Over the past decades, increasing research in metal-organic frameworks (MOFs) being a large family of highly tunable porous materials with intrinsic physical properties, show propitious results for a wide range of applications in adsorption, separation, electrocatalysis, and electrochemical sensors. MOFs have received substantial attention in electrochemical sensors owing to their large surface area, active metal sites, high chemical and thermal stability, and tunable structure with adjustable pore diameters. Benefiting from the superior properties, MOFs and MOF-derived carbon materials act as promising electrode material for the detection of food contaminants. Although several reviews have been reported based on MOF and its nanocomposites for the detection of food contaminants using various analytical methods such as spectrometric, chromatographic, and capillary electrophoresis. But there no significant review has been devoted to MOF/and its derived carbon-based electrodes using electrochemical detection of food contaminants. Here we review and classify MOF-based electrodes over the period between 2017 and 2022, concerning synthetic procedures, electrode fabrication process, and the possible mechanism for detection of the food contaminants which include: heavy metals, antibiotics, mycotoxins, and pesticide residues. The merits and demerits of MOF as electrode material and the need for the fabrication of MOF and its composites/derivatives for the determination of food contaminants are discussed in detail. At last, the current opportunities, key challenges, and prospects in MOF for the development of smart sensing devices for future research in this field are envisioned.
Employing biomass for environmental conservation is regarded as a successful and environmentally friendly technique since they are cost-effective, renewable, and abundant. Biochar (BC), a thermochemically converted biomass, has a considerably lower production cost than the other conventional activated carbons. This material's distinctive properties, including a high carbon content, good electrical conductivity (EC), high stability, and a large surface area, can be utilized in various research fields. BC is feasible as a renewable source for potential applications that may achieve a comprehensive economic niche. Despite being an inexpensive and environmentally sustainable product, research has indicated that pristine BC possesses restricted properties that prevent it from fulfilling the intended remediation objectives. Consequently, modifications must be made to BC to strengthen its physicochemical properties and, thereby, its efficacy in decontaminating the environment. Modified BC, an enhanced iteration of BC, has garnered considerable interest within academia. Many modification techniques have been suggested to augment BC's functionality, including its adsorption and immobilization reliability. Modified BC is overviewed in its production, functionality, applications, and regeneration. This work provides a holistic review of the recent advances in synthesizing modified BC through physical, chemical, or biological methods to achieve enhanced performance in a specific application, which has generated considerable research interest. Surface chemistry modifications require the initiation of surface functional groups, which can be accomplished through various techniques. Therefore, the fundamental objective of these modification techniques is to improve the efficacy of BC contaminant removal, typically through adjustments in its physical or chemical characteristics, including surface area or functionality. In addition, this article summarized and discussed the applications and related mechanisms of modified BC in environmental decontamination, focusing on applying it as an ideal adsorbent, soil amendment, catalyst, electrochemical device, and anaerobic digestion (AD) promoter. Current research trends, future directions, and academic demands were available in this study.
This review critically examines the effectiveness of ion-imprinted membranes (IIMs) in selectively recovering lithium (Li) from challenging sources such as seawater and brine. These membranes feature customized binding sites that specifically target Li ions, enabling selective separation from other ions, thanks to cavities shaped with crown ether or calixarene for improved selectivity. The review thoroughly investigates the application of IIMs in Li extraction, covering extensive sections on 12-crown-4 ether (a fundamental crown ether for Li), its modifications, calixarenes, and other materials for creating imprinting sites. It evaluates these systems against several criteria, including the source solution's complexity, Li+ concentration, operational pH, selectivity, and membrane's ability for regeneration and repeated use. This evaluation places IIMs as a leading-edge technology for Li extraction, surpassing traditional methods like ion-sieves, particularly in high Mg2+/Li+ ratio brines. It also highlights the developmental challenges of IIMs, focusing on optimizing adsorption, maintaining selectivity across varied ionic solutions, and enhancing permselectivity. The review reveals that while the bulk of research is still exploratory, only a limited portion has progressed to detailed lab verification, indicating that the application of IIMs in Li+ recovery is still at an embryonic stage, with no instances of pilot-scale trials reported. This thorough review elucidates the potential of IIMs in Li recovery, cataloging advancements, pinpointing challenges, and suggesting directions for forthcoming research endeavors. This informative synthesis serves as a valuable resource for both the scientific community and industry professionals navigating this evolving field.
The surfaces of NaY zeolite particles were modified by the alkylsilylation of n-octadecyltrichlorosilane (OTS). Two kinds of modified NaY zeolites were prepared; one with its external surface partially and the other fully covered with alkylsilyl groups. Since the size of OTS is bigger than the pore diameter of NaY, it is attached on the external surface, leaving the internal pore accessible to adsorbate molecules. As a result of alkylsilylation, the adsorption properties of these sorbents were improved. The adsorption properties of these materials were tested by their reaction in a mixture of paraquat and blue dye. The results demonstrate that the alkysilylated NaY materials are capable of simultaneous adsorption of paraquat and blue dye. Paraquat was selectively adsorbed into the internal pore of the zeolite whereas the dye on the externally attached alkylsilyl groups of the sorbent; displaying the unique bimodal amphiphilic character of the alkylsilylated NaY zeolites.
The importance of protein detection system for protein functions analyses in recent post-genomic era is rising with the emergence of label-free protein detection methods. We are focusing on a simple and practical label-free optical-detection method called anomalous reflection (AR) of gold. When a molecular layer forms on the gold surface, significant reduction in reflectivity can be observed at wavelengths of 400-500 nm. This allows the detection of molecular interactions by monitoring changes in reflectivity. In this chapter, we describe the AR method with three different application platforms: (1) gold, (2) gold containing alloy/composite (AuAg2O), and (3) metal-insulator-metal (MIM) thin layers. The AuAg2O composite and MIM are implemented as important concepts for signal enhancement process for the AR technique. Moreover, the observed molecular adsorption and activity is aided by a three-dimensional surface geometry, performed using poly(amidoamine) or PAMAM dendrimer modification. The described system is suitable to be used as a platform for high-throughput detection system in a chip format.
The current demands of sustainable green methodologies have increased the use of enzymatic technology in industrial processes. Employment of enzyme as biocatalysts offers the benefits of mild reaction conditions, biodegradability and catalytic efficiency. The harsh conditions of industrial processes, however, increase propensity of enzyme destabilization, shortening their industrial lifespan. Consequently, the technology of enzyme immobilization provides an effective means to circumvent these concerns by enhancing enzyme catalytic properties and also simplify downstream processing and improve operational stability. There are several techniques used to immobilize the enzymes onto supports which range from reversible physical adsorption and ionic linkages, to the irreversible stable covalent bonds. Such techniques produce immobilized enzymes of varying stability due to changes in the surface microenvironment and degree of multipoint attachment. Hence, it is mandatory to obtain information about the structure of the enzyme protein following interaction with the support surface as well as interactions of the enzymes with other proteins. Characterization technologies at the nanoscale level to study enzymes immobilized on surfaces are crucial to obtain valuable qualitative and quantitative information, including morphological visualization of the immobilized enzymes. These technologies are pertinent to assess efficacy of an immobilization technique and development of future enzyme immobilization strategies.
Lead contamination present in wastewater is one of the major problems due to its toxicity and persistence. This issue increased dramatically and led to the environmental and health concerns worldwide. Therefore, this study aims to remove lead from synthetic wastewater effluent by adsorption process. In this study, nanomaterial called graphene oxide (GO) is used as an adsorbent due to its mechanical strength and high surface area. The parameters were optimized using Fractional factorial design under response surface method. GO demonstrates high adsorption capacity, qmax = 500 mg/g at 100 mg/L of initial lead concentration and at optimum pH 9. Adsorption isotherm of lead was also investigated to evaluate the adsorption capacity. The equilibrium data of graphene oxide adsorption was better represented by the Langmuir isotherm and was achieved within 60 minutes. The results showed that GO has potential to be an important adsorbent for lead removal. In the future, GO might be imbedded as adsorbent in the membrane fabrication for wastewater treatment.
Biochar/layered double hydroxide (LDH) composites have gained considerable attention in recent times as low-cost sustainable materials for applications in water treatment. This paper critically evaluates the latest development in applications of biochar/LDH composites in water treatment with an emphasis on adsorption and catalytic degradation of various pollutants. The adsorption of various noxious contaminants, i.e., heavy metals, dyes, anions, and pharmaceuticals onto biochar/LDH composites are described in detail by elaborating the adsorption mechanism and regeneration ability. The synergistic effect of LDH with biochar exhibited significant improvement in specific surface area, surface functional groups, structure heterogeneity, stability, and adsorption characteristics of the resulting biochar/LDH composites. The major hurdles and challenges associated with the synthesis and applications of biochar/LDH composites in water remediation are emphasized. Finally, a roadmap is suggested for future research to assure the effective applications of biochar/LDH composites in water purification.
Commercial titanium dioxide Degussa P25 (TiO2) was used for the adsorption of reactive red 120
(RR120) dye in a batch system. The optimization functions such as solution pH (3-12), adsorbent dosage (0.02 g-1.2 g), and initial dye concentration (30-400 mg/L) were studied. The equilibrium adsorption data for RR120 dye was analyzed by two types of isotherm models which are Langmuir and Freundlich models. The adsorption at equilibrium showed a better fit for linear Langmuir isotherm with the adsorption capacity, qmax of 18.62 mg/g at 303 K. The adsorption kinetic was well-described by pseudosecond order model. TiO2 showed a decent outcome due to the ability to adsorb target pollutants with theadded advantage of providing large hydroxyl groups (OH) on the surface of TiO2 so that pollutants can be adsorbed by interacting on the surface of OH.
Cross-linked chitosan-epichlorohydrin was prepared for the adsorption of Reactive Red 4 (RR4).
Response surface methodology (RSM) with 3–level Box-Behnken design (BBD) was employed to
optimize the RR4 dye removal efficiency from aqueous solution. The adsorption key parameters that were selected such as adsorbent dose (A: 0.5 – 1.5 g), pH (B: 4 – 10) and time (30 – 80 min). The F-value of BBD model for RR4 removal efficiency was 185.36 (corresponding p-value < 0.0001). The results illustrated that the highest RR4 removal efficiency (70.53%) was obtained at the following conditions: adsorbent dose (1.0 g), pH 4 and time of 80 min.
Palm oil sludge (POS) is an organic waste generated from the palm oil industry. POS causes environmental pollution if it is improperly disposed. In this study, the potential of activated POS biochar, as an adsorbent for the removal of SO2 gas was tested. POS biochar was physically activated using CO2 gas. The effects of activation preparation variables i.e. activation temperature (300-700 °C), activation time (30-150 min) and CO2 flow rate (100-500 ml/min) were investigated using design expert version 8.0.7.1 software. Central Composite Design (CCD) was used to develop a quadratic model to correlate the operating variables with the activated biochar adsorption capacity. Analysis of variance (ANOVA) was performed to identify the significant factors on the experimental design response. The optimum preparation conditions of activated POS biochar were found to be at activation temperature of 442 °C, activation time of 63 min and CO2 flow rate of 397 ml/min. The maximum adsorption capacity at the optimum conditions was recorded as 16.65 mg/g. The adsorption capacity increased significantly after the activation process. Characteristics of the activated POS biochar proposed that SO2 was physically adsorbed. Furthermore, it was found that the adsorption capacity can be further enhanced by increasing the reaction temperature to 100 °C or with 15% of relative humidity in the inlet gas. The prepared adsorbents can be regenerated by thermal treatment.
Metallic transition metal dichalcogenides (TMDs)1-8 are good catalysts for the hydrogen evolution reaction (HER). The overpotential and Tafel slope values of metallic phases and edges9 of two-dimensional (2D) TMDs approach those of Pt. However, the overall current density of 2D TMD catalysts remains orders of magnitude lower (~10-100 mA cm-2) than industrial Pt and Ir electrolysers (>1,000 mA cm-2)10,11. Here, we report the synthesis of the metallic 2H phase of niobium disulfide with additional niobium (2H Nb1+xS2, where x is ~0.35)12 as a HER catalyst with current densities of >5,000 mA cm-2 at ~420 mV versus a reversible hydrogen electrode. We find the exchange current density at 0 V for 2H Nb1.35S2 to be ~0.8 mA cm-2, corresponding to a turnover frequency of ~0.2 s-1. We demonstrate an electrolyser based on a 2H Nb1+xS2 cathode that can generate current densities of 1,000 mA cm-2. Our theoretical results reveal that 2H Nb1+xS2 with Nb-terminated surface has free energy for hydrogen adsorption that is close to thermoneutral, facilitating HER. Therefore, 2H Nb1+xS2 could be a viable catalyst for practical electrolysers.
This study tested the technical feasibility of pyrite and/or persulfate oxidation system for arsenic (As) removal from aqueous solutions. The effects of persulfate on As removal by the pyrite in the integrated treatment were also investigated. Prior to the persulfate addition into the reaction system, the physico-chemical interactions between As and the pyrite alone in aqueous solutions were explored in batch studies. The adsorption mechanisms of As by the adsorbent were also presented. At the same As concentration of 5 mg/L, it was found that As(III) attained a longer equilibrium time (8 h) than As(V) (2 h), while the pyrite worked effectively at pH ranging from 6 to 11. At optimum conditions (0.25 g/L of pyrite, pH 8.0 and 5 mg/L of As(III) concentration), the addition of persulfate (0.5 mM) into the reaction promoted a complete removal of arsenic from the solutions. Consequently, this enabled the treated effluents to meet the arsenic maximum contaminant limit (MCL) of <10 μg/L according to the World Health Organization (WHO)'s requirements. The redox mechanisms, which involved electron transfer from the S22- of the pyrite to Fe3+, supply Fe2+ for persulfate decomposition, oxidizing As(III) to As(V). The sulfur species played roles in the redox cycle of the Fe3+/Fe2+ of the pyrite by giving its electrons, while the As(III) oxidation to As(V) was attributed to the pyrite. Overall, this work reveals the applicability of the pyrite as an adsorbent for water treatment and the importance of persulfate addition to promote a complete As removal from aqueous solutions.
This study investigated the feasibility of integrated ammonium stripping and/or coconut shell waste-based activated carbon (CSWAC) adsorption in treating leachate samples. To valorize unused biomass for water treatment application, the adsorbent originated from coconut shell waste. To enhance its performance for target pollutants, the adsorbent was pretreated with ozone and NaOH. The effects of pH, temperature, and airflow rate on the removal of ammoniacal nitrogen (NH3-N) and refractory pollutants were studied during stripping alone. The removal performances of refractory compounds in this study were compared to those of other treatments previously reported. To contribute new knowledge to the field of study, perspectives on nutrients removal and recovery like phosphorus and nitrogen are presented. It was found that the ammonium stripping and adsorption treatment using the ozonated CSWAC attained an almost complete removal (99%) of NH3-N and 90% of COD with initial NH3-N and COD concentrations of 2500 mg/L and 20,000 mg/L, respectively, at optimized conditions. With the COD of treated effluents higher than 200 mg/L, the combined treatments were not satisfactory enough to remove target refractory compounds. Therefore, further biological processes are required to complete their biodegradation to meet the effluent limit set by environmental legislation. As this work has contributed to resource recovery as the driving force of landfill management, it is important to note the investment and operational expenses, engineering applicability of the technologies, and their environmental concerns and benefits. If properly managed, nutrient recovery from waste streams offers environmental and socio-economic benefits that would improve public health and create jobs for the local community.
The water reservoirs are getting polluted due to increasing amounts of micropollutants such as pharmaceuticals, organic polymers and suspended solids. Powdered activated carbon (PAC) has been proved to be a promising solution for the purification of water without having harmful impacts on the environment. Parameters such as PAC dosing, wastewater hardness, the effect of coagulant and flocculant were evaluated in a batch scale study. These parameters were further applied on a pilot plant scale for the performance evaluation of PAC based removal of micropollutants concerning the contact time and PAC dosing with main focus on recirculation of PAC sludge. The obtained optimum dose was 10-20 mg/L providing 84.40-91.30% removal efficiency of suspended solid micropollutants (MPs) and this efficiency increased to 88.90-93.00% along with coagulant which further raised by the addition of polymer and recirculation process at batch scale. On pilot plant scale, the concentration in contact reactor and PAC removal effectiveness of dissolved air flotation, lamella separator and sedimentation tank were compared. Constant optimisation resulted in a concentration ranging from 2.70 to 3.40 g/L at dosing of PAC 10 mg/L, coagulant 2.00 mg/L and polymer 0.50 mg/L. PAC doses of 10-20 mg/L with 15-30 min contact time proved best for above 70-80% elimination. The recirculation system has also proved an efficient technique because the PAC's adsorption capacity was practically completely used. Small PAC dosages yielded high micropollutants elimination.
There is limited information on the optimal processes to remove heavy metals in greywater. A Response Surface Methodology (RSM) via the Box-Behnken Design (BBD) approach was applied in this study to investigate and optimise the process variables of activation time (1.5-2.5 h), impregnation ratio (0.25-0.75) and zinc chloride (ZnCl2) percentage (20-60%) for the removal of heavy metal ions (Cd, Cu, Pb and Ni) associated with greywater treatment. The quadratic model was chosen to describe the effects of the process variables (activation time, impregnation ratio, ZnCl2 percentage) on predicting the responses (heavy metal ions removal) with low p-values (
Four porous coordination networks have been synthesized from 1,4-benzenedicarboxylate with Cl, Br, I, and NO2 substituents whose different spatial differences are sufficient to influence the coordination mode of adjacent carboxyl moieties to unlock an inter-penetrating framework to give isostructural structures. Their size and polarity differences account for the diverging CO2 adsorption performances.
Mesoporous carbon is a promising material having multiple applications. It can act as a catalytic support and can be used in energy storage devices. Moreover, mesoporous carbon controls body's oral drug delivery system and adsorb poisonous metal from water and various other molecules from an aqueous solution. The accuracy and improved activity of the carbon materials depend on some parameters. The recent breakthrough in the synthesis of mesoporous carbon, with high surface area, large pore-volume, and good thermostability, improves its activity manifold in performing functions. Considering the promising application of mesoporous carbon, it should be broadly illustrated in the literature. This review summarizes the potential application of mesoporous carbon in many scientific disciplines. Moreover, the outlook for further improvement of mesoporous carbon has been demonstrated in detail. Hopefully, it would act as a reference guidebook for researchers about the putative application of mesoporous carbon in multidimensional fields.
Metal nanoclusters have been considered as a new class of chemical sensors due to their unique electronic structures and the particular physicochemical properties. The interaction of N2 molecule with neutral and ionic magnesium nanoclusters Mg17q(q=0,±1), as well as neutral magnesium nanoclusters with the centrality of beryllium and calcium Mg16M (M=Be, Mg, and Ca) have been investigated using CAM-B3LYP/6-311+G(d) level of theory in the gas phase. The electronic properties of magnesium nanoclusters were significantly affected by the adsorption of N2 molecule. The NBO analysis revealed a charge transfer from the adsorbed N2 molecule to the nanocluster. Based on the adsorption energies and enthalpies, a thermodynamically favorable chemisorption process was predicted for the Mg16Ca-N2 complex. The negative value of the Gibbs free energy of Mg16Ca-N2 confirmed the spontaneous adsorption process. The estimated recovery time for Mg16Ca-N2 complex for 8-MR (0.089 s) and 4-MRs (0.075 s) illustrated a possible desorption process for N2 molecule from the surface of Mg16Ca. Our finding also revealed the Mg16Ca has the ability to use as a sensor for detection and absorption of N2 molecule.
The importance of zeolite surface area and pore volume in adsorption processes has been much reported in literature. In addition to that, structural framework and pore network system may also influence the adsorption capacity and selectivity of methane on zeolite. This paper discusses the characteristics of methane adsorption based on several physical properties of the adsorbents such as surface area, pore volume, pore network system and its interaction with adsorbate. The study, using FTIR spectroscopy showed that the adsorbed methane at room temperature was detected in the FTIR region between 3200 cm–1 – 1200 cm–1. Based on the physical properties of the adsorbents and the FTIR spectra of adsorbed methane, the surface area was not the only factor that determined methane adsorption; in fact the type of pore network system of the adsorbent also affected the interaction, thus affecting the adsorption of methane in zeolite.