Nickel augmented biochar for sustaining produced water treatment to decarbonize oil and gas industrial waste using anaerobic-aerobic granular cylindrical periodic discontinuous batch reactors.

This study assessed the efficacy of granular cylindrical periodic discontinuous batch reactors (GC-PDBRs) for produced water (PW) treatment by employing eggshell and waste activated sludge (WAS) derived Nickel (Ni) augmented biochar. The synthesized biochar was magnetized to further enhance its contribution towards achieving carbon neutrality due to carbon negative nature, Carbon dioxide (CO2) sorption, and negative priming effects. The GC-PDBR1 and GC-PDBR2 process variables were optimized by the application of central composite design (CCD). This is to maximize the decarbonization rate. Results showed that the systems could reduce total phosphorus (TP) and chemical oxygen demand (COD) by 76-80% and 92-99%, respectively. Optimal organic matter and nutrient removals were achieved at 80% volumetric exchange ratio (VER), 5 min settling time and 3000 mg/L mixed liquor suspended solids (MLSS) concentration with desirability values of 0.811 and 0.954 for GC-PDBR1 and GC-PDBR2, respectively. Employing four distinct models, the biokinetic coefficients of the GC-PDBRs treating PW were calculated. The findings indicated that First order (0.0758-0.5365) and Monod models (0.8652-0.9925) have relatively low R2 values. However, the Grau Second-order model and Modified Stover-Kincannon model have high R2 values. This shows that, the Grau Second Order and Modified Stover-Kincannon models under various VER, settling time, and MLSS circumstances, are more suited to explain the removal of pollutants in the GC-PDBRs. Microbiological evaluation demonstrated that a high VER caused notable rises in the quantity of several microorganisms. Under high biological selective pressure, GC-PDBR2 demonstrated a greater percentage of nitrogen removal via autotrophic denitrification and a greater number of nitrifying bacteria. The overgrowth of bacteria such as Actinobacteriota spp. Bacteroidota spp, Gammaproteobacteria, Desulfuromonas Mesotoga in the phylum, class, and genus, has positively impacted on granule formation and stability. Taken together, our study through the introduction of intermittent aeration GC-PDBR systems with added magnetized waste derived biochar, is an innovative approach for simultaneous aerobic sludge granulation and PW treatment, thereby providing valuable contributions in the journey toward achieving decarbonization, carbon neutrality and sustainable development goals (SDGs).

Enhancing Li+ recovery in brine mining: integrating next-gen emotional AI and explainable ML to predict adsorption energy in crown ether-based hierarchical nanomaterials.

Artificial intelligence (AI) is being employed in brine mining to enhance the extraction of lithium, vital for the manufacturing of lithium-ion batteries, through improved recovery efficiencies and the reduction of energy consumption. An innovative approach was proposed combining Emotional Neural Networks (ENN) and Random Forest (RF) algorithms to elucidate the adsorption energy (AE) (kcal mol-1) of Li+ ions by utilizing crown ether (CE)-incorporated honeycomb 2D nanomaterials. The screening and feature engineering analysis of honeycomb-patterned 2D materials and individual CE were conducted through Density Functional Theory (DFT) and Gaussian 16 simulations. The selected honeycomb-patterned 2D materials encompass graphene, silicene, and hexagonal boron nitride, while the specific CEs evaluated are 15-crown-5 and 18-crown-6. The crown-passivated 2D surfaces held a significant adsorption site through van der Waals forces for efficient recovery of Li+ ions. ENN predicted the targeted adsorption sites with high precision and minimal deviation. The eTAI (XAI) based Shapley Additive exPlanations (SHAP) was also explored for insight into the feature importance of CE embedded 2D nanomaterials for the recovery of Li+ ions. The extreme gradient boosting algorithm (XGBoost) model demonstrated a RT-2-MAPE = 0.4618% and ENN-2-MAPE = 0.4839% for the feature engineering analysis. This research would be an insight into the AI-driven nanotechnology that presents a viable and sustainable approach for the extraction of natural resources through the application of brine mining.

Anodic voltage performance of conducting polymer-functionalized boron nitride nanosheets: a DFT assessment.

The search for low-diffusion barriers and high-capacity anode materials is considered a key step in boosting the efficiency of metal-ion batteries. Herein, we investigate the impact of a series of conducting polymers (CPs), namely, polyacetylene (PA), polypyrrole (PP), poly-p-phenylene (PPPh), and polythiophene (PT), on enhancing the material design and anodic performance of boron nitride nanosheet (BNNS)-based Li-ion and Na-ion batteries. For this purpose, first principle DFT simulations, utilizing both clustered and periodic models, are systematically performed to assess the stability of such nanostructures and their electronic behavior as potential anodic materials. It is revealed that frontier molecular orbitals calculated for BNNSs are stabilized upon association with the series of CPs, resulting in a reduction in the energy gaps of CP-BNNSs by nearly 50%, which in turn improves the charge transfer properties and cell reaction kinetics. A remarkable improvement in the cell voltage is predicted for PP and PT functionalized BNNSs, reaching approximately 3.5 V for Li+ and 3.0 V for Na+ ions. The outcome of the study emphasizes the influence of the size of metal ions, whether mono- or di-valent, and the nature of adsorbed conducting polymers. Manipulating the electronic features of boron nitride nanostructured surfaces through non-covalent functionalization with conducting polymers could pave the way for the design of highly efficient energy storage anodic CP-BNNS-based systems.

One-step Formation of Urea from Carbon Dioxide and Nitrogen Using Water Microdroplets.

Water (H2O) microdroplets are sprayed onto a graphite mesh covered with a CuBi2O4 coating using a 1:1 mixture of N2 and CO2 as the nebulizing gas. The resulting microdroplets contain urea [CO(NH2)2] as detected by both mass spectrometry and 13C nuclear magnetic resonance. This gas-liquid-solid heterogeneous catalytic system synthesizes urea in one step on the 0.1 ms time scale. The conversion rate reaches 2.7 mmol g-1 h-1 at 25 °C and 12.3 mmol g-1 h-1 at 65 °C, with no external voltage applied. Water microdroplets serve as the hydrogen source and the electron transfer medium for N2 and CO2 in contact with CuBi2O4. Water-gas and water-solid contact electrification are speculated to drive the reaction process. This strategy couples N2 fixation and CO2 utilization in an ecofriendly process to produce urea, converting a greenhouse gas into a value-added product.

Facile engineering of mesoporous silica for the effective removal of anionic dyes from wastewater: Insights from DFT and experimental studies.

The discharge of dye effluents from the textile industries has become a major environmental issue due to its potential to impart serious harm to human health and aquatic life. Mesoporous silica due to its high chemical stability, large surface area, tunable morphologies, large pore volume and pore size and cost-effectiveness is commonly used to remove such dyes before recycling of the wastewater for agricultural, domestic, and industrial applications. However, the low colloidal stability, the fast aggregation of the silica particles and the slow etching of the silica surface often results in the fast deactivation of the adsorbents and limits their long-term applications. In this study, we report the functionalization of mesoporous silica (SBA-15) with ZnO nanoparticles for the effective removal of anionic dyes. The Zn-silica exhibited highly positive surface with a dipole moment of 172 Debye and high charge transfer efficacy with an energy bandgap (ΔE) of 3.35 eV as revealed by quantum chemical DFT simulations. It achieved excellent removal of Alizarin red dye reaching a removal efficiency of 99.99 % and an adsorption capacity of 50 mg/g. In the presence of heavy metal ions commonly present in wastewater (Cd2+, Co2+, Zn2+, Ni2+, Cu2+ and Hg2+), the Zn-silica maintain excellent stability, high selectivity, and reusability within 5 cycles without a significant decline in efficiency. This study thus presents an effective way of wastewater purification on cost-effective adsorbents for meeting the water scarcity demands.

Integrated clustering analysis for delineating seawater intrusion and heavy metals in Arabian Gulf Coastal groundwater of Saudi Arabia.

The intrusion of seawater (SWI) into coastal aquifers is a major concern worldwide, affecting the quantity and quality of groundwater resources. The region of Saudi Arabia that lies along the eastern coast has been affected by SWI, making it crucial to accurately identify and monitor the affected areas. This investigation aimed to map the degree of seawater intrusion in a complex aquifer system in the study area using an integrated clustering analysis approach. The study collected 41 groundwater samples from wells penetrating multi-layered aquifers, and the samples were analyzed for physicochemical properties and major ions. Clustering analysis methods, including Hierarchical Clustering Analysis (double-clustering) (HCA-DC), K-mean (KMC), and fuzzy k-mean clustering (FKM), were employed to evaluate the spatial distribution and association of the groundwater properties. The results revealed that the analyzed GW samples were divided into four clusters with varying degrees of SWI. Clusters A, B, C, and D contained GW samples with very low (fsea of 1.9%), high (fsea of 14.9%), intermediate (fsea of 7.9%), and low (fsea of 5.2%) degrees of SWI, respectively. FKM clustering exhibited superior performance with a silhouette score of 0.83. Additionally, the study found a direct correlation between the degree of SWI and increased concentrations of boron, strontium, and iron, demonstrating SWI's impact on heavy metal levels. Notably, the boron concentration in cluster B, which endured high SWI, exceeded WHO guidelines. The study demonstrates the value of clustering analysis for accurately monitoring SWI and associated heavy metals. The findings can guide policies to mitigate SWI impacts and benefit groundwater-dependent communities. Further research can help develop effective strategies to mitigate SWI effects on groundwater quality and availability.

Highly Permeable Sulfonated Polydopamine Integrated MXene Membranes for Efficient Surfactant-Stabilized Oil-in-Water Separation.

MXene is an incredibly promising two-dimensional material with immense potential to serve as a high-performing separating or barrier layer to develop advanced membranes. Despite the significant progress made in MXene membranes, two major challenges still exist: (i) effectively stacking MXene nanosheets into defect-free membranes and (ii) the high fouling tendency of MXene-based membranes. To address these issues, we employed sulfonated polydopamine (SPD), which simultaneously serves as a binding agent to promote the compact assembling of Ti3C2Tx MXenes (MX) nanosheets and improves the antifouling properties of the resulting sulfonated polydopamine-functionalized MX (SPDMX) membranes. The SPDMX membrane was tested for challenging surfactant-stabilized oil-in-water separation with an impressive efficiency of 98%. Moreover, an ultrahigh permeability of 1620 LMH/bar was also achieved. The sulfonation of PD helps in improving the antifouling characteristics of SPDMX by developing a strong hydration layer and enhancing the oleophobicity of the membrane. The underwater SPDMX membrane appeared superoleophobic with an oil contact angle of 153°, whereas the ceramic membrane exhibited an oil contact angle of 137°. The SPDMX membranes showed an improved flux recovery (31%) compared to the nonsulfonated counterpart. This work highlights the appropriate functionalization of MXene as a promising approach to developing MXene membranes with high permeation flux and better antifouling characteristics for oily wastewater treatment.

3D porous polymers for selective removal of CO2 and H2 storage: experimental and computational studies.

In this article, newly designed 3D porous polymers with tuned porosity were synthesized by the polycondensation of tetrakis (4-aminophenyl) methane with pyrrole to form M1 polymer and with phenazine to form M2 polymer. The polymerization reaction used p-formaldehyde as a linker and nitric acid as a catalyst. The newly designed 3D porous polymers showed permanent porosity with a BET surface area of 575 m2/g for M1 and 389 m2/g for M2. The structure and thermal stability were investigated by solid 13C-NMR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). The performance of the synthesized polymers toward CO2 and H2 was evaluated, demonstrating adsorption capacities of 1.85 mmol/g and 2.10 mmol/g for CO2 by M1 and M2, respectively. The importance of the synthesized polymers lies in their selectivity for CO2 capture, with CO2/N2 selectivity of 43 and 51 for M1 and M2, respectively. M1 and M2 polymers showed their capability for hydrogen storage with a capacity of 66 cm3/g (0.6 wt%) and 87 cm3/g (0.8 wt%), respectively, at 1 bar and 77 K. Molecular dynamics (MD) simulations using the grand canonical Monte Carlo (GCMC) method revealed the presence of considerable microporosity on M2, making it highly selective to CO2. The exceptional removal capabilities, combined with the high thermal stability and microporosity, enable M2 to be a potential material for flue gas purification and hydrogen storage.

Experimental Investigation of a Plate-Frame Water Gap Membrane Distillation System for Seawater Desalination.

This study presented a detailed investigation into the performance of a plate-frame water gap membrane distillation (WGMD) system for the desalination of untreated real seawater. One approach to improving the performance of WGMD is through the proper selection of cooling plate material, which plays a vital role in enhancing the gap vapor condensation process. Hence, the influence of different cooling plate materials was examined and discussed. Furthermore, two different hydrophobic micro-porous polymeric membranes of similar mean pore sizes were utilized in the study. The influence of key operating parameters, including the feed water temperature and flow rate, was examined against the system vapor flux and gained output ratio (GOR). In addition, the used membranes were characterized by means of different techniques in terms of surface morphology, liquid entry pressure, water contact angle, pore size distribution, and porosity. Findings revealed that, at all conditions, the PTFE membrane exhibits superior vapor flux and energy efficiency (GOR), with 9.36% to 14.36% higher flux at a 0.6 to 1.2 L/min feed flow rate when compared to the PVDF membrane. The copper plate, which has the highest thermal conductivity, attained the highest vapor flux, while the acrylic plate, which has an extra-low thermal conductivity, recorded the lowest vapor flux. The increasing order of GOR values for different cooling plates is acrylic < HDPE < copper < aluminum < brass < stainless steel. Results also indicated that increasing the feed temperature increases the vapor flux almost exponentially to a maximum flux value of 30.36 kg/m2hr. The system GOR also improves in a decreasing pattern to a maximum value of 0.4049. Moreover, a long-term test showed that the PTFE membrane, which exhibits superior hydrophobicity, registered better salt rejection stability. The use of copper as a cooling plate material for better system performance is recommended, while cooling plate materials with very low thermal conductivities, such as a low thermally conducting polymer, are discouraged.

Low Overpotential Electrochemical Reduction of CO2 to Ethanol Enabled by Cu/CuxO Nanoparticles Embedded in Nitrogen-Doped Carbon Cuboids.

The electrochemical conversion of CO2 into value-added chemicals is a promising approach for addressing environmental and energy supply problems. In this study, electrochemical CO2 catalysis to ethanol is achieved using incorporated Cu/CuxO nanoparticles into nitrogenous porous carbon cuboids. Pyrolysis of the coordinated Cu cations with nitrogen heterocycles allowed Cu nanoparticles to detach from the coordination complex but remain dispersed throughout the porous carbon cuboids. The heterogeneous composite Cu/CuxO-PCC-0h electrocatalyst reduced CO2 to ethanol at low overpotential in 0.5 M KHCO3, exhibiting maximum ethanol faradaic efficiency of 50% at -0.5 V vs. reversible hydrogen electrode. Such electrochemical performance can be ascribed to the synergy between pyridinic nitrogen species, Cu/CuxO nanoparticles, and porous carbon morphology, together providing efficient CO2 diffusion, activation, and intermediates stabilization. This was supported by the notably high electrochemically active surface area, rich porosity, and efficient charge transfer properties.

Hemin-Modified Multi-Walled Carbon Nanotube-Incorporated PVDF Membranes: Computational and Experimental Studies on Oil-Water Emulsion Separations.

The separation of oil/water emulsions has attracted considerable attention for decades due to the negative environmental impacts brought by wastewater. Among the various membranes investigated for separation, polyvinylidene fluoride (PVDF) membranes have shown significant advantages of ease of fabrication, high selectivity, and fair pore distribution. However, PVDF membranes are hydrophobic and suffer from severe fouling resulting in substantial flux decline. Meanwhile, the incorporation of wettable substrates during fabrication has significantly impacted the membrane performance by lowering the fouling propensity. Herein, we report the fabrication of an iron-containing porphyrin (hemin)-modified multi-walled carbon nanotube incorporated PVDF membrane (HA-MWCNT) to enhance fouling resistance and the effective separation of oil-in-water emulsions. The fabricated membrane was thoroughly investigated using the FTIR, SEM, EDX, AFM, and contact angle (CA) analysis. The HA-MWCNT membrane exhibited a water CA of 62° ± 0.5 and excellent pure water permeance of 300.5 L/m2h at 3.0 bar (400% increment), in contrast to the pristine PVDF, which recorded a CA of 82° ± 0.8 and water permeance of 59.9 L/m2h. The hydrophilic HA-MWCNT membrane further showed an excellent oil rejection of >99% in the transmembrane pressure range of 0.5−2.5 bar and a superb flux recovery ratio (FRR) of 82%. Meanwhile, the classical molecular dynamics (MD) simulations revealed that the HA-MWCNT membrane had greater solvent-accessible pores, which enhanced water permeance while blocking the hydrocarbons. The incorporation of the hemin-modified MWCNT is thus an excellent strategy and could be adopted in the design of advanced membranes for oil/water separation.

Designing of nanotextured inorganic-organic hybrid PVDF membrane for efficient separation of the oil-in-water emulsions.

The separation of the emulsified oil/water is one of the critical environmental challenges. The PVDF membranes have been found helpful for separation, but rapid fouling makes them less attractive in treating oil-in-water emulsions. The design of antifouling membranes has become an area of deep interest. Herein, developing a novel modified PVDF ultrafiltration membrane was reported by doping the pyrrole and solidifying it in a ferric-containing coagulation bath, resulting in a unique nanotextured PVDF membrane (CCB-Fe/PPnp-PVDF) to separate the oil/water emulsions. The resultant CCB-Fe/PPnp-PVDF membrane was thoroughly characterized using the FTIR, FE-SEM, EDX, mapping, AFM, and contact analyzer. The hydrophilicity of the CCB-Fe/PPnp-PVDF was substantially improved, and the water contact angle was reduced from 81Ö¯ ± 0.9Ö¯ to 44Ö¯ ± 1.7Ö¯. The CCB-Fe/PPnp-PVDF membrane flux increased by 121% compared to the pristine PVDF membrane, with high separation efficiency of 99%. The hydrophilic nanotextured surface of the CCB-Fe/PPnp-PVDF membrane showed good antifouling behavior, with a flux recovery ratio (FRR) of more than 96%. Irreversible flux was just less than 4%. The high flux recovery ratio indicated that the nanotextured surface produced by the Fe/PPnp had prevented the blockage of the membrane pores and compact cake layer formation, which makes it an excellent membrane for oil/water emulsion separation. This strategy can be adopted for designing advanced membranes for separation applications.

Selective Removal of Iron, Lead, and Copper Metal Ions from Industrial Wastewater by a Novel Cross-Linked Carbazole-Piperazine Copolymer.

A novel cross-linked Copolymer (MXM) was synthesized by the polycondensation reaction of 3,6-Diaminocarbazole and piperazine with p-formaldehyde as a cross-linker. The Copolymer was fully characterized by solid 13C-NMR and FT-IR. The thermal stability of MXM was investigated by TGA and showed that the Copolymer was stable up to 300 °C. The synthesized polyamine was tested for the removal of iron (Fe2+), lead (Pb2+), and copper (Cu2+) ions from aqueous and industrial wastewater solutions. The effect of pH, concentration and time on the adsorption of iron (Fe2+), lead (Pb2+), and copper (Cu2+) ions was investigated. The adsorption of the studied ions from aqueous solutions onto the MXM polymer occurs following the Freundlich isotherm and pseudo-second-order kinetic models. The intraparticle diffusion model showed that the adsorption mechanism is controlled by film diffusion. The regeneration of MXM showed practical reusability with a loss in capacity of 2-5% in the case of Fe2+ and Cu2+ ions. The molecular simulation investigations revealed similarities between experimental and theoretical calculations. Industrial wastewater treatment revealed the excellent capabilities and design of MXM to be a potential adsorbent for the removal of heavy metal ions.

A First-Principles Study on the Multilayer Graphene Nanosheets Anode Performance for Boron-Ion Battery.

Advanced battery materials are urgently desirable to meet the rapidly growing demand for portable electronics and power. The development of a high-energy-density anode is essential for the practical application of B3+ batteries as an alternative to Li-ion batteries. Herein, we have investigated the performance of B3+ on monolayer (MG), bilayer (BG), trilayer (TG), and tetralayer (TTG) graphene sheets using first-principles calculations. The findings reveal significant stabilization of the HOMO and the LUMO frontier orbitals of the graphene sheets upon adsorption of B3+ by shifting the energies from -5.085 and -2.242 eV in MG to -20.08 and -19.84 eV in 2B3+@TTG. Similarly, increasing the layers to tetralayer graphitic carbon B3+@TTG_asym and B3+@TTG_sym produced the most favorable and deeper van der Waals interactions. The cell voltages obtained were considerably enhanced, and B3+/B@TTG showed the highest cell voltage of 16.5 V. Our results suggest a novel avenue to engineer graphene anode performance by increasing the number of graphene layers.

The Role of Sulphonic and Phosphoric Pendant Groups on the Diffusion of Monovalent Ions in Polyelectrolyte Membranes: A Molecular Dynamics Study.

Lithium-ion consumption has risen significantly in recent years due to its use in portable devices. Alternative sources of lithium, which include the recovery from brine using the sustainable and eco-friendly electrodialysis technology, has been explored. This technology, however, requires effective cation-exchange membranes that allow the selective permeation of lithium ions. In this study, we have investigated, via molecular dynamics simulations, the role of the two common charged groups, the sulfonic and the phosphoric groups, in promoting the adsorption of monovalent ions from brine comprising Li+, Na+, Mg2+, and Ca2+ ions. The analysis of the mean square displacement of the ions revealed that Li+ and Na+ ions exhibit superior diffusion behaviors within the polyelectrolyte system. The O-atoms of the charged groups bind strongly with the divalent ions (Mg2+ and Ca2+), which raises their diffusion energy barrier and consequently lowers their rate of permeation. In contrast, the monovalent ions exhibit weaker interactions, with Na+ being slightly above Li+, enabling the permeation of Li+ ions. The present study demonstrates the role of both charged groups in cation-exchange membranes in promoting the diffusion of Li+ and Na+ ions, and could serve as a guide for the design of effective membranes for the recovery of these ions from brine.

Porous Fluorocarbon from Rice Husk for the Efficient Separation of Gases.

A porous fluorocarbon sorbent is synthesized from rice husk (RH) in a microwave reactor and then evaluated for the adsorption of different gases (CH4, CO2, and N2). The fluorocarbon is characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Raman spectroscopy, Thermal gravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Significant enhancement in the surface area of activated carbon material is obtained from 29 to 531 m2 g-1 after removing naturally present silica in RH. Results reveal that rice husk fluorocarbon (RHF) has a higher adsorption affinity for CO2 (1.8 mmol g-1) than that of the sulfonated rice husk (RHS) (1.4 mmol g-1) at 298 K while the corresponding separation factor of CO2/CH4 is 4 and 3; respectively. Higher separation factors of 12 and 10 are observed for the binary system of CO2/N2, respectively. Quantum chemical density functional theory (DFT) calculations agree with the experimental observations. They reveal that RHF exhibits strong columbic interactions with considerable interaction energies of -87.85, -76.75, and -55.65 kcal mol-1 with CO2, CH4, and N2 gases; respectively. Finally, the adsorption process results are highly reproducible, with a small decrease in the adsorption capacity of less than 5% after repeated trials.

Impact of Polypyrrole Functionalization on the Anodic Performance of Boron Nitride Nanosheets: Insights From First-Principles Calculations.

Lithium-ion batteries (LIBs) have displayed superior performance compared to other types of rechargeable batteries. However, the depleting lithium mineral reserve might be the most discouraging setback for the LIBs technological advancements. Alternative materials are thus desirable to salvage these limitations. Herein, we have investigated using first-principles DFT simulations the role of polypyrrole, PP functionalization in improving the anodic performance of boron nitride nanosheet, BNNS-based lithium-ion batteries and extended the same to sodium, beryllium, and magnesium ion batteries. The HOMO-LUMO energy states were stabilized by the PP functional unit, resulting in a significantly reduced energy gap of the BNNS by 45%, improved electronic properties, and cell reaction kinetics. The cell voltage, ΔEcell was predicted to improve upon functionalization with PP, especially for Li-ion (from 1.55 to 2.06 V) and Na-ion (from 1.03 to 1.37 V), the trend of which revealed the influence of the size and the charge on the metal ions in promoting the energy efficiency of the batteries. The present study provides an insight into the role of conducting polymers in improving the energy efficiency of metal-ion batteries and could pave the way for the effective design of highly efficient energy storage materials.

Rice husk derived Aminated Silica for the efficient adsorption of different gases.

In this present work, we successfully prepared aminated silica (ASiO2) from rice husk ash (RHA) and functionalized with 3-aminopropyltriethoxysilane (APTES). Physical and chemical properties of the synthesized material were investigated by various techniques SEM-EDX, XPS, FTIR, TGA. The surface area of RHA was 223 m2/g, while for ASiO2 was 101 m2/g. Molecular level DFT calculations revealed that the functionalization of ASiO2 resulted in a significant decrease in the HOMO-LUMO energy gap, a reduction in hardness, and a consequent increase in charge transfer characteristics. The adsorption behavior at low pressure (1 atm.) of aminated silica on different gases CO2, CH4, H2, and N2 at temperatures 77, 273, 298 K was studied. The adsorption of hydrogen was reported for the first time on aminated silica with an excellent adsorption capacity of 1.2 mmol/g. The ASiO2 exhibited excellent performance in terms of gas separation in binary mixtures of CO2/CH4, CO2/N2 and CO2/H2 at 273, and 298 K, respectively. The catalyst further exhibits high stability during three cycles with less than 10% variation in the separation capacity.

Novel Porous Organic Polymer for the Concurrent and Selective Removal of Hydrogen Sulfide and Carbon Dioxide from Natural Gas Streams.

Natural gas sweetening currently requires multistep, complex separation processes to remove the acid gas contaminants, carbon dioxide and hydrogen sulfide. In addition to being widely recognized as energy inefficient and cost-intensive, the effectiveness of this conventional process also suffers considerably because of limitations of the sorbent materials it employs. Herein, we report a new porous organic polymer, termed KFUPM-5, that is demonstrated to be effective in the concurrent separation of both hydrogen sulfide and carbon dioxide from a mixed gas stream at ambient conditions. To understand the ability of KFUPM-5 to selectively capture these gas molecules, we performed both pure-component thermodynamic and mixed gas kinetic adsorption studies and correlated these results with theoretical molecular simulations. Our results show that the underlying polar backbone of KFUPM-5 provides favorable adsorption sites for the selective capture of these gas molecules. The outcome of this work lends credence to the prospect that, for the first time, porous organic polymers can serve as sorbents for industrial natural gas sweetening processes.

A selective detection approach for copper(ii) ions using a hydrazone-based colorimetric sensor: spectroscopic and DFT study.

The development of an efficient and miniaturized analytical approach to determine trace levels of toxic ions in aqueous fluids presents a current research challenge. Hydrazone-based chemosensors are considered potential candidates due to their high sensitivity and selectivity towards heavy metal ions. Computational techniques can be properly implemented to elucidate possible modes of ligand-metal interaction and provide an in-depth understanding of the chemistry involved. The present study reports the use of 3-hydroxy-5-nitrobenzaldehyde-4-hydroxybenzoylhydrazone (3-HNHBH) ligand for highly sensitive, quick and re-usable colorimetric sensing of copper(ii) ions in aqueous media. DFT calculations suggest that the complexation of 3-HNHBH with copper(ii) ions adopts a seesaw coordination geometry and results in the largest HOMO-LUMO gap and most effective coulombic interaction compared to Zn and Ni counterparts. It demonstrated a high selectivity towards copper ions with a detection limit of 0.34 µg L-1. The ligand was readily regenerated using a 0.5 M HCl solution, indicating its feasibility to be used as a re-usable sensor for the convenient detection of copper ions in aqueous media. The influence of metal interference, pH and solvents on the selectivity and regeneration of the ligand was also investigated.