Low-temperature oxidative removal of benzene from the air using titanium carbide (MXene)-Supported platinum catalysts.

MXenes are an emerging class of two-dimensional (2D) inorganic materials with great potential for versatile applications such as adsorption and catalysis. Here, we describe the synthesis of a platinized titanium carbide MXene (Pt@Ti3C2) catalyst with varying amounts of platinum (0.1%-2 wt.%) for the low-temperature oxidation of benzene, an aromatic volatile organic compound often found in industrial flue gas. A 1% formulation of Pt@Ti3C2-R allowed near-complete (97%) oxidation of benzene to CO2 at 225 °C with a steady-state reaction rate (r) of 0.119 mol g-1·h-1. This low-temperature catalytic oxidation reaction was promoted by an increase in the lattice oxygen (O*)/Pt2+ species (active sites) of 1%Pt@Ti3C2-R from 45.3/34.6% to 71.0/61.1% through pre-thermal reduction under H2 flow, as revealed by X-ray photoelectron spectroscopy, temperature-programmed reduction, and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses. The cataltyic activity of 1% Pt@Ti3C2-R against benzene was assessed under the control of the key process variables (e.g., catalyst mass, flow rate, benzene concentration, relative humidity, and time-on-stream) to help optimize the oxidation reaction process. The results provide new insights into the use of platinum-based 2D MXene catalysts for low-temperature oxidative removal of benzene from the air.

Radiation synthesis and chemical modifications of p(AAm-co-AAc) hydrogel for improving their adsorptive removal of metal ions from polluted water.

The research focuses on utilizing gamma irradiation to synthesize polyacrylic acid-co-polyacrylamide p(AAm-co-AAc) hydrogels. The effect of synthetic parameters on physicochemical features of p(AAm-co-AAc) hydrogls were examined, including acrylic acid (AAc): acrylamide (AAm) weight ratios, monomer concentration, and gamma irradiation dosage (kGy). At the optimum synthetic conditions (30 kGy and 75% AAc), different chemical modifications are explored to incorporate sulfonate, hydroxyl, carboxyl, cysteine, thiol, and amine functional groups within the bare hydrogel (Cpd 0) structure. Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analyses confirmed the success development of functionalized hydrogels (namely Cpd 1 to 6) with three-dimensional porous structures. These modified hydrogels include Cpd 1, a sulfonated hydrogel through a sulfonation reaction; Cpd 2, modified via NaOH hydrolysis; Cpd 3, modified using thionyl chloride; Cpd 4, incorporating cysteine modification through reaction with cysteine; Cpd 5, with 4-(Dimethylamino) benzaldehyde; and Cpd 6, modified with 3,4-Dimethylbenzoic acid.The effect of hydrogel composition and surface functionalities on the swelling capacity and interactions with scale-forming/heavy metal ions (e.g., Ba2+, Sr2+, and Cu2+) was investigated in saline water solution (NaCl = 1000 mg/L). Batch adsorption studies reveal that all modified hydrogels exhibited higher removal efficiency for the three metal ions than unmodified p(AAm-co-AAc) hydrogel, validating the key role of surface functionalities in tailoring hydrogel affinity for metal ions adsorption. Amongst these, NaOH-treated hydrogel (Cpd 2) outperformed all other modified ones in the removal of Cu2+, Ba2+, and Sr2+ ions, with maximum capacities of 13.67, 36.4, and 27.31 mg/g, respectively. Based on adsorption isotherm and kinetic modeling, the adsorption process of the three metal ions onto all modified hydrogels better obeyed Freundlich isotherm and pseudo-first-order kinetic models. Thermodynamic studies also indicated that the adsorption behavior of Sr2+ ions can exhibit both exothermic and endothermic characteristics, depending on the nature of hydrogel surface chemistry. Conversely, the adsorption process of Cu2+ and Ba2+ ions onto all modified hydrogels is endothermic, suggesting favorable chemical adsorption mechanisms. These findings reveal that the specific adsorption performance of hydrogel is dependent on the type of modification and the targeted heavy metal ions. Based on the nature of hydrogel surface functionality, surface modifications can change the charge density, hydrophilicity, and overall chemical environment of the hydrogel, offering a versatile approach to optimize the adsorption affinity/selectivity of hydrogel's in removing scale-forming/heavy metals from water solutions.

Effects of gas phase composition on competitive adsorption properties of formaldehyde on titanium dioxide-supported platinum in single and mixture compositions.

Titanium dioxide-supported platinum (Pt@TiO2) is regarded as a highly efficient photothermal catalyst to degrade various volatile organic compounds (VOCs). To learn more about the hybrid adsorption/catalysis process of VOCs on Pt@TiO2, their dynamic adsorption behavior on the catalyst surface was studied using the single and multicomponent gas phase of FA (i.e., the latter with four aromatic compounds of benzene, toluene, m-xylene, and styrene (BTXS)) through the control of key operating variables (e.g., VOCs concentration, relative humidity (RH) levels, and dosage). According to the performance evaluation, the doping of TiO2 with Pt metal ions significantly enhanced the FA adsorption capacity (e.g., by 50 % higher than the pristine TiO2) with increased OH (OII) surface active sites (reactivity) and surface porosity. However, in the co-presence of BTXS and water vapor, the adsorption affinity for FA vapor declined by 2 to 3 folds of magnitude with a competitive inhibition of the adsorption interaction on the Pt@TiO2 surface. According to the kinetic and isotherms analysis, a complex, multilayered physicochemical process appears to govern the adsorption of FA molecules onto Pt@TiO2 surface. Overall, the outcomes of this work are helpful to verify the enhanced removal potential of Pt@TiO2 against FA through sequential adsorption and catalytic reaction mechanisms.

Zinc-doped titanium oxynitride as a high-performance adsorbent for formaldehyde in air.

The potential utility of titanium oxynitride doped with 5% zinc (ZnTON) has been investigated as an adsorbent for the treatment of gaseous formaldehyde (FA) using a fixed-bed adsorption system. The adsorption capacity of ZnTON, when estimated at 10%/100% breakthrough (BT) levels from a dry feed gas consisting of 10 Pa FA, was far superior to two reference materials (i.e., commercial P25-TiO2 and activated carbon (AC)) by factors of 1.7/1.3 and 10/2.5, respectively. The adsorption capacity of ZnTON increased with the increase in the initial feeding concentration of FA (5-12.5 Pa), while decreasing with the rising temperature (25-100 oC). An increase in moisture level (0-100% relative humidity) also led to 5.4- and 2.5-fold reductions in adsorption capacity of ZnTON at 10% and 100% BT levels, respectively. Thermodynamically, the adsorption of FA onto ZnTON is an exothermic (ΔHo = - 9.69 kJ.mol-1) to be feasible in nature based on physisorption mechanism. Further, the adsorption of FA onto ZnTON was governed by surface interactions and monolayer surface coverage (Van der Waal's force/electrostatic attraction), as it obeyed the Langmuir isotherm and pseudo-second-order kinetic models. Regeneration tests indicated a positive effect of moisture on FA desorption and durability of ZnTON (i.e., over three adsorption-desorption cycles). This study offers valuable mechanistic insights into the synthesis of an advanced adsorbent for the efficient removal of hazardous volatile organic compounds under near-ambient conditions.

TiO2-based catalytic systems for the treatment of airborne aromatic hydrocarbons.

Among diverse strategies to manage air quality, catalytic oxidation has been a widely used option to mitigate diverse pollutants such as aromatic volatile organic compounds (VOCs), especially benzene, toluene, and xylene (BTX). For such applications, TiO2-based catalysts have drawn significant research attention for their prominent photo/thermal catalytic activities and photochemical stability. This review has been organized to elaborate on the recent developments achieved in the thermocatalytic, photocatalytic, and photothermal applications of metal/non-metal doped TiO2 catalysts towards BTX vapors and their reaction mechanisms. The performance of the reported TiO2-based catalysts has also been analyzed based on multiple computational metrics such as reaction rate (r), quantum yield (QY), space-time yield, and figure of merit (FOM). At last, the research gap and prospects in the catalytic treatment of BTX are also discussed in association with the feasibility and utility of TiO2-based catalysts in air purification applications.

Potential utility of BiOX photocatalysts and their design/modification strategies for the optimum reduction of CO2.

As an effective means to efficiently control the emissions of carbon dioxide (CO2), photo-conversion of CO2 into solar fuels (or their precursors) is meaningful both as an option to generate cleaner energy and to alleviate global warming. In this regard, bismuth oxyhalide (BiOX, where X = Cl, Br, and I) semiconductors have sparked considerable interest due to their multiple merits (e.g., visible light-harvesting, efficient charge carriers separation, and excellent chemical stability). In this review, the fundamental aspects of BiOX-based photocatalysts are discussed in relation to their modification strategies and associated reduction mechanisms of CO2 to help expand their applicabilities. In this context, their performance is also evaluated in terms of the key performance metrics (e.g., quantum efficiency (QE), space-time yield (STY), and figure of merit (FoM)). Accordingly, the morphology design of BiOX materials is turned out as one of the most efficient strategies for the maximum yield of CO while the introduction of heterojunctions into BiOX materials was more suitable for CH4 formation. As such, the adoption of the proper modification approach is recommended for efficient conversion of CO2.

Microwave-assisted synthesis of MnO2 nanosorbent for adsorptive removal of Cs(I) and Sr(II) from water solutions.

In this study, a flower-like porous δ-MnO2 nanostructure was synthesized by a microwave-assisted hydrothermal process for adsorptive removal of strontium (Sr(II)) and cesium (Cs(I)) from wastewater. The prepared δ-MnO2 nanosorbent exhibited superior affinity for Sr(II) over Cs(I) in the single-solute system, with partition coefficient (PC) values of 10.2 and 2.3 L/g, respectively, at pH 6.0. In the two-solute system, the flower-like δ-MnO2 also adsorbed Sr(II) (PC = 3.81 L/g) more selectively than Cs(I) (PC 1.15 L/g). Further, their adsorption capacities decreased by 12 and 16%, respectively, relative to the single-solute system. In contrast, adsorption of the ions onto δ-MnO2 was affected less sensitively in dual than in single system when changes occurred in environmental variables such as pH (2-8) and ionic strength (1-100 mM). Adsorption kinetics, thermodynamics, and isotherm studies demonstrated the pivotal role of the monolayer surface active sites of endothermic δ-MnO2 (e.g., a complexation interaction with Mn-OH). Furthermore, the δ-MnO2 nanosorbent exhibited good regenerability, retaining more than 80% of its adsorption capacity when tested over four reuse cycles. The overall results of this study are expected to help establish strategies to effectively remove metal contaminants from wastewater using a green and low-cost hierarchical nanosorbent.

Validation of two contrasting capturing mechanisms for gaseous formaldehyde between two different types of strong metal-organic framework adsorbents.

In this research, the adsorption behavior of formaldehyde (FA) onto two types of metal-organic frameworks (MOFs: MOF-199 [M199] and UiO-66-NH2 [U6N]) is investigated against changes in the key process variables (e.g., FA partial pressure (0.5-10 Pa), temperature (30-120 °C), and relative humidity (RH: 0%, 50%, and 100%)). The results revealed that the FA adsorption behavior onto both MOFs is exothermic in nature. Besides, their relative dominance for FA uptake varies interactively with the changes in RH and FA partial pressure levels. As the FA levels increase in dry conditions, their breakthrough volumes (BTV (100% BT)) exhibit contrasting trends: The values of U6N decreased noticeably from 5232 and 3792 L·atm·g-1, while those of M199 increased from 4152 to 5772 L·atm·g-1. The superiority of U6N over M199 in the lower FA level (at<5 Pa) is supported by the Lewis acid-base interactions with amine groups (U6N) in line with kinetic/isotherm studies. Such superiority is also persistent at higher (10 Pa) FA level under all humid conditions in line with its higher moisture stability. However, in dry conditions, the reversal of relative dominance in which M199 exhibits enhanced efficacy for 10 Pa FA uptake (relative to U6N) should reflect its breathing effects with the potent role of pore-diffusion mechanism. This study offers valuable insights into the construction of tunable adsorbents with enhanced adsorptivity toward key targets.

Adsorption of environmental contaminants on micro- and nano-scale plastic polymers and the influence of weathering processes on their adsorptive attributes.

Increases in plastic-related pollution and their weathering can be a serious threat to environmental sustainability and human health, especially during the present COVID-19 (SARS-CoV-2 coronavirus) pandemic. Planetary risks of plastic waste disposed from diverse sources are exacerbated by the weathering-driven alterations in their physical-chemical attributes and presence of hazardous pollutants mediated through adsorption. Besides, plastic polymers act as vectors of toxic chemical contaminants and pathogenic microbes through sorption onto the 'plastisphere' (i.e., plastic-microbe/biofilm-environment interface). In this review, the effects of weathering-driven alterations on the plastisphere are addressed in relation to the fate/cycling of environmental contaminants along with the sorption/desorption dynamics of micro-/nano-scale plastic (MPs/NPs) polymers for emerging contaminants (e.g., endocrine-disrupting chemicals (EDCs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pharmaceuticals and personal care products (PPCPs), and certain heavy metals). The weathering processes, pathways, and mechanisms governing the adsorption of specific environmental pollutants on MPs/NPs surface are thus evaluated in relation to the physicochemical alterations based on several kinetic and isotherm studies. Consequently, the detailed evaluation on the role of the complex associations between weathering and physicochemical properties of plastics should help us gain a better knowledge with respect to the transport, behavior, fate, and toxicological chemistry of plastics along with the proper tactics for their sustainable remediation.

Proof of concept for CUK family metal-organic frameworks as environmentally-friendly adsorbents for benzene vapor.

The utility of metal-organic frameworks (MOFs) such as the CUK family (CUK - Cambridge University-KRICT) has been explored intensively for adsorption/separation of airborne volatile organic compounds (VOCs). In this article, three M-CUK analogs (M = Mg, Co, or Ni) were synthesized hydrothermally under similar conditions to assess the effects of their isostructural properties and metal centers on adsorption of benzene vapor (0.05-1 Pa). A list of performance metrics (e.g., breakthrough volume (BTV) and partition coefficient (PC)) were used to assess the role of the metal type (in M-CUK-1s) in the adsorption of VOCs. Specifically, Co-CUK-1 (average pore size of 8.98 nm) showed 2-3 times greater performance (e.g., in terms of 10% BTV (2012 L atm g-1) and PC (6 mol kg-1 Pa-1)) over other analogs when exposed up to 0.05 Pa benzene vapor. The superiority of mesoporous Co-CUK-1 (e.g., enhanced adsorption diffusion mechanism through favorable metal-π and π- π interactions) can be attributed to the presence of cobalt metal centers (e.g., in reference to Mg- or Ni-CUK-1).

Anisotropic ZnO nanostructures and their nanocomposites as an advanced platform for photocatalytic remediation.

In pursuit of advanced heterogeneous photocatalysts, ZnO has emerged as a promising option for solar-driven heterogeneous photocatalyst with many advantageous properties (e.g., optical band structure and electronic properties). However, as the efficacy of such system can also be limited by a number of demerits (e.g., fast recombination of charge carriers and limited photon absorption), considerable efforts are needed for its effective and practical scale-up. This article provides a detailed literature review of the synthesis and modification of ZnO nanostructures with tuned band structures and controllable morphologies for solar light harvesting. The potential of anisotropic ZnO nanostructures is also discussed with respect to the photocatalytic degradation of organic/inorganic water pollutants. Further, the role of various metal dopants is discussed for the enhancement of photocatalytic activity along with evaluation of their photocatalytic performances under UV-visible or solar irradiation. Finally, our discussions are expanded to describe the prospects of developed ZnO nano-photocatalysts for real-world applications with respect to light-harvesting efficiency and mechanical stability.

A strategy for the enhancement of trapping efficiency of gaseous benzene on activated carbon (AC) through modification of their surface functionalities.

Facile modification is a common, but effective, option to improve the uptake removal capacity of of activated carbon (AC) against diverse target volatile organic compounds (VOCs; e.g., benzene) in gaseous streams. To help design the routes for such modification, this research built strategies to generate three types of modified ACs by incorporating amine/sulfur/amino-silane groups under solvothermal or microwave (MW) thermal conditions. The adsorption performance has been tested using a total of six types of AC sorbents (three modified + three pristine forms) for the capture of 1 Pa benzene (1 atm and 298 K). The obtained results are evaluated in relation to their textural properties and surface functionalities. Accordingly, the enhancement of AC surface basicity (e.g., point of zero charge (PZC) = 10.25), attained via the silylation process, is accompanied by the reduced adsorption of benzene (a weak base). In contrast, ACs amended with amine/sulfur (electron-donating) groups using the MW technique are found to acquire high surface acidity (PZC of 5.99-6.05) to exhibit significantly improved benzene capturing capability (relative to all others). Their uplifted performance is demonstrated in terms of key performance metrics such as breakthrough volume (BTV10%: 163 â†’ 443 L g-1), adsorption capacity (Q10%: 4.82 â†’ 13.6 mg g-1), and partition coefficient (PC10%: 0.516 â†’ 1.67 mol kg-1 Pa-1). Based on the kinetic analysis, the overall adsorption process is found to be governed by pore diffusion as the main rate-determining step, along with surface interaction mechanisms. The results of this research clearly support the critical role of surface chemistry of AC adsorbents and their textural properties in upgrading air/gas purification systems.

Photocatalytic and biocidal activities of ZnTiO2 oxynitride heterojunction with MOF-5 and g-C3N4: A case study for textile wastewater treatment under direct sunlight.

The work aimed to synthesize three heterojunction photocatalysts (Eg = 2.65-2.78 eV) via in-situ encapsulation of 5% zinc doped titanium oxynitride (Zn0.05TiOxNy) catalyst into MOF-5 and bulk (BCN)/sulfur-doped (SCN) g-C3N4 supports using a microwave method. The prepared photocatalysts were characterized and utilized to purify textile industrial wastewater from the organic dye (e.g., methylene blue, MB) and microbial (e.g., E. coli, S. aureus, and C. albicans) contaminants under dark, visible, and solar lights. The output data confirmed the higher activity of Zn0.05TiOxNy@SCN and Zn0.05TiOxNy@MOF-5 for photo-induced microbial growth inactivation (> 90%) under visible light, with photo-biocidal efficiency of 0.91-1.69 mCFU/Einstein. Such a phenomenon is ascribed to the synergism between the high antimicrobial capacity of supports and photoactivity of Zn0.05TiOxNy. Also, Zn0.05TiOxNy@SCN exhibited far superiority to mineralize MB dye (Kphoto of 2.73 × 10-2 min-1) under direct sunlight due to its high photonic (ζ% of 4.4-8.3%)/quantum (QE of 0.56-0.54%) efficiencies for the generation of hydroxyl and superoxide (-•O2/•OH) oxidative species. As a practical case study, all heterojunction photocatalysts also demonstrated high-performance stability (5 cycles) for real textile wastewater treatment under sunlight (efficiency = 76.1-84.6%).

An efficient system for electro-Fenton oxidation of pesticide by a reduced graphene oxide-aminopyrazine@3DNi foam gas diffusion electrode.

A stable rGO-AmPyraz@3DNiF gas diffusion electrode was prepared via modification of 3D nickel foam (3D-NiF) with aminopyrazine functionalized reduced graphene oxide (rGO-AmPyraz) for the electro Fenton (EF) process. The generation capacity of H2O2 and OH radicals by this electrode was assessed relative to 3DNiF and rGO-AmPyraz@indium tin oxide (ITO) electrodes and with/without a coated Fe3O4 plate. The rGO-AmPyraz@3DNiF electrode showed the maximum production of these radicals at 2.2 mmol h-1 and 410 µmol h-1, respectively (pH 3) with the least leaching of Ni2+ such as < 0.5 mg L-1 even after 5 cycles (e.g., relative to 3DNiF (24 mg L-1). Such control on Ni ion leaching was effective all across the tested pH from 3 to 8.5. Its H2O2 generation capacity was far higher than that of the nanocarbon supported on commercially available ITO conductive glass. The mineralization of dichlorvos (at initial concentration: 50 mg L-1) was confirmed with its complete degradation as the concentrations of the end products (e.g., free Cl-1 (5.36 mg L-1) and phosphate (12.89 mg L-1)) were in good agreement with their stoichiometric concentration in dichlorvos. As such, the proposed system can be recommended as an effective electrode to replace nanocarbon-based product commonly employed for EF processes.

An efficient strategy for the enhancement of adsorptivity of microporous carbons against gaseous formaldehyde: Surface modification with aminosilane adducts.

In an effort to develop a cost-effective mitigation tool for volatile organic compounds, particularly formaldehyde (FA), microporous activated carbon (AC) was modified into three different forms of AC-1, AC-2, and AC-3 using a raw commercial AC product (AC-0). First, AC-1 and AC-2 were produced by the modification of AC-0 with N/S heteroatoms using identical mixture of dicyandiamide and thiourea precursors through either solvothermal (AC-1) or microwave-assisted calcination (AC-2) synthesis. Second, aminosilane-functionalized AC (AC-3) was prepared solvothermally using N-[3-(Trimethoxysilyl)propyl]ethylenediamine reagent. The relative adsorption performances for gaseous FA (1 ppm) in terms of 10% breakthrough volume (BTV10: L atm g-1) at near-ambient conditions (25 °C and 1 atm) were AC-3 (132) > AC-2 (66.5) > AC-1 (14.2) > AC-0 (10.4). In a comparison based on partition coefficients (mole kg-1 Pa-1) at BTV10, AC-3 outperformed AC-0 by a factor of 214, while the adsorption performance of AC-2 was 36-times higher than AC-1. The enhanced performance of AC-2 over AC-1 reflected the effect of the microwave synthesis protocol on the improvement of surface chemistry (e.g., N/S doping) and texture (e.g., surface area and pore volume) of AC-based adsorbents as compared to conventional solvothermal method. Further, the prominent role of surface chemistry (e.g., relative to textural properties), as observed with the increases in the amount of doped functional elements (including N:C and silicon:C ratios), is supported by the apparent dependence of performance on the selected modification procedures. Based on kinetic and X-ray photoelectron spectroscopy analyses, the superiority of aminosilylated AC-3 can be attributed to a synergistic effect between physisorption (e.g., pore diffusion) and chemical interactions of the FA carbonyl (C=O) group with amine and silica functionalities (via Mannich coupling [Schiff base] and cycloaddition reaction mechanisms, respectively). This confirms the significance of surface chemistry, relative to pore diffusion, in achieving maximum adsorption of gaseous FA molecules.

Preparation of solar-enhanced AlZnO@carbon nano-substrates for remediation of textile wastewaters.

Photoactive aluminum doped ZnO (AlZnO) was synthesized by sol-gel method. After that, AlZnO photocatalyst was deposited on five carbon-based materials (CBMs) using ultrasonic route followed by solid-state mixing using ball mill. The CBMs used were polyaniline (PANI), carbon nitride (CN), carbon nanotubes (CNT), graphene (G), and carbon nanofibers (CNF). The crystal phases, elemental compositions, morphological, and optical properties of the AlZnO@CBMs composites were investigated. Experimental results revealed that two of AlZnO@CBMs composites exhibited superior bleaching efficiency (100% removal) and photocatalytic stability (three cycles) for 50 µmol/L Methylene Blue (MB) contaminated water after 60 min irradiation in visible light at pH 6.5, 0.7% H2O2, and 5 g/L inorganic salts. Under optimum conditions, AlZnO@CBMs nanocomposites were employed for the treatment of mixed dyestuffs composed of MB, Methyl Orange (MO), Astrazone Blue FRR (BB 69), and Rhodamine B (RhB) dyes under dark, ultraviolet, visible, and direct sunlight. For mixed dyestuffs, the AlZnO@G achieved the highest dye sorption capacity (60.91 µmol dye stuffs/g) with kinetic rate 8.22 × 10-3 min-1 in 90 min via multi-layer physisorption (Freundlich isotherm) on graphene sheet. In additions, AlZnO@CN offered the highest photo-kinetic rate (Kphoto) of ~54.1 × 10-3 min-1 (93.8% after 60 min) under direct sunlight. Furthermore, the selective radical trapping experiment confirmed that the holes and oxidative superoxide radicals are crucial on dyes photodegradation pathway. Owing to their superior performance, AlZnO@G and AlZnO@CN nanocomposites can offer an effective in-situ solar-assisted adsorption/photocatalytic remediation of textile wastewater effluents.

A strategy for the efficient removal of chlorophenols in petrochemical wastewater by organophilic and aminated silica@alginate microbeads: Taguchi optimization and isotherm modeling based on partition coefficient.

Through in situ encapsulation of cetyltrimethylammonium bromide (CTAB) and urea-functionalized SiO2 nanoparticles in alginate hydrogel, two types of new functionalized microbeads, CTAB-SiO2@alginate (organophilic) and urea-SiO2@alginate (aminated), were produced. Their adsorption behavior toward multiple chlorophenols (CPs: e.g., 4-chlorophenol (MCP), 2,4-dichlorophenol (DCP), and 2,4,6-trichlorophenol (TCP)) in petrochemical wastewater was assessed with the aid of Taguchi's L9 orthogonal array at three levels. In terms of the partition coefficient (PC: µmol/g·µM (or L/g)), the use of three-parameter models (hybrid Langmuir-Freundlich and Redlich-Peterson) yielded the best fit (R2 ≈ 1). Furthermore, the performance evaluation in terms of PC metric indicated that CTAB-SiO2@alginate (7.85 L/g) was better to treat total CPs than urea-modified SiO2@alginate microbeads (3.83 L/g). The enhanced performance of the former reflects the significant contribution of CTAB functionality (sp2 carbon tail and quaternary amine (N+) cationic head sites) for accelerating uptake of molecular (or suspended) and ionizable CPs molecules (e.g., with the aid of salting-out effect at a high initial CPs concentration and salinity) via hydrophobic/electrostatic interactions. The high performance of the CTAB-SiO2@alginate was demonstrated against petroleum hydrocarbons, CPs, and phenol contaminants using real petrochemical wastewater (up to three reusable cycles).

An upgraded electro-Fenton treatment of wastewater using nanoclay-embedded graphene composite prepared via exfoliation of pencil rods by submerged liquid plasma.

In this work, two types of electrochemical electrodes were synthesized using two types (i.e., 4 black (4B) and hard black (HB)) of pencil rods during submerged liquid plasma (SLP) process. At high potential (3 kV) electrons, the SLP process offered an effective exfoliation route for the disorientation of the graphite sp2 domain to produce two nanoclay-graphene composite electrodes with a few graphene layers (thickness = 4-9 layers) and high dispersibility (< 19% settlement: 4 h) in polar/non-polar solution (52-53.1% settlement: 4 h). Their performance was then evaluated towards the electro-Fenton (EF) degradation of lindane using a coated Fe3O4 plate (as Fenton catalyst). Accordingly, both 4B- and HB-ENcGe electrodes showed high specific capacitance values (473 and 363 F g-1) at 0.05 A g-1 and excellent triangular charge-discharge patterns (< 9% and 35% reduction of capacitance, respectively after 1000 cycles (charging rate: 0.2 A g-1)). At pH 3 and current density of 6.5 mA cm-2, 4B-ENcGe exhibited superior EF degradation performance (99.4% after 60 min) against 2.5 mg L-1 lindane (H2O2 generation capacity: 2.53 mmol. h-1, current efficiency: 89.4%, and stability: up to 5th cycles). The complete EF-based mineralization of lindane suggests that these electrodes should offer one-step cost-effective treatment for wastewater contaminants.

Recent advances in carbon nanotube sponge-based sorption technologies for mitigation of marine oil spills.

HYPOTHESIS: Oil spills stemming from supertankers, drilling, and natural events represent a serious problem worldwide due to the potential harms to marine ecosystems and aquatic life. To date, various functional absorbents have been developed to treat spilled oil. Among them, carbon nanotube (CNT)-based aerogels and sponges gained attention due to superior performance in uptake and recovery of various types of oil and organic solvents. CNT aerogel/sponge absorbents are demonstrated for a multitude of merits such as: rapid superhydrophobic/superoleophilic absorption (water contact angle > 150°), high capacity (≥100 mg g-1), large surface area (300-400 m2 g-1)), enhanced strength and flexibility (>95% volume reduction and restoration of pristine morphology at <0.25 MPa stress), mesoporous characteristics with high pore density (pore diameter = 80 nm and >99% porosity), recyclability, and easy surface modification. EXPERIMENTS: This review compares CNT sponge-based absorbents with conventional techniques for remediation/recovery of spilled oil. Typically, synthesis of CNT sponges is performed using chemical vapor deposition (CVD) approach in the presence of a catalyst or using sacrificial removal of template. This work summarizes recent progress in strategies for oil-spill treatment based on CNT sponge techniques. The performance of CNT sponges for oil spill removal was evaluated in terms of their adsorption capacity, compressive stressability, and desorption methods (e.g., heat treatment, burning, or squeezing). FINDINGS: CNT sponges were observed to have high performance for removal of oil spills in terms of key performance metrics. This review offers valuable insights into the current state of CNT-mediated oil-spill cleanup technologies and guidance for future research at the same time. This literature survey would help the stakeholders (researchers, scientists, entrepreneurs, and commercial houses) pursue contamination-free water.

Metalloporphyrinic metal-organic frameworks: Controlled synthesis for catalytic applications in environmental and biological media.

Recently, as a new sub-family of porous coordination polymers (PCPs), porphyrinic-MOFs (Porph-MOFs) with biomimetic features have been developed using porphyrin macrocycles as ligands and/or pillared linkers. The control over the coordination of the porphyrin ligand and its derivatives however remains a challenge for engineering new tunable Porph-MOF frameworks by self-assembly methods. The key challenges exist in the following respects: (i) collapse of the large open pores of Porph-MOFs during synthesis, (ii) deactivation of unsaturated metal-sites (UMCs) by axial coordination, and (iii) the tendency of both coordinated moieties (at peripheral meso- and beta-carbon sites) and the N4-pyridine core to coordinate with metal cations. In this respect, this review covers the advances in the design of Porph-MOFs relative to their counterpart covalent organic frameworks (Porph-COFs). The potential utility of custom-designed porphyrin/metalloporphyrins ligands is highlighted. Synthesis strategies of Porph-MOFs are also illustrated with modular design of hybrid guest@host composites (either Porph@MOFs or guest@Porph-MOFs) with exceptional topologies and stability. This review summarizes the synergistic benefits of coordinated porphyrin ligands and functional guest molecules in Porph-MOF composites for enhanced catalytic performance in various redox applications. This review shed lights on the engineering of new tunable hetero-metals open active sites within (metallo)porphyrin-MOFs as out-of-the-box platforms for enhanced catalytic processes in chemical and biological media.