Siliceous mesoporous molecular sieve (Si-MCM-41) material with highly ordered hexagonal pore arrangement was synthesized at 373 K for 8-days duration by hydrothermal method, dried at 393 K and calcined at 823 K in N2 atmosphere. The calcined Si-MCM-41 was later functionalized with 10-50 wt. % monoethanolamine (MEA) by impregnation method and dried in vacuum at 343 K. The MEA-Si-MCM-41 samples were characterized for their physicochemical properties with FTIR, XRD, TGA, HRTEM, FESEM, BET and elemental analysis. XRD results showed that the intensity of the characteristic peaks of Si-MCM-41 reduces with increasing loading of MEA indicating that the MEA molecules are loaded in the pores as well as on the surface of Si-MCM-41. The appearance of FTIR peaks corresponding to N-H, C-N and C-H bonds suggested that Si-MCM-41 has been functionalized with MEA. The presence of Si-O-Si peaks in FTIR spectra of MEA-Si-MCM-41 samples indicates that the hexagonal pore arrangement remains intact and this is supported by HRTEM images. FESEM images show that MEA-Si-MCM-41 samples became agglomerated with increase loading of MEA. TGA analyses show that the MEA-Si-MCM-41 samples are thermally stable up to 528 K. N2 adsorption-desorption isotherms show that the textural properties of Si-MCM-41 material slowly change from a mesoporous material to non-porous material as the MEA loading increases due to pore filling effect during functionalization with MEA. Detection of N, C and H by elemental analysis confirms the presence of MEA in MEA-Si-MCM-41 samples.
The adsorption of CO at polycrystalline copper surface was investigated spectroscopically. It was found that CO adsorbed as a linear adsorbed CO, Cu-COL and was a dominant species on copper surface at low CO concentration. A Cu-COL was electrochemically converted to a bridge bonded CO, Cu-COB at a high CO concentration condition. Increasing the CO surface coverage, qCO will increase the formation of adsorbed bridge bonded CO. A nitrogen gas purging treatment was used to examine the stability of an adsorbed CO through the evacuation process. The result showed that Cu-COB remained intact while Cu-COL was completely removed from the copper surface. It suggests that Cu-COL may involve in a weak bonding to a copper surface such as in a physisorbed interaction, while Cu-COB consists much stronger bonding such as a chemisorbed interaction. The N2 purging treatment also gave an additional prove that Cu-COB was partly converted to Cu(I)-CO at anodic potential regions.
The influence of PANI additions on methanol sensing properties of ZnO thin films at room temperature had been investigated. Commercial polyaniline powder (PANI) was mixed into 3 mL ZnO solution in five different weight percentages namely 1.25, 2.50, 3.75, 5.00 and 6.25% to obtain ZnO/PANI composite solutions. These solutions were spin coated onto glass substrate to form thin films. Microstructural studies by FESEM indicated that ZnO/PANI films showed porous structures with nanosize grains. The thickness of the film increased from 55 to 256 nm, proportionate to increment of PANI. The presence of 2 adsorption peaks at ~310 nm and ~610 nm in UV-Vis spectrum proved that addition of PANI has modified the adsorption peak of ZnO film. Methanol vapour detection showed that addition of PANI into ZnO dramatically improved the sensing properties of the sensor. The sensors also exhibited good repeatability and reversibility. Sensor with the amount of PANI of 3.75 wt% exhibited the highest sensitivity with response and recovery time was about 10 and 80 s, respectively. The possible sensing mechanism of the sensor was also discussed in this article.
This study was conducted to investigate the batch and fixed-bed adsorption properties of boron on curcumin-impregnated activated carbon (Cur-AC). The maximum boron removal was obtained at pH5.5 and 120 min of contact time. Langmuir and Freundlich isotherm models were applied and it was determined that the experimental data conformed to both models. The Langmuir maximum adsorption capacities for Cur-AC (5.00 mg/g) and regenerated Cur-AC (3.61 mg/g) were obviously higher than the capacity for bare activated carbon (0.59 mg/g). Kinetic studies indicated the adsorption of boron conformed to the intra-particle model. The highest boron removal in fixed-bed column adsorption was achieved up to 99% for the first 5 min at an inlet concentration of 890 mg/L and a flow rate of 8.0 mL/min. Thomas and the Yoon-Nelson models gave better fit to the experimental data. Cur-AC can be reused after elution processes with slightly lower adsorption capacity.
Ultrafiltration grade polysulfone-based mixed matrix membranes (MMMs) incorporated with two-dimensional boron nitride nanosheet (BNNS) was prepared via phase inversion method. The amount of BN incorporated was varied and the influence on membrane morphology, contact angle, surface charge, as well as water permeability and humic acid rejection were investigated. Results revealed that the addition of BN to the membrane matrix resulted in profound increase in water permeability (almost tripled to that of neat PSf) and humic acid rejection due to the increase in pore size and surface negative charge. Beyond the morphological changes imparted by the inclusion of BNNS, we postulated that the presence of BNNS within the membrane matrix also contribute to the enhancement in flux and rejection based on surface-slip and selective interlayer transport. Despite the favourable augmentation of water transport and filtration performance, the MMMs suffered with fouling problem due to the entrapment of foulant within the enlarged pores and the membrane valleys. Its inherent adsorptive character could be a disadvantage when utilized as membrane filler.
The environment sustenance and preservation of global climate are known as the crucial issues of the world today. Currently, the crisis of global warming due to CO2 emission has turned into a paramount concern. To address such a concern, diverse CO2 capture and sequestration techniques (CCS) have been introduced so far. In line with this, Metal Organic Frameworks (MOFs) have been considered as the newest and most promising material for CO2 adsorption and separation. Due to their outstanding properties, this new class of porous materials a have exhibited a conspicuous potential for gas separation technologies especially for CO2 storage and separation. Thus, the present review paper is aimed to discuss the adsorption properties of CO2 on the MOFs based on the adsorption mechanisms and the design of the MOF structures. In addition, the main challenge associated with using this prominent porous material has been mentioned.
In this work, graphene oxide (GO) and its reduced graphene oxide-zinc oxide nanocomposite (rGO-ZnO) was used for the removal of Cr (VI) from aqueous medium. By employing a variety of characterization techniques, morphological and structural properties of the adsorbents were determined. The adsorption study was done by varying concentration, temperature, pH, time, and amount of adsorbent. The results obtained confirmed that rGO-ZnO is a more economical and promising adsorbent for removing Cr (VI) as compared to GO. Kinetic study was also performed, which suggested that sorption of Cr (VI) follows the pseudo-first-order model. For equilibrium study, non-linear Langmuir was found a better fitted model than its linearized form. The maximum adsorption capacity calculated for GO and rGO-ZnO nanocomposite were 19.49 mg/g and 25.45 mg/g, respectively. Endothermic and spontaneous nature of adsorption was detected with positive values of ΔS (change in entropy), which reflects the structural changes happening at the liquid/solid interface.
Lead (Pb) is one of the toxic heavy metals that pollute the environment as a result of industrial activities. This study aims to optimize Pb removal from water by using horizontal free surface flow constructed wetland (HFSFCW) planted with Scirpus grossus. Optimization was conducted using response surface methodology (RSM) under Box-Behnken design with the operational parameters of initial Pb concentration, retention time, and aeration. Optimization results showed that 37 mg/L of initial Pb concentration, 32 days of retention time, and no aeration were the optimum conditions for Pb removal by using the systems. Validation test was run under two different conditions, namely, non-bioaugmented and bioaugmented with rhizobacteria (Bacillus cereus, B. pumilus, B. subtilis, Brevibacillus choshinensis, and Rhodococcus rhodochrous). Results of the validation test showed that Pb removal in water achieved 99.99% efficiency with 0.2% error from the RSM prediction, while the adsorption of Pb by plants reached 5160.18 mg/kg with 10.6% error from the RSM prediction. The bioaugmentation of the five rhizobacterial species showed a slight improvement in Pb removal from water and Pb adsorption by plants. However, no significant improvement was achieved (p
Water pollution due to the discharge of untreated industrial effluents is a serious environmental and public health issue. The presence of organic pollutants such as polycyclic aromatic hydrocarbons (PAHs) causes worldwide concern because of their mutagenic and carcinogenic effects on aquatic life, human beings, and the environment. PAHs are pervasive atmospheric compounds that cause nervous system damage, mental retardation, cancer, and renal kidney diseases. This research presents the first usage of palm kernel shell biochar (PKSB) (obtained from agricultural waste) for PAH removal from industrial wastewater (oil and gas wastewater/produced water). A batch scale study was conducted for the remediation of PAHs and chemical oxygen demand (COD) from produced water. The influence of operating parameters such as biochar dosage, pH, and contact time was optimized and validated using a response surface methodology (RSM). Under optimized conditions, i.e., biochar dosage 2.99 g L-1, pH 4.0, and contact time 208.89 min, 93.16% of PAHs and 97.84% of COD were predicted. However, under optimized conditions of independent variables, 95.34% of PAH and 98.21% of COD removal was obtained in the laboratory. The experimental data were fitted to the empirical second-order model of a suitable degree for the maximum removal of PAHs and COD by the biochar. ANOVA analysis showed a high coefficient of determination value (R2 = 0.97) and a reasonable second-order regression prediction. Additionally, the study also showed a comparative analysis of PKSB with previously used agricultural waste biochar for PAH and COD removal. The PKSB showed significantly higher removal efficiency than other types of biochar. The study also provides analysis on the reusability of PKSB for up to four cycles using two different methods. The methods reflected a significantly good performance for PAH and COD removal for up to two cycles. Hence, the study demonstrated a successful application of PKSB as a potential sustainable adsorbent for the removal of micro-pollutants from produced water.
Corrosion inhibitory effects of new synthesized compound namely 5,5'- ((1Z,1'Z)-(1,4-phenylenebis(methanylylidene))bis(azanylylidene))bis(1,3,4-thiadiazole-2-thiol) (PBB) on mild steel in 1.0 M HCl was investigated at different temperatures using open circuit potential (OCP), potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). Results showed that PBB inhibited mild steel corrosion in acid solution and indicated that the inhibition efficiencies increased with the concentration of inhibitor, but decreased proportionally with temperature. Changes in impedance parameters suggested the adsorption of PBB on the mild steel surface, leading to the formation of protective films.
This study reports on the synthesis of bi-metal compound (BMC) adsorbents based on commercial coconut activated carbon (CAC), surface-modified with metal acetate (ZnAc2), metal oxide (ZnO), and the basic compounds potassium hydroxide (KOH) and sodium hydroxide (NaOH). The adsorbents were then characterized by scanning electron microscopy and elemental analysis, microporosity analysis through Brunauer-Emmett-Teller (BET) analysis, and thermal stability via thermogravimetric analysis. Adsorption-desorption test was conducted to determine the adsorption capacity of H2S via 1 L adsorber and 1000 ppm H2S balanced 49.95% for N2 and CO2. Characterization results revealed that the impregnated solution homogeneously covered the adsorbent surface, morphology, and properties. The adsorption test result reveals that the ZnAc2/ZnO/CAC_B had a higher H2S breakthrough adsorption capacity and performed at larger than 90% capability compared with a single modified adsorbent (ZnAc2/CAC). Therefore, the synthesized BMC adsorbents have a high H2S loading, and the abundance and low cost of CAC may lead to favorable adsorbents in H2S captured.
Water treatment is a worldwide issue. This review aims to present current problems and future challenges in water treatments with the existing methodologies. Carbon nanotube production, characterization, and prospective uses have been the subject of considerable and rigorous research around the world. They have a large number of technical uses because of their distinct physical characteristics. Various catalyst materials are used to make carbon nanotubes. This review's primary focus is on integrated and single-treatment technologies for all kinds of drinking water resources, including ground and surface water. Inorganic non-metallic matter, heavy metals, natural organic matter, endocrine-disrupting chemicals, disinfection by-products and microbiological pollutants are among the contaminants that these treatment systems can remediate in polluted drinking water resources. Significant advances in the antibacterial and adsorption capabilities of carbon-based nanomaterials have opened up new options for excluding organic/inorganic and biological contaminants from drinking water in recent years. The advancements in multifunctional nanocomposites synthesis pave the possibility for their use in enhanced wastewater purification system design. The adsorptive and antibacterial characteristics of six main kinds of carbon nanomaterials are single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphene oxide, fullerene and single-walled carbon nanohorns. This review potentially addressed the essential metallic and polymeric nanocomposites, are described and compared. Barriers to use these nanoparticles in long-term water treatment are also discussed.
The performance of lysozyme adsorption by the aminated nanofiber membrane immobilized with Reactive Green 19 (RG19) dyes was evaluated in batch and flow systems. The physicochemical properties of the dye-immobilized nanofiber membrane were characterized. The parameters of batch-mode adsorption of lysozyme (e.g., pH, initial dye concentration, and lysozyme concentration) were optimized using the Taguchi method. In a flow process, the factors influencing the dynamic binding performance for lysozyme adsorption in the chicken egg white (CEW) solution include immobilized dye concentration, adsorption pH value, feed flow rate, and feed CEW concentration. The impact of these operating conditions on the lysozyme purification process was investigated. Under optimal conditions, the recovery yield and purification factor of lysozyme achieved from the one-step adsorption process were 98.52% and 143 folds, respectively. The dye-affinity nanofiber membrane also did not exhibit any significant loss in its binding capacity and purification performance after five consecutive uses.
The main objectives of this study are to synthesize a new solid-supported ionic liquid (SSIL) that has a covalent bond between the solid support, i.e., activated silica gel, with thiosalicylate-based ionic liquid and to evaluate the performance of this new SSIL as an extractant, labelled as Si-TS-SSIL, and to remove Pb(II) ions from an aqueous solution. In this study, 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium thiosalicylate ([MTMSPI][TS]) ionic liquid was synthesized and the formation of [MTMSPI][TS] was confirmed through structural analysis using NMR, FTIR, IC, TGA, and Karl Fischer Titration. The [MTMSPI][TS] ionic liquid was then chemically immobilized on activated silica gel to produce a new thiosalicylate-based solid-supported ionic liquid (Si-TS-SSIL). The formation of these covalent bonds on Si-TS-SSIL was confirmed by solid-state NMR analysis. Meanwhile, BET analysis was performed to study the surface area of the activated silica gel and the prepared Si-TS-SSIL (before and after washing with solvent) with the purpose to show that all physically immobilized [MTMSPI][TS] has been washed off from Si-TS-SSIL, leaving only chemically immobilized [MTMSPI][TS] on Si-TS-SSIL before proceeding with removal study. The removal study of Pb(II) ions from an aqueous solution was carried out using Si-TS-SSIL as an extractant, whereby the amount of Pb(II) ions removed was determined by AAS. In this removal study, the experiments were carried out at a fixed agitation speed (400 rpm) and fixed amount of Si-TS-SSIL (0.25 g), with different contact times ranging from 2 to 250 min at room temperature. The maximum removal capacity was found to be 8.37 mg/g. The kinetics study was well fitted with the pseudo-second order model. Meanwhile, for the isotherm study, the removal process of Pb(II) ions was well described by the Freundlich isotherm model, as this model exhibited a higher correlation coefficient (R2), i.e., 0.99, as compared to the Langmuir isotherm model.
Inverse vulcanized polysulfides have been used as low-cost and effective adsorbents to remediate heavy metals in wastewater. Inverse vulcanization introduces sustainable polysulfide synthesis by solving the rapid desulfurization problem of unstable polysulfides, and provides superior performance compared to conventional commercial adsorbents. The review discussed the brief applications of the inverse vulcanized polysulfides to remove heavy metal wastewater and emphasized the modified synthesis processes for enhanced uptake ratios. The characteristics of polysulfide adsorbents, which play a vital role during the removal process are highlighted with a proper discussion of the interaction between metal ions and polysulfides. The review paper concludes with remarks on the future outlook of these low-cost adsorbents with high selectivity to heavy metals. These polysulfide adsorbents can be prepared using a wide variety of crosslinker monomers including organic hydrocarbons, cooking oils, and agro-based waste materials. They have shown good surface area and excellent metal-binding capabilities compared to the commercially available adsorbents. Proper postmodification processes have enabled the benefits of repetitive uses of the polysulfide adsorbents. The improved surface area obtained by appropriate choice of crosslinkers, modified synthesis techniques, and regeneration through post-modification has made inverse vulcanized polysulfides capable of removing.
The inherent toxicity, mutagenicity and carcinogenicity of dyes that are discharged into aquatic ecosystems, harming the health of humans and animals. ZIF-8 based composites are regarded as good adsorbents for the breakdown of dyes in order to remove or degrade them. In the course of this research, metal-organic framework materials known as ZIF-8 and its two stable composites, ZIF-8/BiCoO3 (MZBC) and ZIF-8/BiYO3 (MZBY), were produced via a hydrothermal process and solvothermal process, respectively, for the dangerous Congo red (CR) dye removal from the solution in water using adsorption method. According to the findings, the most significant amount of CR dye that could be adsorbed is onto MZBC, followed by MZBY and ZIF-8. The pseudo-second-order kinetic model was used effectively to match the data for adsorption behavior and was confirmed using the Langmuir isotherm equation. There is a possibility that the pH and amount of adsorbent might influence the adsorption behavior of the adsorbents. According to the experiment results, the technique featured an endothermic adsorption reaction that spontaneously occurred. The higher adsorption capability of MZBC is because of the large surface area. This results in strong interactions between the functional groups on the surface of MZBC and CR dye molecules. In addition to the electrostatic connection between functional group Zn-O-H on the surface of ZIF-8 in MZBC and the -NH2 or SO3 functional group areas in CR molecules, it also includes the strong π-π interaction of biphenyl rings.
This work is scrutinizing the development of metallized biochar as a low-cost bio-sorbent for low temperature CO2 capture with high adsorption capacity. Accordingly, single-step pyrolysis process was carried out in order to synthesize biochar from rambutan peel (RP) at different temperatures. The biochar product was then subjected to wet impregnation with several magnesium salts including magnesium nitrate, magnesium sulphate, magnesium chloride and magnesium acetate which then subsequently heat-treated with N2. The impregnation of magnesium into the biochar structure improved the CO2 capture performance in the sequence of magnesium nitrate > magnesium sulphate > magnesium chloride > magnesium acetate. There is an enhancement in CO2 adsorption capacity of metallized biochar (76.80 mg g-1) compare with pristine biochar (68.74 mg g-1). It can be justified by the synergetic influences of physicochemical characteristics. Gas selectivity study verified the high affinity of biochar for CO2 capture compared with other gases such as air, methane, and nitrogen. This investigation also revealed a stable performance of the metallized biochar in 25 cycles of CO2 adsorption and desorption. Avrami kinetic model accurately predicted the dynamic CO2 adsorption performance for pristine and metallized biochar.
Heavy metals released by various industries are among the major pollutants found in water resources. In this research, biosorption technique was employed to remove cadmium (Cd2+) from an aqueous system using a novel biosorbent developed from okara waste (OW), a residue from soya bean-based food and beverage processing. Characterisation results revealed that the OW biosorbent contained functional groups such as hydroxyl-, carboxyl- and sulphur-based functional groups, and the surface of the biosorbent was rough with multiple fissures which might be the binding sites for the pollutant. The effects of dosage, solution pH, initial Cd2+ concentration, temperature and contact time were investigated using batch adsorption mode. The biosorption equilibrium and kinetic were best described by the Langmuir and Elovich models, respectively. The maximum biosorption capacities predicted by the Langmuir model were 10.91-14.80 mg/g at 30-70 °C, and the biosorption process was favourable as evident from 0 < RL < 1. The uptake of Cd2+ by the OW biosorbent was spontaneous and endothermic. The plausible biosorption mechanisms of this study could be ionic exchange, hydrogen bonding and electrostatic interactions. The Cd2+ loaded OW biosorbent could be regenerated using 0.4 M of HCl solution and regeneration was studied for 4 adsorption-desorption cycles. The present investigation supported that OW can be reused as a value-added biosorbent product for the removal of Cd2+ from the contaminated water.
Eggshell is a food waste produced worldwide in substantial amount with very limited recycling activity. In this study, the potential of ethanol-treated calcined eggshell was tested as sorbent for SO2 and H2S. Three variables were selected in the preparation of sorbents via response surface methodology (RSM), i.e., concentration of ethanol in water (50%, 70%, 90%), reaction temperature (20 °C, 40 °C, 60 °C), and contact time (30, 60, 90 min). Central composite design (CCD) was used to develop a quadratic model to correlate the operating variables with the adsorption capacity. Analysis of variance (ANOVA) was performed to identify the significant factors of the experimental design. It was found that the reaction temperature during the sorbent preparation was the most significant factor. The optimum preparation conditions using RSM were found at 20 °C of reaction temperature with 76.37% of ethanol concentration for 67 min of reaction time. The maximum adsorption capacity for the optimized sorbent was found to be 27.75 mg/g and 9.55 mg/g for SO2 and H2S, respectively. The prepared sorbent was more selective towards SO2 compared with H2S. Moreover, the presence of 40% of relative humidity in the inlet gas further enhanced the adsorption capacity of both gases. The ethanol-treated calcined eggshell was further substantiated by FESEM, BET, FTIR, XRD, and XRF. Results showed potential usage of eggshell as a sorbent for SO2 and H2S gases.
Removal of H2S (hydrogen sulfide) from biogas is anticipated for higher energy conversion of methane (CH4), while reducing the detrimental impacts of corroding the metal parts in the plant and its hazardous effect on humans and the environment. The introduction of microwave (MW) heating and nitrogen-modification could generate superior adsorbent features, contributing to high H2S removal. Up to date, there is no work reported on the influence of physicochemical characteristics of nitrogen-modified carbon synthesized via MW and conventional heating (TH) methods and their performance in H2S removal. Palm shell activated carbon (PSAC) was functionalized with nitrogen groups via urea impregnation, followed by the synthesis of MW and TH at 950 °C, 500 ml/min of N2 flow rate and 30 min of heating time. MW and TH heating effects on the modified PSAC adsorbent were analysed and compared towards hydrogen sulfide (H2S) removal. PSAC with nitrogen functionalization produced using MW heating (PSAC-MW) demonstrates superior performance, with an adsorption capacity of 356.94 mg/g. The adsorbent sample generated using MW heating exhibited notable properties, including a large surface area and a sponge-like structure, with new pores developed within the current pores. Instead of that, there was an observation of 'hot spot' appearance during the MW heating process, which is believed to be responsible for the development of physical and chemical characteristics of the adsorbent. Thus, it is believed that MW heating was assisted in the development of the adsorbent's properties and at the same time contributed to the high removal of H2S at low adsorption temperature. The utilization of biomass-based adsorbent (PSAC) for H2S removal can address the lignocellulosic waste disposal problem, while mitigating the H2S release from the biogas production plants thus has several environmental merits. This indirectly contributed to zero-waste generation, while overcoming the adverse effects of H2S.