Synthesis of Calcium Peroxide Nanoparticles with Starch as a Stabilizer for the Degradation of Organic Dye in an Aqueous Solution.

One of the most significant environmental problems in the world is the massive release of dye wastewater from the dyeing industry. Therefore, the treatment of dyes effluents has received significant attention from researchers in recent years. Calcium peroxide (CP) from the group of alkaline earth metal peroxides acts as an oxidizing agent for the degradation of organic dyes in water. It is known that the commercially available CP has a relatively large particle size, which makes the reaction rate for pollution degradation relatively slow. Therefore, in this study, starch, a non-toxic, biodegradable and biocompatible biopolymer, was used as a stabilizer for synthesizing calcium peroxide nanoparticles (Starch@CPnps). The Starch@CPnps were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmet-Teller (BET), dynamic light scattering (DLS), thermogravimetric analysis (TGA), energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM). The degradation of organic dyes, methylene blue (MB), using Starch@CPnps as a novel oxidant was studied using three different parameters: initial pH of the MB solution, calcium peroxide initial dosage and contact time. The degradation of the MB dye was carried out via a Fenton reaction, and the degradation efficiency of Starch@CPnps was successfully achieved up to 99%. This study shows that the potential application of starch as a stabilizer can reduce the size of the nanoparticles as it prevents the agglomeration of the nanoparticles during synthesis.

Effective Removal of Glyphosate from Aqueous Systems Using Synthesized PEG-Coated Calcium Peroxide Nanoparticles: Kinetics Study, H2O2 Release Performance and Degradation Pathways.

Glyphosate (N-phosphonomethyl glycine) is a non-selective, broad-spectrum organophosphate herbicide. Its omnipresent application with large quantity has made glyphosate as a problematic contaminant in water. Therefore, an effective technology is urgently required to remove glyphosate and its metabolites from water. In this study, calcium peroxide nanoparticles (nCPs) were functioned as an oxidant to produce sufficient hydroxyl free radicals (·OH) with the presence of Fe2+ as a catalyst using a Fenton-based system. The nCPs with small particle size (40.88 nm) and high surface area (28.09 m2/g) were successfully synthesized via a co-precipitation method. The synthesized nCPs were characterized using transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), Brunauer-Emmett-Teller analysis (BET), dynamic light scattering (DLS), and field emission scanning electron microscopy (FESEM) techniques. Under the given conditions (pH = 3.0, initial nCPs dosage = 0.2 g, Ca2+/Fe2+ molar ratio = 6, the initial glyphosate concentration = 50 mg/L, RT), 99.60% total phosphorus (TP) removal and 75.10% chemical oxygen demand (COD) removal were achieved within 75 min. The degradation process fitted with the Behnajady-Modirshahla-Ghanbery (BMG) kinetics model. The H2O2 release performance and proposed degradation pathways were also reported. The results demonstrated that calcium peroxide nanoparticles are an efficient oxidant for glyphosate removal from aqueous systems.

Synthesis of Controlled-Release Calcium Peroxide Nanoparticles Coated with Dextran for Removal of Doxycycline from Aqueous System.

Nanoscale calcium peroxide (nCP) has turned out to be one of the effective and environmentally friendly approaches for wastewater remediation purposes. The rapid hydrolysis of nCPs and burst oxygen release caused by the high surface-to-volume ratio of nCPs could surpass the appropriate demand for oxygenation and pollutant degradation in the aqueous system. Thus, coated oxidants (COs) have been prepared using polymeric materials to ensure long-term efficacy and slow-release capability. Therefore, the nCPs were first prepared using dextran as a stabilizer to prevent irreversible agglomeration by the chemical precipitation method and had an average mean size of 2.33 ± 0.81 nm. The synthesized nCPs were then coated with dextran to produce dextran-coated nCPs. Their characteristics and effectiveness in doxycycline (DOX) degradation were assessed. The characterization of nCPs and dextran-coated nCPs was performed using X-ray diffractometry (XRD), field emission scanning electron microscopy (FESEM), fourier transform infrared spectroscopy (FTIR), Brunauer, Emmett and Teller analysis (BET), dynamic light scattering (DLS) and thermogravimetric analysis (TGA) techniques. This work suggests that dextran-coated nCPs are beneficial in wastewater treatment practice in terms of the long-term efficacy of DOX degradation potential.

Molecular Dynamics Simulation of Nanocellulose-Stabilized Pickering Emulsions.

While the economy is rapidly expanding in most emerging countries, issues coupled with a higher population has created foreseeable tension among food, water, and energy. It is crucial for more sustainable valorization of resources, for instance, nanocellulose, to address the core challenges in environmental sustainability. As the complexity of the system evolved, the timescale of project development has increased exponentially. However, research on the design and operation of integrated nanomaterials, along with energy supply, monitoring, and control infrastructure, has seriously lagged. The development cost of new materials can be significantly reduced by utilizing molecular simulation technology in the design of nanostructured materials. To realize its potential, nanocellulose, an amphiphilic biopolymer with the presence of rich -OH and -CH structural groups, was investigated via molecular dynamics simulation to reveal its full potential as Pickering emulsion stabilizer at the molecular level. This work has successfully quantified the Pickering stabilization mechanism profiles by nanocellulose, and the phenomenon could be visualized in three stages, namely the initial homogenous phase, rapid formation of micelles and coalescence, and lastly the thermodynamic equilibrium of the system. It was also observed that the high bead order was always coupled with a high volume of phase separation activities, through a coarse-grained model within 20,000 time steps. The outcome of this work would be helpful to provide an important perspective for the future design and development of nanocellulose-based emulsion products, which cater for food, cosmeceutical, and pharmaceutical industries.

Insights into the p-nitrophenol adsorption by amidoxime-modified poly(acrylonitrile-co-acrylic acid): characterization, kinetics, isotherm, thermodynamic, regeneration and mechanism study.

This study performs an appraisal of the adsorptive capacity of amidoxime-modified poly(acrylonitrile-co-acrylic acid) or abbreviated as (AO-modified poly(AN-co-AA)) for the p-nitrophenol (PNP) adsorption, from aquatic environments via batch system. The AO-modified poly(AN-co-AA) polymer was developed with redox polymerization, and then altered by using hydroxylamine hydrochloride (HH). Tools used to describe the physicochemical and morphological characteristics of the AO-modified poly(AN-co-AA) were Fourier transform infrared (FTIR) spectroscopy, CHN elemental analysis, X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The adsorption kinetics were examined by pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion kinetic models. Meanwhile, the isotherms were investigated by Langmuir, Freundlich, Temkin and Redlich-Peterson models. It was found that the adsorption was best fitted with pseudo-second order, and agreed with both Langmuir and Freundlich isotherm models. It was described best with the Freundlich isotherm due to highest R 2 (0.999). The maximum adsorption capacity was 143.06 mg g-1 at 298 K, and thermodynamic functions showed that the adsorption process was exothermic. Also, following five regeneration cycles, the adsorbent recorded 71.7% regeneration efficiency. The finding in this study indicates that the AO-modified poly(AN-co-AA) is an effective adsorbent to remove PNP from an aqueous solution.

Simultaneous Adsorption of Malachite Green and Methylene Blue Dyes in a Fixed-Bed Column Using Poly(Acrylonitrile-Co-Acrylic Acid) Modified with Thiourea.

Proper remediation of aquatic environments contaminated by toxic organic dyes has become a research focus globally for environmental and chemical engineers. This study evaluates the adsorption potential of a polymer-based adsorbent, thiourea-modified poly(acrylonitrile-co-acrylic acid) (T-PAA) adsorbent, for the simultaneous uptake of malachite green (MG) and methylene blue (MB) dye ions from binary system in a continuous flow adsorption column. The influence of inlet dye concentrations, pH, flow rate, and adsorbent bed depth on adsorption process were investigated, and the breakthrough curves obtained experimentally. Results revealed that the sorption capacity of the T-PAA for MG and MB increase at high pH, concentration and bed-depth. Thomas, Bohart-Adams, and Yoon-Nelson models constants were calculated to describe MG and MB adsorption. It was found that the three dynamic models perfectly simulate the adsorption rate and behavior of cationic dyes entrapment. Finally, T-PAA adsorbent demonstrated good cyclic stability. It can be regenerated seven times (or cycles) with no significant loss in adsorption potential. Overall, the excellent sorption capacity and multiple usage make T-PAA polymer an attractive adsorbent materials for treatment of multicomponent dye bearing effluent in a fixed-bed column system.

Sustainability assessment of Indonesian cement manufacturing via integrated life cycle assessment and analytical hierarchy process method.

Cement is a vital material used in the construction of concrete buildings. World annual cement demand is increasing rapidly along with the improvement in infrastructure development. However, cement manufacturing industries are facing challenges in reducing the environmental impacts of cement production. To resolve this issue, a suitable methodology is crucial to ensure the selected processes are effective and efficient and at the same time environmentally friendly. Different technologies and equipment have potential to produce variations in operational effectiveness, environmental impacts, and manufacturing costs in cement manufacturing industries. Therefore, this work aims to present the sustainability assessment of cement plants by taking into consideration of environmental, social, and economic impacts. Three cement production plants located in Western Indonesian are used as case studies where social impact and environmental impact are evaluated via life cycle assessment (LCA) model. This model is integrated with analytic hierarchy process (AHP), a multi-criteria decision analysis tool in selecting the most sustainable cement manufacturing plant.

Optimization the Process of Chemically Modified Carbon Nanofiber Coated Monolith via Response Surface Methodology for CO2 Capture.

In the present study, a sequence of experiments was performed to assess the influence of the key process parameters on the formation of a carbon nanofiber-coated monolith (CNFCM), using a four-level factorial design in response surface methodology (RSM). The effect of reaction temperature, hydrocarbon flow rate, catalyst and catalyst promoter were examined using RSM to enhance the formation yield of CNFs on a monolith substrate. To calculate carbon yield, a quadratic polynomial model was modified through multiple regression analysis and the best possible reaction conditions were found as follows: a reaction temperature of 800 °C, furfuryl alcohol flow of 0.08525 mL/min, ferrocene catalyst concentration of 2.21 g. According to the characterization study, the synthesized CNFs showed a high graphitization which were uniformly distributed on a monolith substrate. Besides this, the feasibility of carbon dioxide (CO2) adsorption from the gaseous mixture (N2/CO2) under a range of experimental conditions was investigated at monolithic column. To get the most out of the CO2 capture, an as-prepared sample was post-modified using ammonia. Furthermore, a deactivation model (DM) was introduced for the purpose of studying the breakthrough curves. The CO2 adsorption onto CNFCM was experimentally examined under following operating conditions: a temperature of 30-50 °C, pressure of 1-2 bar, flow rate of 50-90 mL/min, and CO2 feed amount of 10-40 vol.%. A lower adsorption capacity and shorter breakthrough time were detected by escalating the temperature. On the other hand, the capacity for CO2 adsorption increased by raising the CO2 feed amount, feed flow rate, and operating pressure. The comparative evaluation of CO2 uptake over unmodified and modified CNFCM adsorbents confirmed that the introduced modification procedure caused a substantial improvement in CO2 adsorption.

Mesoporous Acidic Catalysts Synthesis from Dual-Stage and Rising Co-Current Gasification Char: Application for FAME Production from Waste Cooking Oil.

The main purpose of this work is to investigate the application options of the char produced from gasification plants. Two promising mesoporous acidic catalysts were synthesized using char as a support material. Two char samples were collected from either a dual-stage or a rising co-current biomass gasification plant. The catalysts produced from both gasification char samples were characterized for their physiochemical and morphological properties using N2 physorption measurement, total acidity evaluation through TPD-NH3, functional groups analysis by FT-IR, and morphology determination via FESEM. Results revealed that the dual-stage char-derived mesoporous catalyst (DSC-SO4) with higher specific surface area and acidic properties provided higher catalytic activity for fatty acid methyl esters (FAME) production from waste cooking oil (WCO) than the mesoporous catalyst obtained from char produced by rising co-current gasification (RCC-SO4). Furthermore, the effects of methanol/oil molar ratio (3:1-15:1), catalyst concentration (1-5 wt.% of oil), and reaction time (30-150 min) were studied while keeping the transesterification temperature constant at 65 °C. The optimal reaction conditions for the transesterification of WCO were 4 wt.% catalyst concentration, 12:1 methanol/oil molar ratio, and 90 min operating time. The optimized reaction conditions resulted in FAME conversions of 97% and 83% over DSC-SO4 and RCC-SO4 catalysts, respectively. The char-based catalysts show excellent reusability, since they could be reused six times without any modification.

Synthesis of nanomagnetic sulphonated impregnated Ni/Mn/Na2SiO3 as catalyst for esterification of palm fatty acid distillate.

The deterioration of the environment due to anthropogenic disturbances has become a major concern to scientists and engineers. This study responds to the concern by developing a novel nanomagnetic carbonaceous solid acid catalyst using empty fruit bunches (EFBs) as a precursor. The EFB was sulphonated to obtain acidic EFBs (AEFBs). The impregnation method was performed to incorporate metal oxides, namely, NiO, MnO and Na2SiO3, on the AEFBs. This process resulted in three nanomagnetic catalysts, namely, Na2SiO3-NiO-MnO/AC, NiO-MnO/AC and NiO/AC. According to X-ray diffraction analysis, the crystal size of the NiO/AC, NiO-MnO/AC and Na2SiO3-NiO-MnO/AC catalysts were 13.87, 28.38 and 39.64 nm, respectively, whereas their Brunauer-Emmett-Teller surface areas were 23.78, 12.69 and 16.8 m2 g-1, respectively. To confirm the incorporation of active metallic species (Ni, Mn, Na and SiO) into the carbon surface, we performed X-ray photoelectron spectroscopy. TPD-NH3 absorption showed that the Na2SiO3-Ni-MnO/AC catalysts substantially increased in the active sites and exhibited higher acidity. FESEM images showed the morphology of the surface, pore sizes and agglomeration of the catalysts. Moreover, the vibrating sample magnetometer depicted that the Na2SiO3-Ni-MnO/AC catalyst was ferrimagnetic with magnetisation and magnetic saturation values of 40.27 and 86.04 emu g-1, respectively. The optimal reaction conditions were as follows: PFAD/methanol ratio of 16 : 1, 2 wt% mass of the catalyst, temperature of 120 °C and time of 4 h. Using the synthesised nanomagnetic catalyst exhibited 96% conversion of PFAD to methyl esters. Furthermore, the Na2SiO3-Ni-MnO/AC catalyst was easily separated from the reaction mixture using an external magnet and was recycled six times. The modified nanomagnetic catalyst could be an efficient catalyst for discarded feedstocks for biodiesel production.

Simultaneous Adsorption of Cationic Dyes from Binary Solutions by Thiourea-Modified Poly(acrylonitrile-co-acrylic acid): Detailed Isotherm and Kinetic Studies.

In this study, simultaneous adsorption of cationic dyes was investigated by using binary component solutions. Thiourea-modified poly(acrylonitrile-co-acrylic acid) (TMPAA) polymer was used as an adsorbent for uptake of cationic dyes (malachite green, MG and methylene blue, MB) from aqueous solution in a binary system. Adsorption tests revealed that TMPAA presented high adsorption of MG and MB at higher pH and higher dye concentrations. It suggested that there are strong electrostatic attractions between the surface functional groups of the adsorbent and cationic dyes. The equilibrium analyses explain that both extended Langmuir and extended models are suitable for the description of adsorption data in the binary system. An antagonistic effect was found, probably due to triangular (MG) and linear (MB) molecular structures that mutually hinder the adsorption of both dyes on TMPAA. Besides, the kinetic studies for sorption of MG and MB dyes onto adsorbent were better represented by a pseudo-second-order model, which demonstrates chemisorption between the polymeric TMPAA adsorbent and dye molecules. According to experimental findings, TMPAA is an attractive adsorbent for treatment of wastewater containing multiple cationic dyes.

Study the effect of various wash-coated metal oxides over synthesized carbon nanofibers coated monolith substrates.

In this research work, carbon nanofibers (CNFs) were synthesized on honeycomb monolith substrates using injection chemical vapor deposition (ICVD) technique. The effect of various wash-coated materials and catalyst promoter on the growth rate of CNFs on monolith substrates were examined. The characteristics of the synthesized CNFs-coated monolith composites were examined using Raman spectroscopy, Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and Transmission electron microscopy (TEM) techniques. According to the textural characterization study, the specific surface area and pore volume of CNFs-coated monolith composites were significantly improved as compared to bare monolith which might be attributed to the growth of highly pure and aligned CNFs over monolith substrate. Besides that, the synthesized CNFs-coated monolith possessed extremely well thermal stability up to the temperature of 550 °C which was corresponded to the strong attachment of highly graphitized CNFs over monolith substrates.

Adsorptive Removal of Methylene Blue from Aquatic Environments Using Thiourea-Modified Poly(Acrylonitrile-co-Acrylic Acid).

The paper evaluates the adsorptive potential of thiourea-modified poly(acrylonitrile-co-acrylic acid), (TA-poly(AN-co-AA)) for the uptake of cationic methylene blue (MB) from aquatic environments via a batch system. TA-poly(AN-co-AA) polymer was synthesized through redox polymerization and modified with thiourea (TA) where thioamide groups were introduced to the surface. Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), CHNS and Zetasizer were used to characterize the physico-chemical and morphological properties of prepared TA-poly(AN-co-AA). Afterwards, it was confirmed that incorporation of thioamide groups was successful. The adsorption kinetics and equilibrium adsorption data were best described, respectively, by a pseudo-second-order model and Freundlich model. Thermodynamic analysis showed the exothermic and spontaneous nature of MB uptake by TA-poly(AN-co-AA). The developed TA-poly(AN-co-AA) polymer demonstrated efficient separation of MB dye from the aqueous solution and maintained maximum adsorption capacity after five regeneration cycles. The findings of this study suggested that synthesized TA-poly(AN-co-AA) can be applied successfully to remove cationic dyes from aquatic environments.

Antioxidant Activity, and Volatile and Phytosterol Contents of Strobilanthes crispus Dehydrated Using Conventional and Vacuum Microwave Drying Methods.

The preservation of active constituents in fresh herbs is affected by drying methods. An effective drying method for Strobilanthes crispus which is increasingly marketed as an important herbal tea remains to be reported. This study evaluated the effects of conventional and new drying technologies, namely vacuum microwave drying methods, on the antioxidant activity and yield of essential oil volatiles and phytosterols. These drying methods included convective drying (CD) at 40 °C, 50 °C, and 60 °C; vacuum microwave drying (VMD) at 6, 9, and 12 W/g; convective pre-drying and vacuum microwave finish drying (CPD-VMFD) at 50 °C and 9 W/g; and freeze-drying (FD). GC­MS revealed 33 volatiles, and 2-hexen-1-ol, 2-hexenal, 1-octen-3-ol, linalool, and benzaldehyde were major constituents. The compounds ß-sitosterol and α-linolenic acid were the most abundant phytosterol and fatty acid, respectively, in fresh S. crispus. The highest phenolic content was achieved with CD at 60 °C. The highest antioxidant activity was obtained with CD at 40 °C and VMD at 9 W/g. On the contrary, the highest total volatiles and phytosterols were detected with CD at 50 °C and VMD at 9 W/g, respectively. This study showed that CD and VMD were effective in producing highly bioactive S. crispus. A suitable drying parameter level, irrespective of the drying method used, was an important influencing factor.

Impact of Storage Conditions on the Stability of Predominant Phenolic Constituents and Antioxidant Activity of Dried Piper betle Extracts.

The phenolic constituents in Piper betle are well known for their antioxidant potential; however, current literature has very little information on their stability under the influence of storage factors. Present study evaluated the stability of total phenolic content (TPC) and antioxidant activity together with individual phenolic constituents (hydroxychavicol, eugenol, isoeugenol and allylpyrocatechol 3,4-diacetate) present in dried Piper betle's extract under different storage temperature of 5 and 25 °C with and without light for a period of six months. Both light and temperature significantly influenced TPC and its corresponding antioxidant activity over time. More than 95% TPC and antioxidant activity was retained at 5 °C in dark condition after 180 days of storage. Hydroxychavicol demonstrated the best stability with no degradation while eugenol and isoeugenol displayed moderate stability in low temperature (5 °C) and dark conditions. 4-allyl-1,2-diacetoxybenzene was the only compound that underwent complete degradation. A new compound, 2,4-di-tert-butylphenol, was detected after five weeks of storage only in the extracts exposed to light. Both zero-order and first-order kinetic models were adopted to describe the degradation kinetics of the extract's antioxidant activity. Zero-order displayed better fit with higher correlation coefficients (R² = 0.9046) and the half-life was determined as 62 days for the optimised storage conditions (5 °C in dark conditions).

Kinetic study of lipase-catalyzed glycerolysis of palm olein using Lipozyme TLIM in solvent-free system.

Diacylglycerol (DAG) and monoacylglycerol (MAG) are two natural occurring minor components found in most edible fats and oils. These compounds have gained increasing market demand owing to their unique physicochemical properties. Enzymatic glycerolysis in solvent-free system might be a promising approach in producing DAG and MAG-enriched oil. Understanding on glycerolysis mechanism is therefore of great importance for process simulation and optimization. In this study, a commercial immobilized lipase (Lipozyme TL IM) was used to catalyze the glycerolysis reaction. The kinetics of enzymatic glycerolysis reaction between triacylglycerol (TAG) and glycerol (G) were modeled using rate equation with unsteady-state assumption. Ternary complex, ping-pong bi-bi and complex ping-pong bi-bi models were proposed and compared in this study. The reaction rate constants were determined using non-linear regression and sum of square errors (SSE) were minimized. Present work revealed satisfactory agreement between experimental data and the result generated by complex ping-pong bi-bi model as compared to other models. The proposed kinetic model would facilitate understanding on enzymatic glycerolysis for DAG and MAG production and design optimization of a pilot-scale reactor.