Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized. • The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K. • The potential mechanism for Cr(VI) adsorption by NHPC was put forward. • DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI). To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).     

Hexavalent chromium in drinking water: Chemistry,challenges and future outlook on Sn(II)- and photocatalyst-based treatment

• Wide occurrence of Cr(VI) in US source drinking water. • A strong dependence of occurrence on groundwater sources. • Elucidate Redox and equilibrium chemistry of Cr(VI). • Sn(II)-based and TiO₂-based reductive treatments hold extreme promise. • Key challenges include residual waste, Cr(VI) re-generation and socioeconomic drivers. Chromium (Cr) typically exists in either trivalent and hexavalent oxidation states in drinking water, i.e., Cr(III) and Cr(VI), with Cr(VI) of particular concern in recent years due to its high toxicity and new regulatory standards. This Account presented a critical analysis of the sources and occurrence of Cr(VI) in drinking water in the United States, analyzed the equilibrium chemistry of Cr(VI) species, summarized important redox reaction relevant to the fate of Cr(VI) in drinking water, and critically reviewed emerging Cr(VI) treatment technologies. There is a wide occurrence of Cr(VI) in US source drinking water, with a strong dependence on groundwater sources, mainly due to naturally weathering of chromium-containing aquifers. Challenges regarding traditional Cr(VI) treatment include chemical cost, generation of secondary waste and inadvertent re-generation of Cr(VI) after treatment. To overcome these challenges, reductive Cr(VI) treatment technologies based on the application of stannous tin or electron-releasing titanium dioxide photocatalyst hold extreme promise in the future. To moving forward in the right direction, three key questions need further exploration for the technology implementation, including effective management of residual waste, minimizing the risks of Cr(VI) re-occurrence downstream of drinking water treatment plant, and promote the socioeconomic drivers for Cr(VI) control in the future.     

Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5

• The MCNZVI is prepared as an interesting material for PS activation. • Graphitized carbon shells facilitate electron transfer from Fe⁰. • The MCNZVI exhibits excellent performance to degrade RB5 by ¹O₂. • The MCNZVI has high stability and reusability in the oxidation system. High-efficiency and cost-effective catalysts with available strategies for persulfate (PS) activation are critical for the complete mineralization of organic contaminants in the environmental remediation and protection fields. A nanoscale zero-valent iron-embedded modified mesoporous carbon (MCNZVI) with a core-shell structure is synthesized using the hydrothermal synthesis method and high-temperature pyrolysis. The results showed that nZVI could be impregnated within mesoporous carbon frameworks with a comparatively high graphitization degree, rich nitrogen doping content, and a large surface area and pore volume. This material was used as a persulfate activator for the oxidation removal of Reactive Black 5 (RB5). The effects of the material dosage, PS concentration, pH, and some inorganic anions (i.e., Cl⁻, SO₄²⁻) on RB5 degradation were then investigated. The highest degradation efficiency (97.3%) of RB5 was achieved via PS (20 mmol/L) activation by the MCNZVI (0.5 g/L). The pseudo-first-order kinetics (k = 2.11 × 10⁻² min⁻¹) in the MCNZVI/PS (0.5 g/L, 20 mmol/L) was greater than 100 times than that in the MCNZVI and PS. The reactive oxygen species (ROS), including ¹O₂, SO₄^·−, HO^·, and ·O₂⁻, were generated by PS activation with the MCNZVI. Singlet oxygen was demonstrated to be the primary ROS responsible for the RB5 degradation. The MCNZVI could be reused and regenerated for recycling. This work provides new insights into PS activation to remove organic contamination.     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

Translocation and biotoxicity of metal (oxide) nanoparticles in the wetland-plant system

• Aquatic plants are more likely to absorb TiO₂ NPs that are beneficial to them. • Ag NPs inhibited the growth of aquatic plants under both 5- and 60-day exposure. • CeO₂ NPs had positive/negative impact on plant in 5/60-day exposure, respectively. • TiO₂ NPs presence could enhance the photosynthesis and increase the plant biomass. • The ENPs changed plant activity, which resulted in changes of wetland performance. Engineered nanoparticles (ENPs) threaten the environment through wastewater discharging. Generally, constructed wetlands (CWs) are efficient methods for ENPs removal. However, the biotoxicity of ENPs on plants in CWs is unclear. Here, we investigated the distribution and bio-impacts of different ENPs (Ag NPs, TiO₂ NPs, and CeO₂ NPs) in plants under 5- and 60-day exposure to 1 and 50 mg/L concentrations. Results showed that ENPs appeared in the vascular bundle and mesophyll cell space, which induced the variation in antioxidase activities (e.g., superoxide dismutase [SOD], peroxidase [POD], and catalase [CAT] activities) as well as overproduction of malondialdehyde (MDA). Additionally, Ag NPs inhibited photosynthesis rate and root activity during two exposure phases. CeO₂ NPs had positive and negative impacts on plants in 5- and 60-day exposure, respectively. Inversely, TiO₂ NPs enhanced photosynthesis and root activity under 60-day exposure. Finally, the contents of the C, N, and P elements in plants fluctuated in response to ENPs stress. All results have a positive correlation with the wetland performance under ENPs exposure except for TiO₂ NPs treatment. Overall, our study systematically reveals aquatic plants' responses to ENPs and provides a reference for building ecological treatment systems to purify wastewater containing ENPs.     

In situ synthesis of FeS/Carbon fibers for the effective removal of Cr(VI) in aqueous solution

• FeS/carbon fibers were in situ synthesized with Fe-carrageenan hydrogel fiber. • The double helix structure of carrageenan is used to load and disperse Fe. • Pyrolyzing sulfate groups enriched carrageenan-Fe could easily generate FeS. • The adsorption mechanisms include reduction and complexation reaction. Iron sulfide (FeS) nanoparticles (termed FSNs) have attracted much attention for the removal of pollutants due to their high efficiency and low cost, and because they are environmentally friendly. However, issues of agglomeration, transformation, and the loss of active components limit their application. Therefore, this study investigates in situ synthesized FeS/carbon fibers with an Fe-carrageenan biomass as a precursor and nontoxic sulfur source to ascertain the removal efficiency of the fibers. The enrichment of sulfate groups as well as the double-helix structure in ι-carrageenan-Fe could effectively avoid the aggregation and loss of FSNs in practical applications. The obtained FeS/carbon fibers were used to control a Cr(VI) polluted solution, and exhibited a relatively high removal capacity (81.62 mg/g). The main mechanisms included the reduction of FeS, electrostatic adsorption of carbon fibers, and Cr(III)-Fe(III) complexation reaction. The pseudo-second-order kinetic model and Langmuir adsorption model both provided a good fit of the reaction process; hence, the removal process was mainly controlled by chemical adsorption, specifically monolayer adsorption on a uniform surface. Furthermore, co-existing anions, column, and regeneration experiments indicated that the FeS/carbon fibers are a promising remediation material for practical application.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Recent advances in antimony removal using carbon-based nanomaterials: A review

• The synthesis and physicochemical properties of various CNMs are reviewed. • Sb removal using carbon-based nano-adsorbents and membranes are summarized. • Details on adsorption behavior and mechanisms of Sb uptake by CNMs are discussed. • Challenges and future prospects for rational design of advanced CNMs are provided. Recently, special attention has been deserved to environmental risks of antimony (Sb) element that is of highly physiologic toxicity to human. Conventional coagulation and ion exchange methods for Sb removal are faced with challenges of low efficiency, high cost and secondary pollution. Adsorption based on carbon nanomaterials (CNMs; e.g., carbon nanotubes, graphene, graphene oxide, reduced graphene oxide and their derivatives) may provide effective alternative because the CNMs have high surface area, rich surface chemistry and high stability. In particular, good conductivity makes it possible to create linkage between adsorption and electrochemistry, thereby the synergistic interaction will be expected for enhanced Sb removal. This review article summarizes the state of art on Sb removal using CNMs with the form of nano-adsorbents and/or filtration membranes. In details, procedures of synthesis and functionalization of different forms of CNMs were reviewed. Next, adsorption behavior and the underlying mechanisms toward Sb removal using various CNMs were presented as resulting from a retrospective analysis of literatures. Last, we prospect the needs for mass production and regeneration of CNMs adsorbents using more affordable precursors and objective assessment of environmental impacts in future studies.     

Integration of microbial reductive dehalogenation with persulfate activation and oxidation (Bio-RD-PAO) for complete attenuation of organohalides

•Bio-RD-PAO can effectively and extensively remove organohalides. •Bio-RD alone effectively dehalogenate the highly-halogenated organohalides. •PAO alone is efficient in degrading the lowly-halogenated organohalides. •The impacts of PAO on organohalide-respiring microbial communities remain elusive. •Bio-RD-PAO provides a promising solution for remediation of organohalide pollution. Due to the toxicity of bioaccumulative organohalides to human beings and ecosystems, a variety of biotic and abiotic remediation methods have been developed to remove organohalides from contaminated environments. Bioremediation employing organohalide-respiring bacteria (OHRB)-mediated microbial reductive dehalogenation (Bio-RD) represents a cost-effective and environmentally friendly approach to attenuate highly-halogenated organohalides, specifically organohalides in soil, sediment and other anoxic environments. Nonetheless, many factors severely restrict the implications of OHRB-based bioremediation, including incomplete dehalogenation, low abundance of OHRB and consequent low dechlorination activity. Recently, the development of in situ chemical oxidation (ISCO) based on sulfate radicals (SO₄^·−) via the persulfate activation and oxidation (PAO) process has attracted tremendous research interest for the remediation of lowly-halogenated organohalides due to its following advantages, e.g., complete attenuation, high reactivity and no selectivity to organohalides. Therefore, integration of OHRB-mediated Bio-RD and subsequent PAO (Bio-RD-PAO) may provide a promising solution to the remediation of organohalides. In this review, we first provide an overview of current progress in Bio-RD and PAO and compare their limitations and advantages. We then critically discuss the integration of Bio-RD and PAO (Bio-RD-PAO) for complete attenuation of organohalides and its prospects for future remediation applications. Overall, Bio-RD-PAO opens up opportunities for complete attenuation and consequent effective in situ remediation of persistent organohalide pollution.     

Long-term adaptive evolution of Shewanella oneidensis MR-1 for establishment of high concentration Cr(VI) tolerance

• Shewanella oneidensis MR-1 was acclimated to grow with Cr(VI) of 190 mg/L. • Whole genomes from 7 populations at different acclimation stages were sequenced. • Gene mutations mainly related to efflux pumps and transporters. • An adaptation mechanism of MR-1 to high concentration of Cr(VI) was proposed. Acclimation is the main method to enhance the productivity of microorganisms in environmental biotechnology, but it remains uncertain how microorganisms acquire resistance to high concentrations of pollutants during long-term acclimation. Shewanella oneidensis MR-1 was acclimated for 120 days with increasing hexavalent chromium (Cr(VI)) concentrations from 10 to 190 mg/L. The bacterium was able to survive from the highly toxic Cr(VI) environment due to its enhanced capability to reduce Cr(VI) and the increased cell membrane surface. We sequenced 19 complete genomes from 7 populations of MR-1, including the ancestral strain, the evolved strains in Cr(VI) environment on days 40, 80 and 120 and their corresponding controls. A total of 27, 49 and 90 single nucleotide polymorphisms were found in the Cr(VI)-evolved populations on days 40, 80 and 120, respectively. Nonsynonymous substitutions were clustered according to gene functions, and the gene mutations related to integral components of the membrane, including efflux pumps and transporters, were the key determinants of chromate resistance. In addition, MR-1 strengthened the detoxification of Cr(VI) through gene variations involved in adenosine triphosphate binding, electron carrier activity, signal transduction and DNA repair. Our results provide an in-depth analysis of how Cr(VI) resistance of S. oneidensis MR-1 is improved by acclimation, as well as a genetic understanding of the impact of long-term exposure of microorganisms to pollution.     

Application of Fe(VI) in abating contaminants in water: State of art and knowledge gaps

• The properties of Fe(VI) were summarized. • Both the superiorities and the limitations of Fe(VI) technologies were discussed. • Methods to improve contaminants oxidation/disinfection by Fe(VI) were introduced. • Future research needs for the development of Fe(VI) technologies were proposed. The past two decades have witnessed the rapid development and wide application of Fe(VI) in the field of water de-contamination because of its environmentally benign character. Fe(VI) has been mainly applied as a highly efficient oxidant/disinfectant for the selective elimination of contaminants. The in situ generated iron(III) (hydr)oxides with the function of adsorption/coagulation can further increase the removal of contaminants by Fe(VI) in some cases. Because of the limitations of Fe(VI) per se, various modified methods have been developed to improve the performance of Fe(VI) oxidation technology. Based on the published literature, this paper summarized the current views on the intrinsic properties of Fe(VI) with the emphasis on the self-decay mechanism of Fe(VI). The applications of Fe(VI) as a sole oxidant for decomposing organic contaminants rich in electron-donating moieties, as a bi-functional reagent (both oxidant and coagulant) for eliminating some special contaminants, and as a disinfectant for inactivating microorganisms were systematically summarized. Moreover, the difficulties in synthesizing and preserving Fe(VI), which limits the large-scale application of Fe(VI), and the potential formation of toxic byproducts during Fe(VI) application were presented. This paper also systematically reviewed the important nodes in developing methods to improve the performance of Fe(VI) as oxidant or disinfectant in the past two decades, and proposed the future research needs for the development of Fe(VI) technologies.     

Fabrication of highly efficient Bi2WO6/CuS composite for visible-light photocatalytic removal of organic pollutants and Cr(VI) from wastewater

• A novel Bi₂WO₆/CuS composite was fabricated by a facile solvothermal method. • This composite efficiently removed organic pollutants and Cr(VI) by photocatalysis. • The DOM could promoted synchronous removal of organic pollutants and Cr(VI). • This composite could be applied at a wide pH range in photocatalytic reactions. • Possible photocatalytic mechanisms of organic pollutants and Cr(VI) were proposed. A visible-light-driven Bi₂WO₆/CuS p-n heterojunction was fabricated using an easy solvothermal method. The Bi₂WO₆/CuS exhibited high photocatalytic activity in a mixed system containing rhodamine B (RhB), tetracycline hydrochloride (TCH), and Cr (VI) under natural conditions. Approximately 98.8% of the RhB (10 mg/L), 87.6% of the TCH (10 mg/L) and 95.1% of the Cr(VI) (15 mg/L) were simultaneously removed from a mixed solution within 105 min. The removal efficiencies of TCH and Cr(VI) increased by 12.9% and 20.4%, respectively, in the mixed solution, compared with the single solutions. This is mainly ascribed to the simultaneous consumption electrons and holes, which increases the amount of excited electrons/holes and enhances the separation efficiency of photogenerated electrons and holes. Bi₂WO₆/CuS can be applied over a wide pH range (2–6) with strong photocatalytic activity for RhB, TCH and Cr(VI). Coexisiting dissolved organic matter in the solution significantly promoted the removal of TCH (from 74.7% to 87.2%) and Cr(VI) (from 75.7% to 99.9%) because it accelerated the separation of electrons and holes by consuming holes as an electron acceptor. Removal mechanisms of RhB, TCH, and Cr(VI) were proposed, Bi₂WO₆/CuS was formed into a p-n heterojunction to efficiently separate and transfer photoelectrons and holes so as to drive photocatalytic reactions. Specifically, when reducing pollutants (e.g., TCH) and oxidizing pollutants (e.g., Cr(VI)) coexist in wastewater, the p-n heterojunction in Bi₂WO₆/CuS acts as a “bridge” to shorten the electron transport and thus simultaneously increase the removal efficiencies of both types of pollutants.     

Selective targeted adsorption and inactivation of antibiotic-resistant bacteria by Cr-loaded mixed metal oxides

• LDHs and MMOs was synthesized by ultrasound-assisted one-step co-precipitation. • MMOs performs the best for Cr(VI) and E. coli_NDM-1 simultaneous removal. • Possible antibacterial pathways of Cr-MMOs were proposed. Herein we provide a novel high-efficiency nanocomposite for bacterial capture based on mixed metal oxides (MMOs) with deleterious chromium properties. With both the layer structure of layered double hydroxides (LDHs) and the magnetic properties of Fe, MMOs enrich the location of ionic forms on the surface, providing a good carrier for adsorption of the heavy metal Cr(VI). The capacity for adsorption of Cr(VI) by MMOs can be as high as 98.80 mg/g. The prepared Cr(VI)-MMOs achieved extremely expeditious location of gram-negative antibiotic-resistant E. coli_NDM-1 by identifying lipid bilayers. Cr-MMOs with a Cr loading of 19.70 mg/g had the best bactericidal effect, and the concentration of E. coli_NDM-1 was decreased from ~10⁸ to ~10³ CFU/mL after 30 min of reaction. The binding of nitrogen and phosphorus hydrophilic groups to chromate generated realistic models for density functional theory (DFT) calculations. The specific selectivity of MMOs toward bacterial cells was improved by taking Cr(VI) as a transferable medium, thereby enhancing the antibacterial activity of Cr-MMOs. Under the combined action of chemical and physical reactions, Cr(VI)-MMOs achieved high capacity for inactivation of bacteria. Moreover, the metallic elements ratio in Cr-MMOs remained stable in their initial valence states after inactivation. This guaranteed high removal efficiency for both heavy metals and bacteria, allowing recycling of the adsorbent in practical applications.     

One-pot hydrothermal fabrication of BiVO4/Fe3O4/rGO composite photocatalyst for the simulated solar light-driven degradation of Rhodamine B

• BiVO₄/Fe₃O₄/rGO has excellent photocatalytic activity under solar light radiation. • It can be easily separated and collected from water in an external magnetic field. • BiVO₄/Fe₃O₄/0.5% rGO exhibited the highest RhB removal efficiency of over 99%. • Hole (h⁺) and superoxide radical (O₂^•−) dominate RhB photo-decomposition process. • The reusability of this composite was confirmed by five successive recycling runs. Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application. In this study, a novel ternary magnetic photocatalyst BiVO₄/Fe₃O₄/reduced graphene oxide (BiVO₄/Fe₃O₄/rGO) was synthesized via a facile hydrothermal strategy. The BiVO₄/Fe₃O₄ with 0.5 wt% of rGO (BiVO₄/Fe₃O₄/0.5% rGO) exhibited superior activity, degrading greater than 99% Rhodamine B (RhB) after 120 min solar light radiation. The surface morphology and chemical composition of BiVO₄/Fe₃O₄/rGO were studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The free radicals scavenging experiments demonstrated that hole (h⁺) and superoxide radical (O₂^•−) were the dominant species for RhB degradation over BiVO₄/Fe₃O₄/rGO under solar light. The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field. The BiVO₄/Fe₃O₄/rGO composite was easily separated, and the recycled catalyst retained high photocatalytic activity. This study demonstrates that catalyst BiVO₄/Fe₃O₄/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use. The current study provides a possibility for more practical and sustainable photocatalytic process.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Photocatalytic degradation of the acetaminophen by nanocrystal-engineered TiO2 thin film in batch and continuous system

• Photocatalytic activity was improved in TiO₂ thin film by rapid thermal annealing. • Photoreactor was designed for TiO₂ thin film. • Considerable reusability and durability of prepared photocatalysts were studied. Un-biodegradable pharmaceuticals are one of the major growing threats in the wastewaters. In the current study, TiO₂ thin film photocatalysts were designed by nanocrystal engineering and fabricated for degradation of the acetaminophen (ACE) in a photocatalytic reaction under UV light irradiation in batch and continuous systems. The photocatalyst was prepared by sputtering and then engineered by thermal treatment (annealing at 300℃ (T300) and 650℃ (T650)). The annealing effects on the crystallinity and photocatalytic activity of the TiO₂ film were completely studied; it was found that annealing at higher temperatures increases the surface roughness and grain size which are favorable for photocatalytic activity due to the reduction in the recombination rate of photo-generated electron-hole pairs. For the continuous system, a flat plate reactor (FPR) was designed and manufactured. The photocatalytic performance was decreased with the increase of flow rate because the higher flow rate caused to form the thicker film of the liquid in the reactor and reduced the UV light received by photocatalyst. The reusability and durability of the samples after 6 h of photocatalytic reaction showed promising performance for the T650 sample (annealed samples in higher temperatures).     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.