The use of lanthanum-anchored zinc oxide distorted hexagon (La@ZnO DH) nanoclusters as an active material for the photodegradation of rhodamine B (Rh–B) dye via hydrogen bonding, electrostatic, and π-π interactions is examined herein. The active photocatalyst is derived from porous zeolite imidazole frameworks (ZIF-8) via a combined ultrasonication and calcination process. The distorted hexagon nanocluster morphology with controlled surface area is shown to provide excellent catalytic activity, chemical stability and demarcated pore volume. In addition, the low bandgap (3.57 eV) of La@ZnO DH is shown to expand the degradation of Rh–B under irradiation of UV light as compared to the pristine ZIF-8-derived ZnO photocatalyst due to inhibited recombination of electrons and holes. The outstanding physicochemical stability and enhanced performance of La@ZnO DH could be ascribed to the synergistic interaction among La3+ particles and the ZnO nanoclusters and provide a route for their utilization as a promising catalyst for the detoxification of Rh–B.

Developing low-cost and high-performance biosorbent for water purification continues drawing more and more attention. In this study, cellulose-chitosan composite hydrogels were fabricated via a co-dissolution and regeneration process using a molten salt hydrate (a 60 wt% aqueous solution of LiBr) as a solvent. The addition of chitosan not only introduced functionality for metal adsorption but also increased the specific surface area and improved the mechanical strength of the composite hydrogel, compared to pure cellulose hydrogel. Batch adsorption experiments indicated that the composite hydrogel with 37% cellulose and 63% chitosan exhibited an adsorption capacity of 94.3 mg/g (1.49 mmol/g) toward Cu²⁺ at 23 °C, pH 5, and initial metal concentration of 1500 mg/L, which was 10 times greater than the adsorption capacity of pure cellulose hydrogel. Competitive adsorption from a mixed metals solution revealed that the cellulose-chitosan composite hydrogel exhibited selective adsorption of the metals in the order of Cu²⁺ > Zn²⁺ > Co²⁺. This study successfully demonstrated an innovative method to fabricate biosorbents from abundant and renewable natural polymers (cellulose and chitosan) for removing metal ions from water.

Presently, graphenic nanomaterials are being studied as candidates for wastewater pollutant removal. In this study, two graphite oxides produced from natural graphite with different grain sizes (325 and 10 mesh), their respective reduced graphene oxides and one reduced graphene oxide with nitrogen functional groups were synthesized and tested to remove a surfactant model substrate, Triton X-100, from an aqueous solution. Kinetic experiments were carried out and adjusted to pseudo-first order equation, pseudo-second order equation, Elovich, Chain-Clayton and intra-particle diffusion models. Reduced graphene oxides displayed an instantaneous adsorption due to their accessible and hydrophobic surfaces, while graphite oxides hindered the TX100 adsorption rate due to their highly superficial oxygen content. Results from the adsorption isotherms showed that the Sips model perfectly described the TX100 adsorption behavior of these materials. Higher adsorption capacities were developed with reduced graphene oxides, being maximum for the material produced from the lower graphite grain size (qₑ = 3.55·10⁻⁶ mol/m²), which could be explained by a higher surface area (600 m²/g), a lower amount of superficial oxygen (O/C = 0.04) and a more defected structure (ID/IG = 0.85). Additionally, three commercial high surface area graphites in the range of 100–500 m²/g were evaluated for comparison purposes. In this case, better adsorption results were obtained with a more graphitic material, HSAG100 (qₑ = 1.72·10⁻⁶ mol/m²). However, the best experimental results of this study were obtained using synthesized graphenic materials.

Development of non-noble metal cluster catalysts, aiming at concurrently high activity and stability, for emission control systems has been challenging because of sintering and overcoating of clusters on the support. In this work, we reported the role of well-dispersed copper nanoclusters supported on TiO₂ in CO oxidation under industrially relevant operating conditions. The catalyst containing 0.15 wt% Cu on TiO₂ (0.15 CT) exhibited a high dispersion (59.1%), a large specific surface area (381 m²/gCᵤ), a small particle size (1.77 nm), and abundant active sites (75.8% Cu₂O). The CO oxidation activity measured by the turnover frequency (TOF) was found to be enhanced from 0.60 × 10⁻³ to 3.22 × 10⁻³ molCO·molCᵤ⁻¹·s⁻¹ as the copper loading decreased from 5 to 0.15 wt%. A CO conversion of approximately 60% was still observed in the supported cluster catalyst with a Cu loading of 5 wt% at 240 °C. No deactivation was observed for catalysts with low copper loading (0.15 and 0.30 CT) after 8 h of time-on-stream, which compares favorably with less stable Au cluster-based catalysts reported in the literature. In contrast, catalysts with high copper loading (0.75 and 5 CT) showed deactivation over time, which was ascribed to the increase in copper particle size due to metal cluster agglomeration. This study elucidated the size-activity threshold of TiO₂-supported Cu cluster catalysts. It also demonstrated the potential of the supported Cu cluster catalyst at a typical temperature range of diesel engines at light-load. The supported Cu cluster catalyst could be a promising alternative to noble metal cluster catalysts for emission control systems.

Daunting amounts of microplastics are present in surface waters worldwide. A main category of microplastics is synthetic microfibers, which originate from textiles. These microplastics are generated and released in laundering and are discharged by wastewater treatment plants or enter surface waters from other sources. The polymers that constitute many common synthetic microfibers are mostly denser than water, and eventually settle out in aquatic environments. The interaction of these microfibers with submerged aquatic vegetation has not been thoroughly investigated but is potentially an important aquatic sink in surface waters. In the Laurentian Great Lakes, prolific growth of macrophytic Cladophora creates submerged biomass with a large amount of surface area and the potential to collect and concentrate microplastics. To determine the number of synthetic microfibers in Great Lakes Cladophora, samples were collected from Lakes Erie and Michigan at multiple depths in the spring and summer of 2018. After rinsing and processing the algae, associated synthetic microfibers were quantified. The average loads of synthetic microfibers determined from the Lake Erie and Lake Michigan samples were 32,000 per kg (dry weight (dw)) and 34,000 per kg (dw), respectively, 2–4 orders of magnitude greater than loads previously reported in water and sediment. To further explore this sequestration of microplastics, fresh and aged Cladophora were mixed with aqueous mixtures of microfibers or microplastic in the laboratory to simulate pollution events. Microscopic analyses indicated that fresh Cladophora algae readily interacted with microplastics via adsorptive forces and physical entanglement. These interactions mostly cease upon algal senescence, with an expected release of microplastics in benthic sediments. Collectively, these findings suggest that synthetic microfibers are widespread in Cladophora algae and the affinity between microplastics and Cladophora may offer insights for removing microplastic pollution.Macroalgae in the Laurentian Great Lakes contain high loads of synthetic microfibers, both entangled and adsorbed, which likely account for an important fraction of microplastics in these surface waters.

Hydrochar (HC) serves as a promising adsorbent to remove the cadmium from aqueous solution due to porous structure. The chemical aging method is an efficient and easy-operated approach to improve the adsorption capacity of HC. In this study, four chemical aging hydrochars (CAHCs) were obtained by using nitric acid (HNO₃) with mass fractions of 5% (N5-HC), 10% (N10-HC), and 15% (N15-HC) to age the pristine HC (N0-HC) and remove the Cd²⁺ from the aqueous solution. The results displayed that the N15-HC adsorption capacity was 19.99 mg g⁻¹ (initial Cd²⁺ concentration was 50 mg L⁻¹), which increased by 7.4 folds compared to N0-HC. After chemical aging, the specific surface area and oxygen-containing functional groups of CAHCs were increased, which contributed to combination with Cd²⁺ by physical adsorption and surface complexation. Moreover, ion exchange also occurred during the adsorption process of Cd²⁺. These findings have important implications for wastewater treatment to transform the forestry waste into a valuable adsorbent for Cd²⁺ removal from water.

The present study explores the immobilization of ligninolytic enzyme-laccase on the surface of rice straw biochar and evaluates its application for anthracene biodegradation. The rice straw biochar was acid-treated to generate carboxyl functionality on its surface, followed by detailed morphological and chemical characterization. The surface area of functionalized biochar displayed a two-fold increase compared to the untreated biochar. Laccase was immobilized on functionalized biochar, and an immobilization yield of 66% was obtained. The immobilized enzyme demonstrated operational stability up to six cycles while retaining 40% of the initial activity. Laccase immobilization was further investigated by performing adsorption and kinetic studies, which revealed the highest immobilization concentration of 500 U g⁻¹ at 25 °C. The adsorption followed the Langmuir isotherm model at equilibrium, and the kinetic study confirmed pseudo-second-order kinetics. The equilibrium rate constant (K₂) at 25 °C and 4 °C were 3.6 × 10⁻³ g U⁻¹ min⁻¹ and 4 × 10⁻³ g U⁻¹ min⁻¹ respectively for 100 U g⁻¹ of enzyme loading. This immobilized system was applied for anthracene degradation in the aqueous batch mode, which resulted in complete degradation of 50 mg L⁻¹ anthracene within 24 h of interaction exposure.

In this study, a sustainable NH₂-MIL-101(Al) is synthesized and subjected to characterization for cryogenic CO₂ adsorption, isotherms, and thermodynamic study. The morphology revealed a highly porous surface. The XRD showed that NH₂-MIL-101(Al) was crystalline. The NH₂-MIL-101(Al) decomposes at a temperature (>500 °C) indicating excellent thermal stability. The BET investigation revealed the specific surface area of 2530 m²/g and the pore volume of 1.32 cm³/g. The CO₂ adsorption capacity was found to be 9.55 wt% to 2.31 wt% within the investigated temperature range. The isotherms revealed the availability of adsorption sites with favorable adsorption at lower temperatures indicating the thermodynamically controlled process. The thermodynamics showed that the process is non-spontaneous, endothermic, with fewer disorders, chemisorption. Finally, the breakthrough time of NH₂-MIL-101(Al) is 31.25% more than spherical glass beads. The CO₂ captured by the particles was 2.29 kg m⁻³. The CO₂ capture using glass packing was 121% less than NH₂-MIL-101(Al) under similar conditions of temperature and pressure.

Atmospheric semi-volatile organic compounds (SVOCs) are complex in their chemical and toxicological characteristics with sources from both primary combustion emissions and secondary oxygenated aerosol formation processes. In this study, thermal desorption of PM₂.₅ in association with online measurement of reactive oxygen species (ROS) was carried out to study the role of SVOCs in its gas-particle partitioning. The mass concentrations of PM₂.₅, black carbon (BC) and p-PAHs downstream of a thermodenuder were measured online at different temperature settings (25, 50, 100, and 200 °C) to characterize PM physico-chemical properties. While the mass concentrations of PM₂.₅ and p-PAHs reduced to ∼34% at 200 °C compared to that in ambient temperature, BC mass concentration has decreased by 30% at the highest temperature. Furthermore, the submicron particle size distribution showed reduced particle number concentration in Aitken mode at 200 °C heating. The ROS, measured by Particle-into-Nitroxide-Quencher, also showed reduction and followed a similar trend with PM measurements, where the total ROS decreased by 12%, 31%, and 53% at 50 °C, 100 °C, and 200 °C, respectively, compared to the ambient sample. When a HEPA filter was included in the upstream of samples, 39% of gas phase ROS reduction was observed at 200 °C. This provided a good estimate of the contribution of SVOCs in ROS production in PM₂.₅, where decreased SVOCs concentration at 200 °C increased the percentage of particle surface area. This concludes that the surface chemistry of these organic coatings on the particles is important for assessing the health impacts of PM.

In order to solve the low sorption capacity of pristine biochar for anionic pollutants, e.g., reactive red 120 (RR120), a novel mesoporous Fe-biochar composite was fabricated in this study by combination of Fe-loading and ball-milling methods. The ball-milling Fe-biochar composite could effectively remove RR120 by up to 90.1 mg g⁻¹ at pH of 7.5, and slightly alkaline condition was preferred. Adsorption kinetics showed that ball-milling Fe-biochar composite could quickly sorb RR120 with the rate constant (k₂) of 2.07 g mg⁻¹ min⁻¹ (pH = 7.5). Positive surface charge and large surface area were responsible for the outstanding removal performance of RR120 by ball-milling Fe-biochar composite: (1) The adscititious Fe would be converted to β-FeOOH during pyrolysis, which significantly improved the zeta potential of biochar and thus facilitated the electrostatic adsorption for RR120, which contributed to 42.3% and 85.5% at pH of 3 and 7.5, respectively; (2) Ball-milling effectively increased the specific surface area and uniformed the pore size distribution, which could provide more sorption sites and expedite the diffusion of RR120 molecules, shortening the time from several hours to less than 15 min. Findings of this study not only provide a feasible modification method for biochar to adsorb anionic pollutants efficiently and rapidly, but also help to reveal the roles of Fe-loading and ball-milling in enhancing adsorption capacity.