(methyl methacrylate) (PMMA) outer layer, were prepared for co-adsorptive removal of creatinine and urea from aqueous solution. The DLHF membranes were characterized in terms of morphological, physicochemical, water transport, and creatinine adsorption properties. The membrane was then subjected to an ultrafiltration adsorption study for performance evaluation. The incorporation of AC in membrane, as confirmed by microscopic and surface analyses, has improved the pure water flux up to 25.2 L/(m2 h). A membrane with optimum AC loading (9 wt %) demonstrated the highest maximum creatinine adsorption capacity (86.2 mg/g) based on the Langmuir adsorption isotherm model. In the ultrafiltration adsorption experiment, the membrane removed creatinine and urea with a combined average percent removal of 29.3%. Moreover, the membrane exhibited creatinine and urea uptake recoveries of 98.8 and 81.2%, respectively. The combined action of PMMA and AC in the PSf DLHF membrane has made the adsorption of multiple uremic toxins possible during dialysate recovery.
Boron has been classified as a drinking water pollutant in many countries. It is harmful to many plants, exceptionally sensible plants, and human health. Therefore, boron level needs to be decreased to 0.3 mg/L for drinking water and within 0.5 mg/L to 1 mg/L for irrigation water. In this study, various operational parameters namely pH, contact time and liquid/solid ratio were investigated to determine the potential of using date seed (or date pit or date stone) to remove boron from seawater. This study's main objective was to determine boron adsorption capacities of date seeds prepared by various methods (i.e., powdered, activated, acid-treated and defatted seed) by batch adsorption process using boron contaminated synthetic seawater. The process parameters of the selected biosorbent among the four date seed preparations methods were optimized. The surface characteristics were analyzed by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM). The results showed that acid-treated date seed was the best biosorbent in terms of removing 89.18% boron from aqueous solution at neutral pH, liquid to solid ratio of 5 within 2 hours of reaction time at room temperature (25°C±2°C).
The nanoenvironment of nanobiocatalysts, such as local hydrophobicity, pH and charge density, plays a significant role in optimizing the enzymatic selectivity and specificity. In this study, Kluyveromyces lactis β-galactosidase (Gal) was assembled onto polystyrene nanofibers (PSNFs) to form PSNF-Gal nanobiocatalysts. We proposed that local hydrophobicity on the nanofiber surface could expel water molecules so that the transgalactosylation would be preferable over hydrolysis during the bioconversion of lactose, thus improve the galacto-oligosaccharides (GOS) yield. PSNFs were fabricated by electro-spinning and the operational parameters were optimized to obtain the nanofibers with uniform size and ordered alignment. The resulting nanofibers were functionalized for enzyme immobilization through a chemical oxidation method. The functionalized PSNF improved the enzyme adsorption capacity up to 3100mg/g nanofiber as well as enhanced the enzyme stability with 80% of its original activity. Importantly, the functionalized PSNF-Gal significantly improved the GOS yield and the production rate was up to 110g/l/h in comparison with 37g/l/h by free β-galactosidase. Our research findings demonstrate that the localized nanoenvironment of the PSNF-Gal nanobiocatalysts favour transgalactosylation over hydrolysis in lactose bioconversion.
Chitosan nanoparticles are exhalation prone and agglomerative to pulmonary inhalation. Blending nanoparticles with lactose microparticles (∼5 µm) could mutually reduce their agglomeration through surface adsorption phenomenon. The chitosan nanoparticles of varying size, size distribution, zeta potential, crystallinity, shape and surface roughness were prepared by spray drying technique as a function of chitosan, surfactant and processing conditions. Lactose-polyethylene glycol 3000 (PEG3000) microparticles were similarly prepared. The chitosan nanoparticles, physically blended with fine lactose-PEG3000 microparticles, exhibited a comparable inhalation performance with the commercial dry powder inhaler products (fine particle fraction between 20% and 30%). Cascade impactor analysis indicated that the aerosolization and inhalation performance of chitosan nanoparticles was promoted by their higher zeta potential and circularity, and larger size attributes of which led to reduced inter-nanoparticulate aggregation and favored nanoparticles interacting with lactose-PEG3000 micropaticles that aided their delivery into deep and peripheral lungs.