Heavy metal sequestration from wastewater by metal-organic frameworks: a state-of-the-art review of recent progress.

Metal-organic frameworks (MOFs) have emerged as highly promising adsorbents for removing heavy metals from wastewater due to their tunable structures, high surface areas, and exceptional adsorption capacities. This review meticulously examines and summarizes recent advancements in producing and utilizing MOF-based adsorbents for sequestering heavy metal ions from water. It begins by outlining and contrasting commonly employed methods for synthesizing MOFs, such as solvothermal, microwave, electrochemical, ultrasonic, and mechanochemical. Rather than delving into the specifics of adsorption process parameters, the focus shifts to analyzing the adsorption capabilities and underlying mechanisms against critical metal(loid) ions like chromium, arsenic, lead, cadmium, and mercury under various environmental conditions. Additionally, this article discusses strategies to optimize MOF performance, scale-up production, and address environmental implications. The comprehensive review aims to enhance the understanding of MOF-based adsorption for heavy metal remediation and stimulate further research in this critical field. In brief, this review article presents a comprehensive overview of the contemporary information on MOFs as an effective adsorbent and the challenges being faced by these adsorbents for heavy metal mitigation (including stability, cost, environmental issues, and optimization), targeting to develop a vital reference for future MOF research.

Amine-Decorated Methacrylic Acid-based Inverse Vulcanized Polysulfide for Effective Mercury Removal from Wastewater.

Mercury [Hg(II)] contamination is an indefatigable global hazard that causes severe permanent damage to human health. Extensive research has been carried out to produce mercury adsorbents; however, they still face certain challenges, limiting their upscaling. Herein, we report the synthesis of a novel amine-impregnated inverse vulcanized copolymer for effective mercury removal. Poly(S-MA) was prepared using sulfur and methacrylic acid employing the inverse vulcanization method, followed by functionalization. The polyethylenimine (PEI) was impregnated on poly(S-MA) to increase the adsorption active sites. The adsorbent was then characterized byusing Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). FTIR spectroscopy confirmed the formation of the copolymer, and successful impregnation of PEI and SEM revealed the composite porous morphology of the copolymer. Amine-impregnated copolymer [amine@poly(S-MA)] outperformed poly(S-MA) in mercury as it showed 20% superior performance with 44.7 mg/g of mercury adsorption capacity. The adsorption data best fit the pseudo-second-order, indicating that chemisorption is the most effective mechanism, in this case, indicating the involvement of NH2 in mercury removal. The adsorption is mainly a monolayer on a homogeneous surface as indicated by the 0.76 value of Redlich-Peterson exponent (g), which describes the adsorption nature advent from the R2 value of 0.99.

A comprehensive review of synthesis kinetics and formation mechanism of geopolymers.

Geopolymers are synthesized by alkali or acid activation of aluminosilicate materials. This paper critically reviews the synthesis kinetics and formation mechanism of geopolymers. A variety of mechanistic tools such as Environmental Scanning Electron Microscopy (ESEM) and in situ Energy Dispersive X-ray diffractometry (EDXRD), in situ Isothermal Conduction Calorimetry (ICC), in situ Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), 1H low-field Nuclear Magnetic Resonance (NMR) and Isothermal Conduction Calorimetry (ISC), and others and phenomenological models such as the John-Mehl-Avrami-Kolmogorov (JMAK) model, modified Jandar model, and exponential and Knudson linear dispersion models were used to study the geopolymerization kinetics and many mechanisms were proposed for the synthesis of geopolymers. The mechanistic tools and phenomenological models provided new insights about geopolymerization kinetics and formation mechanisms but each of the techniques used possesses some limitations. These limitations need to be removed and new methods or techniques must be developed to overcome these challenges and get more detailed information about all types of geopolymers. The formation mechanism consists of three to four stages such as dissolution of raw materials, polymerization of silica and alumina, condensation, and reorganization. The Si/Al ratio above the Si/Al ratio of reactants is more suitable and it increases the rate or degree of reaction and produces a higher compressive strength geopolymer. The Na/Al ratio of 1, water-to-solid (W/S) ratio of 0.30-0.45, a temperature in the range of 30 °C to 85 °C, and a curing time of 24 hours are the best for the synthesis of geopolymers. The growing demand for geopolymers in various fields requires the development of new advanced techniques for further understanding of kinetics and mechanisms for tailoring the properties of geopolymers for specific applications.

Co-anaerobic digestion of sawdust and chicken manure with plant herbs: Biogas generation and kinetic study.

Plant herbs specifically serai wangi (SW) and peppermint (PPM) are selected for its insect repellent properties as the use of chicken manure (CM) in anaerobic digestion (AD) potentially attract flies due to the digestate produced. Hence, the addition of SW and PPM in the AD system of CM could deter flies' infestation while producing biogas. Previous work has shown that AD of sawdust (SD) and CM with these plant herbs were able to produce biogas and reduce the flies attraction towards the digestate. However, the combination of SW and PPM for AD of CM has yet to be investigated. This work describes the effect of mixing SW and PPM on the co-AD of SDCM with respect to biogas production, methane yield and kinetic analysis. The mixture of SW and PPM was varied at different concentrations. The composition of methane in biogas was characterized every 10 days by using gas chromatography (GC) equipped with a thermal conductivity detector (TCD). The results suggest that co-AD of 10SW10PPM exhibited the highest biogas production (52.28 mL/gvs) and methane yield (30.89 mL/gvs), which the purity of methane increased by 18.52% as compared to SDCM. However, increasing the concentration of SW and PPM does not significantly improve the overall process. High R2 (0.927-0.999), low RMSE (0.08-0.61) and low prediction error (<10.00%) were displayed by the modified Gompertz, logistic and Cone models. In contrast, Monod and Fitzhugh model is not preferred for the co-AD of SDCM with a mixture of SW and PM, as a high prediction error is obtained throughout the study. Increasing the dosage of PPM decreases the maximum cumulative methane yield, ranging from 31.76 to 7.01 mL/gvs for modified Gompertz and 89.56 to 19.31 mL/gvs for logistic model. The Modified Gompertz obtained a lag phase of 10.01-28.28 days while the logistic model obtained a lag phase of 37.29-52.48 days.

Synthesis and performance evaluation of slow-release fertilizers produced from inverse vulcanized copolymers obtained from industrial waste.

To improve crop nutrient uptake efficacy (NUE) and better manage fertilization, slow-release fertilizers (SRFs) are developed by either coating the urea granules or making a composite. Several materials have already been developed, nevertheless, scalability of those materials is still a challenge due to their inherit drawbacks (such as hydrophilicity, crystallinity, non-biodegradability, etc.). Herein, we utilized a biodegradable, green and sustainable copolymer produced from industrial waste (sulfur-petroleum industry waste and myrcene-citrus industry waste) to coat the urea using a facile coating method to develop novel SRFs and achieve better agronomic and environmental advantages. The copolymer was first synthesized using a facile, solvent-free one-pot method called inverse vulcanization followed by Fourier transform infrared spectroscopy (FTIR) analysis to confirm the successful reaction between myrcene and sulfur subsequently coating the copolymer on urea granule. The morphology and coating thickness of coated fertilizers were analysed using scanning electron microscopy (SEM), followed by a nitrogen release test in distilled water and a soil burial test to confirm the biodegradability. The nitrogen release test revealed that the SRF with the maximum coating thickness of 1733 µm releases only 16% of its total nitrogen after 4 days of incubation compared to the pristine urea which releases all its nutrient within 1 day. The soil burial test confirms the biodegradability of the copolymer, as after 50 days of incubation in soil the copolymer loses almost 18.25% of its total weight indicating that the copolymer is degrading.

Fly ash geopolymer as a coating material for controlled-release fertilizer based on granulated urea.

Nitrogen loss from urea fertiliser due to its high solubility characteristics has led to the invention of controlled release urea (CRU). Majority of existing CRU coatings are produced from a non-biodegradable, toxic and expensive synthetic polymers. This study determines the feasibility of fly ash-based geopolymer as a coating material for urea fertilizer. The effects of fly ash particle size (15.2 µm, 12.0 µm, and 8.6 µm) and solid to liquid (S : L) ratio (3 : 1, 2.8 : 1, 2.6 : 1, 2.4 : 1 and 2.2 : 1) on the geopolymer coating, the characterization such as FTIR analysis, XRD analysis, surface area and pore size analysis, setting time analysis, coating thickness, and crushing strength, and the release kinetics of geopolymer coated urea in water and soil were determined. Lower S : L ratio was beneficial in terms of workability, but it had an adverse impact on geopolymer properties where it increased porosity and decreased mechanical strength to an undesirable level for the CRU application. Geopolymer coated urea prepared from the finest fly ash fraction and lowest S : L ratio demonstrated high mechanical strength and slower urea release profile. Complete urea release was obtained in 132 minutes in water and 15 days in soil from geopolymer-coated urea whereas for uncoated urea it took only 20 minutes in water and 3 days in soil. Thus, geopolymer can potentially be used as a coating material for urea fertilizer to replace commonly used expensive and biodegradable polymer-based coatings.

Current perspectives, future challenges and key technologies of biohydrogen production for building a carbon-neutral future: A review.

The ever-increasing quantity of greenhouse gases in the atmosphere can be attributed to the rapid increase in the world population as well as the expansion of globalization. Hence, achieving carbon neutrality by 2050 stands as a challenging task to accomplish. Global industrialization had necessitated the need to enhance the current production systems to reduce greenhouse gases emission, whilst promoting the capture of carbon dioxide from atmosphere. Hydrogen is often touted as the fuel of future via substituting fossil-based fuels. In this regard, renewable hydrogen happens to be a niche sector of novel technologies in achieving carbon neutrality. Microalgae-based biohydrogen technologies could be a sustainable and economical approach to produce hydrogen from a renewable source, while simultaneously promoting the absorption of carbon dioxide. This review highlights the current perspectives of biohydrogen production as an alternate source of energy. In addition, future challenges associated with biohydrogen production at large-scale application, storage and transportation are included. Key technologies in producing biohydrogen are finally described in building a carbon-neutral future.

Sulfur enriched slow-release coated urea produced from inverse vulcanized copolymer.

Slow-release fertilizers are developed to enhance the nutrient use efficiency (NUE), by coating urea with less water soluble or hydrophobic material. Diverse range of materials have been utilized to coat urea, however, their inherit non-biodegradability, hydrophilicity, crystallinity, and high synthesis cost limits their scalability. Herein, we reported the preparation of a novel slow-release sulfur enriched urea fertilizers using sustainable hydrophobic, biodegradable, crosslinked copolymer made from sulfur and rubber seed oil (Poly(S-RSO)) through the use of dip coating method. Scanning electron microscopy (SEM) was employed to study the fertilizers morphology and estimate the coating film thickness. A nitrogen release test was carried out in distilled water, which revealed that the coated fertilizers with a coating thickness of 165 µm, 254 µm and 264 µm released only 65 % of its total nutrient content after 2, 19 and 43 days of incubation, respectively: hence, showing an excellent slow-release property. In soil, fertilizer with 264 µm coating thickness released only 17 % nitrogen after 20 days of incubation, in line with the European standard (EN 13266, 2001). The release kinetic data best fits the Ritger-Peppas model with a R2 value of 0.99 and the n value of 0.65 indicated the release was mainly due to diffusion. Submerged cultivation (SmC) demonstrated the potential of poly(S-RSO) to enhance sulfur oxidation; it was observed that the copolymer oxidation was 50 % greater than that of elemental sulfur. A comparison between the newly developed fertilizers and existing coated fertilizers was also presented. On the whole, the results demonstrated outstanding slow-release characteristics and improved sulfur oxidation.

A Degradable Inverse Vulcanized Copolymer as a Coating Material for Urea Produced under Optimized Conditions.

Global enhancement of crop yield is achieved using chemical fertilizers; however, agro-economy is affected due to poor nutrient uptake efficacy (NUE), which also causes environmental pollution. Encapsulating urea granules with hydrophobic material can be one solution. Additionally, the inverse vulcanized copolymer obtained from vegetable oils are a new class of green sulfur-enriched polymer with good biodegradation and better sulfur oxidation potential, but they possess unreacted sulfur, which leads to void generations. In this study, inverse vulcanization reaction conditions to minimize the amount of unreacted sulfur through response surface methodology (RSM) is optimized. The copolymer obtained was then characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). FTIR confirmed the formation of the copolymer, TGA demonstrated that copolymer is thermally stable up to 200 °C temperature, and DSC revealed the sulfur conversion of 82.2% (predicted conversion of 82.37%), which shows the goodness of the model developed to predict the sulfur conversion. To further maximize the sulfur conversion, 5 wt% diisopropenyl benzene (DIB) as a crosslinker is added during synthesis to produce terpolymer. The urea granule is then coated using terpolymer, and the nutrient release longevity of the coated urea is tested in distilled water, which revealed that only 65% of its total nutrient is released after 40 days of incubation. The soil burial of the terpolymer demonstrated its biodegradability, as 26% weight loss happens in 52 days of incubation. Thus, inverse vulcanized terpolymer as a coating material for urea demonstrated far better nutrient release longevity compared with other biopolymers with improved biodegradation; moreover, these copolymers also have potential to improve sulfur oxidation.