Nowadays, microplastic pollution is one of the globally urgent concerns as a result of discharging plastic products into the atmosphere, aquatic and soil environments. Microplastics have average size of less than 5 mm, are non-biodegradable, accumulative, and highly persistent substances. Thousands of tons of microplastics are still accumulated in various environments, posing an enormous threat to human health and living creatures. Here, we review the occurrence and analytical methods, and impact of microplastics in the environments including soil, aquatic media, and atmosphere. Analytical methods including visual observation, Fourier-transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and pyrolysis-gas chromatography-mass spectrometry were evaluated. We elucidated the environmental and human health impacts of microplastics with emphasis on life malfunction, immune disruption, neurotoxicity, diseases and other tangible health risks. This review also found some shortages of analytical equivalence and/or standardization, inconsistence in sampling collection and limited knowledge of microplastic toxicity. It is hopeful that the present work not only affords a more insight into the potential dangers of microplastics on human health but also urges future researches to establish new standardizations in analytical methods.
Tautomerism alters the structure and properties of materials, which can be exploited to control their chemical and biological activities. The role of pH-induced tautomerism of polyvinylpyrrolidone (PVP) was determined by measuring the size, stability, and antioxidant and antibacterial properties of microwave synthesized-silver nanoparticles (AgNPs). TEM and XRD analyses confirmed the formation of face-centered cubic silver nanoparticles. PVP stabilized the AgNPs by interaction with the carbonyl or hydroxyl groups depending on the tautomerization under different pH conditions. At pH 4, PVP was stable in the keto tautomer, stabilizing Ag through electron donation of oxygen atoms in the carbonyl group, producing smaller AgNPs with a higher zeta potential. At pH 7 and 9, the enol tautomer PVP stabilized the AgNPs via oxygen atoms in the hydroxyl group, forming large nanoparticles. The keto form of PVP improved the stability and antioxidant and antibacterial properties of AgNPs compared with the enol form. This study also excluded the antioxidant contribution of PVP via hydrogen donation to free radicals. A facile method for controlling the size of AgNPs by adapting the pH-induced tautomerism of PVP that affects their stability and antioxidant and antibacterial activities is thus reported.
In this work, mesostructured silica nanoparticles (MSN(AP)) with high adsorptivity were prepared by a modification with 3-aminopropyl triethoxysilane (APTES) as a pore expander. The performance of the MSN(AP) was tested by the adsorption of MB in a batch system under varying pH (2-11), adsorbent dosage (0.1-0.5 g L(-1)), and initial MB concentration (5-60 mg L(-1)). The best conditions were achieved at pH 7 when using 0.1 g L(-1) MSN(AP) and 60 mg L(-1)MB to give a maximum monolayer adsorption capacity of 500.1 mg g(-1) at 303 K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Harkins-Jura isotherms and fit well to the Freundlich isotherm model. The adsorption kinetics was best described by the pseudo-second order model. The results indicate the potential for a new use of mesostructured materials as an effective adsorbent for MB.
Fibrous silica-titania (FST) catalysts were synthesized by microemulsion followed by silica seed-crystal crystallization methods under various molar ratios of toluene to water (T/W). The catalysts were characterized by XRD, UV-DRS, FESEM, TEM, AFM, N2 adsorption-desorption, FTIR, and ESR. The results revealed that altering the T/W ratio affected the growth of the silica and titania and led to different size, fiber density, silica-titania structure, and number of hydroxyl groups, as well as oxygen vacancies in the FSTs, which altered their behavior toward subsequent application. Photodegradation of ibuprofen (IBP) are in the following order: FST(6:1) (90%) > FST(5:1) (84%) > FST(7:1) (79%) > commercial TiO2 (67%). A kinetics study using Langmuir-Hinshelwood model illustrated that the photodegradation followed the pseudo-first-order and adsorption was the rate-limiting step. Optimization by response surface methodology (RSM) showed that the pH, initial concentration, and catalyst dosage were the remarkable parameters in photodegradation of IBP. The FST (6:1) maintained its photocatalytic activities for up to five cycles reaction without serious catalyst deactivation, and was also able to degrade other endocrine-disrupting chemicals, indicating its potential use for the treatment of those chemicals in wastewater.
Each year, nearly 30 million tons of pineapple fruit are harvested for food and drinking industries, along with the release of a huge amount of pineapple wastes. Without the proper treatment, pineapple wastes can cause adverse impacts on the environment, calling for new technologies to convert them into valuable products. Here, we review the production and application of adsorbents derived from pineapple wastes. The thermal processing or chemical modification improved the surface chemistry and porosity of these adsorbents. The specific surface areas of the pineapple wastes-based adsorbents were in range from 4.2 to at 522.9 m2·g-1. Almost adsorption systems followed the pseudo second order kinetic model, and Langmuir isotherm model. The adsorption mechanism was found with the major role of electrostatic attraction, complexation, chelation, and ion exchange. The pineapple wastes based adsorbents could be easily regenerated. We suggest the potential of the pineapple wastes towards circular economy.
Ternary CuO/AgO/FSZr photocatalysts were fabricated via the hydrothermal and electrochemical methods with three different CuO loading (1, 3 and 5 wt%), indicated as 1CuO/AgO/FSZr, 3CuO/AgO/FSZr and 5CuO/AgO/FSZr. The photocatalytic reaction was tested towards simultaneous chromium (VI) photoreduction and p-cresol photooxidation and the performance in order as follow: 3CuO/AgO/FSZr > 5CuO/AgO/FSZr > 1CuO/AgO/FSZr > AgO/FSZr > FSZr. CuO/AgO/FSZr photocatalysts showed an improvement in photocatalytic activity compared to AgO/FSZr and FSZr due to the reduction potential of chromium (VI) aligned closer to the conduction band of CuO and provided abundant free active electrons (e-) and holes (h+) with efficient transportation and migration. Interestingly, the 3CuO/AgO/FSZr was established as the best photocatalyst with 98% reduction of chromium (VI) and 83% oxidation of p-cresol simultaneously, owing to its strong corporation between the metal oxides and support and higher total pore volume. The Langmuir-Hinshelwood model were employed for kinetics which followed the pseudo-first-order kinetics model well. Based on the simultaneous photocatalytic mechanism, chromium (VI) and p-cresol were directly reduced and oxidized by e- and h+, respectively. The response surface methodology (RSM) discovered that the quadratic term initial concentration of chromium (VI) is the main significant factor in photocatalytic performance. The optimum parameters for simultaneous photoredox of chromium (VI) and p-cresol predicted from RSM are 9.6 mg L-1 of chromium (VI) concentration, 9.8 mg L-1 of p-cresol concentration and 0.32 g L-1 of catalyst dosage. Under these conditions the error between the predicted and experimental values is only 3.7%. The 3CuO/AgO/FSZr sustained the photocatalytic performance after reused for five cycles and could oxidized various organic pollutants as well as reduced chromium (VI) simultaneously.
Red mud as industrial waste from bauxite was utilized as a precursor for the synthesis of mesoporous ZSM-5. A high concentration of iron oxide in red mud was successfully removed using alkali fusion treatment. Mesoporous ZSM-5 was synthesized using cetyltrimethylammonium bromide (CTABr) as a template via dual-hydrothermal method, and the effect of crystallization time was investigated towards the formation of mesopores. Characterization using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 adsorption-desorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated the formation of cubic crystallite ZSM-5 with high surface area and mesopore volume within 6 h of crystallization. Increasing the crystallization time revealed the evolution of highly crystalline ZSM-5; however, the surface area and mesoporosity were significantly reduced. The effect of mesoporosity was investigated on the adsorption of methylene blue (MB). Kinetic and thermodynamic analysis of MB adsorption on mesoporous ZSM-5 was carried out at a variation of adsorption parameters such as the concentration of MB solution, the temperatures of solution, and the amount of adsorbent. Finally, methanol, 1-butanol, acetone, hydrochloric acid (HCl), and acetonitrile were used as desorbing agents to investigate the reusability and stability of mesoporous ZSM-5 as an adsorbent for MB removal.
Nowadays, emerging hazardous pollutants have caused many harmful effects on the environment and human health, calling for the state of the art methods for detection, qualification, and treatment. Metal-organic frameworks are porous, flexible, and versatile materials with unique structural properties, which can solve such problems. In this work, we reviewed the synthesis, activation, and characterization, and potential applications of NH2-MIL-53(Al). This material exhibited intriguing breathing effects, and obtained very high surface areas (182.3-1934 m2/g) with diverse morphologies. More importantly, NH2-MIL-53(Al) based materials could be used for the detection and removal of various toxic pollutants such as organic dyes, pharmaceuticals, herbicides, insecticides, phenols, heavy metals, and fluorides. We shed light on plausible adsorption mechanisms such as hydrogen bonds, π-π stacking interactions, and electrostatic interactions onto NH2-MIL-53(Al) adsorbents. Interestingly, NH2-MIL-53(Al) based adsorbents could be recycled for many cycles with high stability. This review also recommended that NH2-MIL-53(Al) based materials can be a good platform for the environmental remediation fields.
Tetracycline (TCC) and sulfadiazine (SDZ) are two of the most consumed antibiotics for human therapies and bacterial infection treatments in aquafarming fields, but their accumulative residues can result in negative effects on water and aquatic microorganisms. Removal techniques are therefore required to purify water before use. Herein, we concentrate on adsorptive removal of TCC and SDZ using cobalt@carbon nanotubes (Co@CNTs) derived from Co-ZIF-67. The presence of CNTs on the edge of nanocomposites was observed. Taguchi orthogonal array was designed with four variables including initial concentration (5-20 mg L-1), dosage (0.05-0.2 g L-1), time (60-240 min), and pH (2-10). Concentration and pH were found to be main contributors to adsorption of tetracycline and sulfadiazine, respectively. The optimum condition was found at concentration 5 mg L-1, dosage 0.2 g L-1, contact time 240 min, and pH 7 for both TCC and SDZ removals. Confirmation tests showed that Co@CNTs-700 removed 99.6% of TCC and 97.3% of SDZ with small errors (3-5.5%). Moreover, the kinetic and isotherm were studied, which kinetic and isotherm data were best fitted with pseudo second-order model and Langmuir. Maximum adsorption capacity values for TCC and SDZ were determined at 118.4-174.1 mg g-1 for 180 min. We also proposed the main role of interactions such as hydrogen bonding, π-π stacking, and electrostatic attraction in the adsorption of antibiotics. With high adsorption performance, Co@CNTs-700 is expected to remove antibiotics efficiently from wastewater.
The growing concern of water pollution is a critical issue stemming from industrialization and urbanization. One of the specific concerns within this broader problem is the toxicity associated with chromium (Cr), especially in its Cr (VI) form. Transition metal carbides/nitrides (MXenes) are attractive materials for the treatment of water due to their unique properties such as layered structure, high surface area, conductivity, flexibility, scalable manufacture, and surface functions. Adsorption and photocatalysis reactions are the two promising methods for the removal of Cr (VI) by using MXenes. Still, most of the previous reviews were limited to the single application area. Hence, this review covers recent developments in MXene-based composites, highlighting their dual role as both adsorbents and photocatalysts in the removal of Cr (VI). MXene-based composites are found to be effective in both adsorption and photodegradation of Cr (VI). Most MXene-based composites have demonstrated exceptional removal efficiency for Cr (VI), achieving impressive adsorption capacities ranging from 100 to 1500 mg g-1 and degradation percentages between 80% and 100% in a relatively short period. The active functional groups present on the surface of MXene have a viable impact on the adsorption and photodegradation performance. The mechanism of Cr (VI) removal is explained, with MXenes playing a key role in electrostatic attraction for adsorption and as co-catalysts in photocatalysis. However, MXene-based composites have limitations such as instability, competition with co-existing ions, and regeneration challenges. Further research is needed to address these limitations. Additionally, MXene-based composites hold promise for addressing water contamination, heavy metal removal, hydrogen production, energy storage, gas sensing, and biomedical applications.
The present study highlights the treatment of industrial effluent, which is one of the most life-threatening factors. Herein, for the first time, two types of NiO (green and black) photocatalysts were prepared by facile chemical precipitation and thermal decomposition methods separately. The synthesized NiO materials were demonstrated with various instrumental techniques for finding their characteristics. The X-ray diffraction studies (XRD) and X-ray photoelectron spectroscopy (XPS) revealed the presence of Ni2O3 in black NiO material. The transmission electron microscopic (TEM) images engrained the nanospherical shaped green NiO and nanoflower shaped black NiO/Ni2O3 materials. Further, the band gap of black NiO nanoflower was 2.9 eV compared to green NiO having 3.8 eV obtained from UV-vis spectroscopy. Meanwhile, both NiO catalysts were employed for visible light degradation, which yields a 60.3% efficiency of black NiO comparable to a 4.3% efficiency of green NiO within 180 min of exposure. The higher degrading efficiency of black NiO was due to the presence of Ni2O3 and the development of pores, which was evident from the Barrett-Joyner-Halenda (BJH) method. Type IV hysteresis was observed in black NiO nanoflowers with high surface area and pore size measurements. This black NiO/Ni2O3 synthesized from the thermal decomposition method has promoted better photocatalytic degradation of 4-chlorophenol upon exposure to visible light and is applicable for other industrial pollutants.
The production of low-cost solid adsorbents for carbon dioxide (CO2) capture has gained massive consideration. Biomass wastes are preferred as precursors for synthesis of CO2 solid adsorbents, due to their high CO2 adsorption efficiency, and ease of scalable low-cost production. This review particularly focuses on waste biomass-derived adsorbents with their CO2 adsorption performances. Specifically, studies related to carbon (biochar and activated carbon) and silicon (silicates and geopolymers)-based adsorbents were summarized. The impact of experimental parameters including nature of biomass, synthesis route, carbonization temperature and type of activation methods on the CO2 adsorption capacities of biomass-derived pure carbon and silicon-based adsorbents were evaluated. The development of various enhancement strategies on biomass-derived adsorbents for CO2 capture and their responsible factors that impact adsorbent's CO2 capture proficiency were also reviewed. The possible CO2 adsorption mechanisms on the adsorbent's surface were highlighted. The challenges and research gaps identified in this research area have also been emphasized, which will help as further research prospects.
Photocatalysis utilizing semiconductors offer a cost-effective and promising solution for the removal of pollutants. MXene and perovskites, which possess desirable properties such as a suitable bandgap, stability, and affordability, have emerged as a highly promising material for photocatalytic activity. However, the efficiency of MXene and perovskites is limited by their fast recombination rates and inadequate light harvesting abilities. Nonetheless, several additional modifications have been shown to enhance their performance, thereby warranting further exploration. This study delves into the fundamental principles of reactive species for MXene-perovskites. Various methods of modification of MXene-perovskite-based photocatalysts, including Schottky junction, Z-scheme and S-scheme are analyzed with regard to their operation, differences, identification techniques and reusability. The assemblance of heterojunctions is demonstrated to enhance photocatalytic activity while also suppressing charge carrier recombination. Furthermore, the separation of photocatalysts through magnetic-based methods is also investigated. Consequently, MXene-perovskite-based photocatalysts are seen as an exciting emerging technology that necessitates further research and development.
Saponin is a plant-derived chemical with an amphiphilic glycoconjugate structure extracted from sapindaceae plants like Sapindus rarak. This study investigated saponin extract of Sapindus rarak as a natural template for formation of mesoporous zeolite Y. Surface area and mesoporosity of zeolite Y were improved with optimization of Sapindus rarak extract (SRE) concentration (Y-Ln; n = 2, 5, 10 or 15 mL), reaching 216.26 m2 mesoporous area and 0.214 cm3 g-1 mesoporous volume for Y-L10 samples. A different loading of Ni was impregnated onto Y-L10 zeolite to improve Lewis/Brønsted acidity as catalysts in the deoxygenation of Reutealis trisperma oil (RTO) into hydrocarbon fuels. Impregnating 15% Ni on NaY zeolite enhanced Lewis acidity to 0.4556 mmol g-1, producing 48.8% liquid oil with 85.43% degree of deoxygenation. A high selectivity towards C15 and C17 hydrocarbon was analyzed from liquid yield, indicating the contributing factor from Lewis acidity and mesoporosity to enhance deoxygenation and prevent the hydrocracking reaction.
Conversion of red mud (RM) that contains a high level of silica, alumina and iron minerals into heterogenous catalysts, offers a route for the utilization of abundant toxic by-products of bauxite refining. In this study, the conversion of red mud into mesoporous Fe-aluminosilicate produced selective catalysts for the deoxygenation of waste cooking oil to green diesel hydrocarbons. Direct conversion of red mud in the presence cetyltrimethylammonium bromide into Fe-aluminosilicate (RM-CTA) produced a highly mesoporous structure with oligomeric Fe2O3 clusters within the pores. When red mud was treated with citric acid (RM-CA-CTA), a wide distribution of Fe2O3 particles was obtained on the aluminosilicate external surface. TEM analysis showed a well-defined hexagonal mesoporosity of Fe-aluminosilicate obtained from untreated red mud, while the treated red mud produced lower regularity mesopores. RM-CTA exhibits 60% WCO conversion and 83.72% selectivity towards liquid products with 80.44% diesel hydrocarbon (C11-C18) yield. The high selectivity was due to the high acidity of Fe-aluminosilicate to dissociate the C-O bond and the regularity of mesostructure for efficient hydrocarbon diffusion, preventing a cracking reaction.
Mesoporous silica nanoparticles (MSNs) were synthesized with variable microwave power in the range of 100-450 W, and the resulting enhancement of MSN crystal growth was evaluated for the adsorption and release of ibuprofen. X-ray diffraction (XRD) revealed that the MSN prepared under the highest microwave power (MSN450) produced the most crystallized and prominent mesoporous structure. Enhancement of the crystal growth improved the hexagonal order and range of silica, which led to greater surface area, pore width and pore volume. MSN450 exhibited higher ibuprofen adsorption (98.3 mg/g), followed by MSN300(81.3 mg/g) and MSN100(74.1 mg/g), confirming that more crystallized MSN demonstrated higher adsorptivity toward ibuprofen. Significantly, MSN450 also contained more hydroxyl groups that provided more adsorption sites. In addition, MSN450 exhibited comparable ibuprofen adsorption with conventionally synthesized MSN, indicating the potential of microwave treatment in the synthesis of related porous materials. In vitro drug release was also investigated with simulated biological fluids and the kinetics was studied under different pH conditions. MSN450 showed the slowest release rate of ibuprofen, followed by MSN300 and MSN100. This was due to the wide pore diameter and longer range of silica order of the MSN450. Ibuprofen release from MSN450 at pH 5 and 7 was found to obey a zero-order kinetic model, while release at pH 2 followed the Kosmeyer-Peppas model.
In this work, two low-cost wastes, bivalve shell (BS) and Zea mays L. husk leaf (ZHL), were investigated to adsorb malachite green (MG) from aqueous solutions. The ZHL was treated with calcined BS to give the BS-ZHL, and its ability to adsorb MG was compared with untreated ZHL, calcined BS and Ca(OH)(2)-treated ZHL under several different conditions: pH (2-8), adsorbent dosage (0.25-2.5 g L(-1)), contact time (10-30 min), initial MG concentration (10-200 mg L(-1)) and temperature (303-323 K). The equilibrium studies indicated that the experimental data were in agreement with the Langmuir isotherm model. The use of 2.5 g L(-1) BS-ZHL resulted in the nearly complete removal of 200 mg L(-1) of MG with a maximum adsorption capacity of 81.5 mg g(-1) after 30 min of contact time at pH 6 and 323 K. The results indicated that the BS-ZHL can be used to effectively remove MG from aqueous media.
In this study, calcined Lapindo volcanic mud (LVM) was used as an adsorbent to remove an anionic dye, methyl orange (MO), from an aqueous solution by the batch adsorption technique. Various conditions were evaluated, including initial dye concentration, adsorbent dosage, contact time, solution pH, and temperature. The adsorption kinetics and equilibrium isotherms of the LVM were studied using pseudo-first-order and -second-order kinetic equations, as well as the Freundlich and Langmuir models. The experimental data obtained with LVM fits best to the Langmuir isotherm model and exhibited a maximum adsorption capacity (q(max)) of 333.3 mg g(-1); the data followed the second-order equation. The intraparticle diffusion studies revealed that the adsorption rates were not controlled only by the diffusion step. The thermodynamic parameters, such as the changes in enthalpy, entropy, and Gibbs free energy, showed that the adsorption is endothermic, random and spontaneous at high temperature. The results indicate that LVM adsorbs MO efficiently and could be utilized as a low-cost alternative adsorbent for the removal of anionic dyes in wastewater treatment.
Electrochemical dechlorination of chlorobenzenes in the presence of various arene mediators such as naphthalene, biphenyl, phenanthrene, anthracene, and pyrene, was studied. The amount of mediator required was able to be reduced to 0.01 equiv. for all mediators except for anthracene, with the complete dechlorination of mono-, 1,3-di- and 1,2,4-trichlorobenzene still achieved. This catalytic amount of mediator plays an important role in accelerating the dechlorination through the rapid formation of radical anions prior to reduction of the chlorobenzenes.
Environmental pollution, climate change, and fossil fuel extinction have aroused serious global interest in the search for alternative energy sources. The dry reforming of methane (DRM) could be a good technique to harness syngas, a starting material for the FT energy process from greenhouse gases. Noble metal DRM catalysts are effective for the syngas generation but costly. Therefore, they inevitably, must be replaced by their Ni-based contemporaries for economic reasons. However, coking remains a strong challenge that impedes the industrialization of the FT process. This article explains the secondary reactions that lead to the production of detrimental graphitic coke deposition on the surface of active nickel catalyst. The influence of nickel particle size, impact of extra surface oxygen species, interaction of Ni catalysts with metal oxide supports/promoters, and larger fraction of exposed nickel active sites were addressed in this review. Size of active metal determines the conversion, surface area, metal dispersion, surface reactions, interior diffusion effects, activity, and yield. The influence of oxygen vacancy and coke deposition on highly reported metal oxide supports/promoters (Al2O3, MgO and La2O3) was postulated after studying CIFs (crystallographic information files) obtained from the Crystallography open database (COD) on VESTA software. Thus, overcoming excessive coking by La2O3 promotion is strongly advised in light of the orientation of the crystal lattice characteristics and the metal-support interaction can be used to enhance activity and stability in hydrogen reforming systems.