RESUMEN
Poly(butylene succinate-co-furandicarboxylate) (PBSF) and poly(butylene adipate-co-furandicarboxylate) (PBAF) are novel furandicarboxylic acid-based biodegradable copolyesters with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene succinate-co-terephthalate) (PBST) and poly(butylene adipate-co-terephthalate) (PBAT). In this study, quantum chemistry techniques after molecular dynamics simulations are employed to investigate the degradation mechanism of PBSF and PBAF catalyzed by Candida antarctica lipase B (CALB). Computational analysis indicates that the catalytic reaction follows a four-step mechanism resembling the ping-pong bibi mechanism, with the initial two steps being acylation reactions and the subsequent two being hydrolysis reactions. Notably, the first step of the hydrolysis is identified as the rate-determining step. Moreover, by introducing single-point mutations to expand the substrate entrance tunnel, the catalytic distance of the first acylation step decreases. Additionally, energy barrier of the rate-determining step is decreased in the PBSF system by site-directed mutations on key residues increasing hydrophobicity of the enzyme's active site. This study unprecedently show the substrate binding pocket and hydrophobicity of the enzyme's active site have the potential to be engineered to enhance the degradation of copolyesters catalyzed by CALB.
Asunto(s)
Proteínas Fúngicas , Lipasa , Poliésteres , Lipasa/metabolismo , Lipasa/química , Proteínas Fúngicas/metabolismo , Proteínas Fúngicas/química , Poliésteres/química , Poliésteres/metabolismo , Biodegradación Ambiental , Simulación de Dinámica Molecular , Hidrólisis , Modelos QuímicosRESUMEN
Cerium and cobalt loaded Co-Ce/TiO2 catalyst prepared by impregnation method was investigated for photothermal catalytic toluene oxidation. Based on catalyst characterizations (XPS, EPR and H2-TPR), redox cycle between Co and TiO2 (Co2+ + Ti4+ â Co3+ + Ti3+) results in the formation of Co3+, Ti3+ and oxygen vacancies, which play important roles in toluene catalytic oxidation reaction. The introduction of Ce brings in the dual redox cycles (Co2+ + Ti4+ â Co3+ + Ti3+, Co2+ + Ce4+ â Co3+ + Ce3+), further promoting the elevation of reaction sites amount. Under full spectrum irradiation with light intensity of 580 mW/cm2, Co-Ce/TiO2 catalyst achieved 96% of toluene conversion and 73% of CO2 yield, obviously higher than Co/P25 and Co/TiO2. Co-Ce/TiO2 efficiently maintains 10-hour stability test under water vapor conditions and exhibits better photothermal catalytic performance than counterparts under different wavelengths illumination. Photothermal catalytic reaction displays improved activities compared with thermal catalysis, which is attributed to the promotional effect of light including photocatalysis and light activation of reactive oxygen species.
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Cerio , Cobalto , Oxidación-Reducción , Titanio , Tolueno , Titanio/química , Cobalto/química , Catálisis , Tolueno/química , Cerio/química , Modelos Químicos , Procesos FotoquímicosRESUMEN
Catalytic reduction of nitrate over bimetallic catalysts has emerged as a technology for sustainable treatment of nitrate-containing groundwater. However, the structure of bimetallic has been much less investigated for catalyst optimization. Herein, two main types of Pd-Cu bimetallic nanocrystal structures, heterostructure and intermetallic, were prepared and characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results show that two individual Pd and Cu nanocrystals with a mixed interface exist in the heterostructure nanocrystals, while Pd and Cu atoms are uniformly distributed across the intermetallic Pd-Cu nanocrystals. The catalytic nitrate reduction experiments were carried out in a semibatch reactor under constant hydrogen flow. The nitrate conversion rate of the heterostructure Pd-Cu nanocrystals supported on α-Al2O3, γ-Al2O3, SBA-15, and XC-72R exhibited 3.82-, 6.76-, 4.28-, 2.44-fold enhancements relative to the intermetallic nanocrystals, and the nitrogen and nitrite were the main products for the heterostructure and intermetallic Pd-Cu nanocrystals, respectively. This indicates that the catalytic nitrate reduction over Pd-Cu catalyst is sensitive to the bimetallic structures of the catalysts, and heterostructure bimetallic nanocrystals exhibit better catalytic performances on both the activity and selectivity, which may provide new insights into the design and optimization of catalysts to improve catalytic activity and selectivity for nitrate reduction in water.
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Cobre , Nitratos , Oxidación-Reducción , Paladio , Catálisis , Cobre/química , Paladio/química , Nitratos/química , Nanopartículas del Metal/química , Nanopartículas/química , Contaminantes Químicos del Agua/química , Modelos QuímicosRESUMEN
In the context of peaking carbon dioxide emissions and carbon neutrality, development of feasible methods for converting CO2 into high value-added chemicals stands out as a hot subject. In this study, P[D+COO-][Br-][DBUH+], a series of novel heterogeneous dual-ionic poly(ionic liquid)s (PILs) were synthesized readily from 2-(dimethylamino) ethyl methacrylate (DMAEMA), bromo-substituted aliphatic acids, organic bases and divinylbenzene (DVB). The structures, compositions and morphologies were characterized or determined by nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), infrared spectroscopy (IR), scanning electron microscopes (SEM), and Brunauer-Emmett-Teller analysis (BET), etc. Application of the P[D+COO-][Br-][DBUH+] series as catalysts in converting CO2 into cyclic carbonates showed that P[D+COO-][Br-][DBUH+]-2/1/0.6 was able to catalyze epiclorohydrin-CO2 cycloaddition the most efficiently. This afforded chloropropylene carbonate (CPC) in 98.4% yield with ≥ 99% selectivity in 24 hr under solvent- and additive-free conditions at atmospheric pressure. Reusability experiments showed that recycling of the catalyst 6 times only resulted in a slight decline in the catalytic performance. In addition, it could be used for the synthesis of a variety of differently substituted cyclic carbonates in good to excellent yields. Finally, key catalytic active sites were probed, and a reasonable mechanism was proposed accordingly. In summary, this work poses an efficient strategy for heterogenization of dual-ionic PILs and provides a mild and environmentally benign approach to the fixation and utilization of carbon dioxide.
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Dióxido de Carbono , Carbonatos , Líquidos Iónicos , Líquidos Iónicos/química , Dióxido de Carbono/química , Carbonatos/química , Catálisis , Modelos QuímicosRESUMEN
Sulfur trioxide (SO3) as a condensable particle matter has a significant influence on atmospheric visibility, which easily arouses formation of haze. It is imperative to control the SO3 emission from the industrial flue gas. Three commonly used basic absorbents, including Ca(OH)2, MgO and NaHCO3 were selected to explore the effects of temperature, SO2 concentration on the SO3 absorption, and the reaction mechanism of SO3 absorption was further illustrated. The suitable reaction temperature for various absorbents were proposed, Ca(OH)2 at the high temperatures above 500°C, MgO at the low temperatures below 320°C, and NaHCO3 at the temperature range of 320-500°C. The competitive absorption between SO2 and SO3 was found that the addition of SO2 reduced the SO3 absorption on Ca(OH)2 and NaHCO3, while had no effect on MgO. The order of the absorption selectivity of SO3 follows MgO, NaHCO3 and Ca(OH)2 under the given conditions in this work. The absorption process of SO3 on NaHCO3 follows the shrinking core model, thus the absorption reaction continues until NaHCO3 was exhausted with the utilization rate of nearly 100%. The absorption process of SO3 on Ca(OH)2 and MgO follows the grain model, and the dense product layer hinders the further absorption reaction, resulting in low utilization of about 50% for Ca(OH)2 and MgO. The research provides a favorable support for the selection of alkaline absorbent for SO3 removal in application.
Asunto(s)
Contaminantes Atmosféricos , Dióxido de Azufre , Dióxido de Azufre/química , Contaminantes Atmosféricos/química , Contaminantes Atmosféricos/análisis , Óxidos de Azufre/química , Modelos Químicos , Óxido de Magnesio/química , Hidróxido de Calcio/químicaRESUMEN
Reducing the cost of RuO2/TiO2 catalysts is still one of the urgent challenges in catalytic HCl oxidation. In the present work, a Ce-doped TiO2 supported RuO2 catalyst with a low Ru loading was developed, showing a high activity in the catalytic oxidation of HCl to Cl2. The results on some extensive characterizations of both Ce-doped TiO2 carriers and their supported RuO2 catalysts show that the doping of Ce into TiO2 can effectively change the lattice parameters of TiO2 to improve the dispersion of the active RuO2 species on the carrier, which facilitates the production of surface Ru species to expose more active sites for boosting the catalytic performance even under some harsh reaction conditions. This work provides some scientific basis and technical support for chlorine recycling.
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Cerio , Ácido Clorhídrico , Oxidación-Reducción , Titanio , Titanio/química , Catálisis , Cerio/química , Ácido Clorhídrico/química , Compuestos de Rutenio/química , Cloruros/química , Modelos Químicos , Cloro/químicaRESUMEN
Post-etching method using dilute acid solutions is an effective technology to modulate the surface compositions of metal-oxide catalysts. Here the α-MnO2 catalyst treated with 0.1 mol/L nitric acid exhibits higher ozone decomposition activity at high relative humidity than the counterpart treated with acetic acid. Besides the increases in surface area and lattice dislocation, the improved activity can be due to relatively higher Mn valence on the surface and newly-formed Brønsted acid sites adjacent to oxygen vacancies. The remnant nitro species deposited on the catalyst by nitric acid treatment is ideal hydrophobic groups at ambient conditions. The decomposition route is also proposed based on the DRIFTS and DFT calculations: ozone is facile to adsorb on the oxygen vacancy, and the protonic H of Brønsted acid sites bonds to the terminal oxygen of ozone to accelerate its cleavage to O2, reducing the reaction energy barrier of O2 desorption.
Asunto(s)
Humedad , Compuestos de Manganeso , Óxidos , Ozono , Ozono/química , Óxidos/química , Compuestos de Manganeso/química , Catálisis , Modelos QuímicosRESUMEN
Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy. Therefore, the method has received much attention. In this work, Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization. Bimetallic centers (Cu, Fe) with enhanced intrinsic activity demonstrated higher removal efficiency. Meanwhile, the 2D nanosheet reduced the mass transfer barrier between the catalyst and nitrate and increased the reaction kinetics. Therefore, the catalysts with a 2D structure showed much better removal efficiency than other structures (3D MOFs and Bulk MOFs). Under optimal conditions, Cu/Fe-2D MOF exhibited high nitrate removal efficiency (87.8%) and ammonium selectivity (89.3%) simultaneously. The ammonium yielded up to significantly 907.2 µg/(hr·mgcat) (7793.8 µg/(hr·mgmetal)) with Faradaic efficiency of 62.8% at an initial 100 mg N/L. The catalyst was proved to have good stability and was recycled 15 times with excellent effect. DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF. This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.
Asunto(s)
Amoníaco , Cobre , Hierro , Estructuras Metalorgánicas , Nitratos , Contaminantes Químicos del Agua , Amoníaco/química , Cobre/química , Nitratos/química , Estructuras Metalorgánicas/química , Hierro/química , Contaminantes Químicos del Agua/química , Catálisis , Modelos Químicos , Oxidación-Reducción , CinéticaRESUMEN
Phthalic acid esters (PAEs) are a group of compounds widespread in the environment. To investigate the occurrence and accumulation characteristics of PAEs, surface water samples were collected from the Three Gorges Reservoir area, China. The total concentrations of 11 analyzed PAEs (∑11PAEs) in the collected water samples ranging from 197.7 to 1,409.3 ng/L (mean ± IQR: 583.1 ± 308.4 ng/L). While DEHP was the most frequently detected PAE, DnBP and DnNP were the most predominant PAEs in the analyzed water samples with a mean contribution of 63.3% of the ∑11PAEs. The concentrations of the ∑11PAEs in the water samples from the upper reaches of the Yangtze River were significantly higher than those from the middle reaches. To better understand the transport and fate of the PAEs, seven detected PAEs were modeled by Quantitative Water Air Sediment Interaction (QWASI). The simulated and measured values were close for most PAEs, and differences are within one order of magnitude even for the worst one. For all simulated PAEs, water and particle inflow were main sources in the reservoir, whereas water outflow and degradation in water were important removal pathways. The contribution ratios of different sources/losses varied from PAEs, depending on their properties. The calculated risk quotients of DnNP in the Three Gorges Reservoir area whether based on monitoring or simulating results were all far exceeded the safety threshold value, implying the occurrence of this PAE compound may cause potential adverse effects for the aquatic ecology of the Three Gorges Reservoir area.
Asunto(s)
Monitoreo del Ambiente , Ésteres , Ácidos Ftálicos , Contaminantes Químicos del Agua , Ácidos Ftálicos/análisis , China , Contaminantes Químicos del Agua/análisis , Ésteres/análisis , Ríos/química , Modelos QuímicosRESUMEN
Oxidation of organic amines (OAs) or aromatic hydrocarbons (AHs) produces carbonyls, which further react with OAs to form carbonyl-amine condensation products, threatening environmental quality and human health. However, there is still a lack of systematic understanding of the carbonyl-amine condensation reaction processes of OAs or between OAs and AHs, and subsequent environmental health impact. This work systematically investigated the carbonyl-amine condensation coupled ozonolysis kinetics, reaction mechanism, secondary organic aerosol (SOA) formation and cytotoxicity from the mixture of dipropylamine (DPA) and styrene (STY) by a combined method of product mass spectrometry identification, particle property analysis and cell exposure evaluation. The results from ozonolysis of DPA and STY mixture revealed that STY inhibited the ozonolysis of DPA to different degrees to accelerate its own decay rate. The barycenter of carbonyl-amine condensation reactions was shifted from inside of DPA to between DPA and STY, which accelerated STY ozonolysis, but slowed down DPA ozonolysis. For the first time, ozonolysis of DPA and STY mixture to complex carbonyl-amine condensation products through the reactions of DPA with its carbonyl products, DPA with STY's carbonyl products and DPA's bond breakage product with STY's carbonyl products was confirmed. These condensation products significantly contributed to the formation and growth of SOA. The SOA containing particulate carbonyl-amine condensation products showed definite cytotoxicity. These findings are helpful to deeply and comprehensively understand the transformation, fate and environmental health effects of mixed organics in atmospheric environment.
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Aerosoles , Contaminantes Atmosféricos , Aminas , Ozono , Estireno , Ozono/química , Aminas/química , Aminas/toxicidad , Cinética , Estireno/química , Estireno/toxicidad , Contaminantes Atmosféricos/química , Contaminantes Atmosféricos/toxicidad , Humanos , Oxidación-Reducción , Modelos QuímicosRESUMEN
Herein, three supported catalysts, CuO/Al2O3, CeO2/Al2O3, and CuO-CeO2/Al2O3, were synthesized by the convenient impregnation method to reveal the effect of CeO2 addition on catalytic performance and reaction mechanism for toluene oxidation. Compared with CuO/Al2O3, the T50 and T90 (the temperatures at 50% and 90% toluene conversion, respectively) of CuO-CeO2/Al2O3 were reduced by 33 and 39 °C, respectively. N2 adsorption-desorption experiment, XRD, SEM, EDS mapping, Raman, EPR, H2-TPR, O2-TPD, XPS, NH3-TPD, Toluene-TPD, and in-situ DRIFTS were conducted to characterize these catalysts. The excellent catalytic performance of CuO-CeO2/Al2O3 could be attributed to its strong copper-cerium interaction and high oxygen vacancies concentration. Moreover, in-situ DRIFTS proved that CuO-CeO2/Al2O3 promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene. This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.
Asunto(s)
Cerio , Cobre , Oxidación-Reducción , Tolueno , Tolueno/química , Catálisis , Cobre/química , Cerio/química , Modelos Químicos , Contaminantes Atmosféricos/químicaRESUMEN
The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol (SOA). However, to date, the reactivity of C2 Criegee intermediates (CH3CHOO) in areas contaminated with acidic gas remains poorly understood. Herein, high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations are used to explore the reaction of CH3CHOO and H2SO4 both in the gas phase and at the air-water interface. In the gas phase, the addition reaction of CH3CHOO with H2SO4 to generate CH3HC(OOH)OSO3H (HPES) is near-barrierless, regardless of the presence of water molecules. BOMD simulations show that the reaction at the air-water interface is even faster than that in the gas phase. Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids, ammonias, and water molecules to form stable clusters, meanwhile the oligomerization reaction of CH3CHOO with HPES in the gas phase is both thermochemically and kinetically favored. Also, it is noted that the interfacial HPES- ion can attract H2SO4, NH3, (COOH)2 and HNO3 for particle formation from the gas phase to the water surface. Thus, the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions, but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.
Asunto(s)
Ácidos Sulfúricos , Ácidos Sulfúricos/química , Aerosoles , Modelos Químicos , Contaminantes Atmosféricos/química , Simulación de Dinámica Molecular , Atmósfera/químicaRESUMEN
Li6ZnO4 was chemically modified by nickel addition, in order to develop different compositions of the solid solution Li6Zn1-xNixO4. These materials were evaluated bifunctionally; analyzing their CO2 capture performances, as well as on their catalytic properties for H2 production via dry reforming of methane (DRM). The crystal structures of Li6Zn1-xNixO4 solid solution samples were determined through X-ray diffraction, which confirmed the integration of nickel ions up to a concentration around 20 mol%, meanwhile beyond this value, a secondary phase was detected. These results were supported by XPS and TEM analyses. Then, dynamic and isothermal thermogravimetric analyses of CO2 capture revealed that Li6Zn1-xNixO4 solid solution samples exhibited good CO2 chemisorption efficiencies, similarly to the pristine Li6ZnO4 chemisorption trends observed. Moreover, a kinetic analysis of CO2 isothermal chemisorptions, using the Avrami-Erofeev model, evidenced an increment of the constant rates as a function of the Ni content. Since Ni2+ ions incorporation did not reduce the CO2 capture efficiency and kinetics, the catalytic properties of these materials were evaluated in the DRM process. Results demonstrated that nickel ions favored hydrogen (H2) production over the pristine Li6ZnO4 phase, despite a second H2 production reaction was determined, methane decomposition. Thereby, Li6Zn1-xNixO4 ceramics can be employed as bifunctional materials.
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Dióxido de Carbono , Hidrógeno , Metano , Hidrógeno/química , Metano/química , Dióxido de Carbono/química , Níquel/química , Catálisis , Modelos QuímicosRESUMEN
Catalytic hydrogenation of CO2 to ethanol is a promising solution to address the greenhouse gas (GHG) emissions, but many current catalysts face efficiency and cost challenges. Cobalt based catalysts are frequently examined due to their abundance, cost-efficiency, and effectiveness in the reaction, where managing the Co0 to Coδ+ ratio is essential. In this study, we adjusted support nature (Al2O3, MgO-MgAl2O4, and MgO) and reduction conditions to optimize this balance of Co0 to Coδ+ sites on the catalyst surface, enhancing ethanol production. The selectivity of ethanol reached 17.9% in a continuous flow fixed bed micro-reactor over 20 mol% Co@MgO-MgAl2O4 (CoMgAl) catalyst at 270 °C and 3.0 MPa, when reduced at 400 °C for 8 h. Characterisation results coupled with activity analysis confirmed that mild reduction condition (400 °C, 10% H2 balance N2, 8 h) with intermediate metal support interaction favoured the generation of partially reduced Co sites (Coδ+ and Co0 sites in single atom) over MgO-MgAl2O4 surface, which promoted ethanol synthesis by coupling of dissociative (CHx*)/non-dissociative (CHxO*) intermediates, as confirmed by density functional theory analysis. Additionally, the CoMgAl, affordably prepared through the coprecipitation method, offers a potential alternative for CO2 hydrogenation to yield valuable chemicals.
Asunto(s)
Dióxido de Carbono , Cobalto , Etanol , Dióxido de Carbono/química , Etanol/química , Hidrogenación , Cobalto/química , Catálisis , Nanopartículas/química , Modelos QuímicosRESUMEN
Humic acid (HA), a principal constituent of natural organic matter (NOM), manifests ubiquitously across diverse ecosystems and can significantly influence the environmental behaviors of Cd(II) in aquatic systems. Previous studies on NOM-Cd(II) interactions have primarily focused on the immobilization of Cd(II) solids, but little is known about the colloidal stability of organically complexed Cd(II) particles in the environment. In this study, we investigated the formation of HA-Cd(II) colloids and quantified their aggregation, stability, and transport behaviors in a saturated porous media representative of typical subsurface conditions. Results from batch experiments indicated that the relative quantity of HA-Cd(II) colloids increased with increasing C/Cd molar ratio and that the carboxyl functional groups of HA dominated the stability of HA-Cd(II) colloids. The results of correlation analysis between particle size, critical aggregation concentration (CCC), and zeta potential indicated that both Derjaguin-Landau-Verwey-Overbeek (DLVO) and non-DLVO interactions contributed to the enhanced colloidal stability of HA-Cd(II) colloids. Column results further confirmed that the stable HA-Cd(II) colloid can transport fast in a saturated media composed of clean sand. Together, this study provides new knowledge of the colloidal behaviors of NOM-Cd(II) nanoparticles, which is important for better understanding the ultimate cycling of Cd(II) in aquatic systems.
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Cadmio , Coloides , Sustancias Húmicas , Contaminantes Químicos del Agua , Sustancias Húmicas/análisis , Cadmio/química , Coloides/química , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/análisis , Nanopartículas del Metal/química , Modelos Químicos , Nanopartículas/químicaRESUMEN
Fischer-Tropsch synthesis (FTS) wastewater retaining low-carbon alcohols and acids are organic pollutants as a limiting factor for FTS industrialization. In this work, the structure-capacity relationships between alcohol-acid adsorption and surface species on graphene were reported, shedding light into their intricate interactions. The graphene oxide (GO) and reduced graphene oxide (rGO) were synthesized via improved Hummers method with flake graphite (G). The physicochemical properties of samples were characterized via SEM, XRD, XPS, FT-IR, and Raman. The alcohol-acid adsorption behaviors and adsorption quantities on G, GO, and rGO were measured via theoretical and experimental method. It was revealed that the presence of COOH, C=O and CO species on graphene occupy the adsorption sites and increase the interactions of water with graphene, which are unfavorable for alcohol-acid adsorption. The equilibrium adsorption quantities of alcohols and acids grow in pace with carbon number. The monolayer adsorption occurs on graphene was verified via model fitting. rGO has the highest FTS modeling wastewater adsorption quantity (110 mg/g) due to the reduction of oxygen species. These novel findings provide a foundation for the alcohol-acid wastewater treatment, as well as the design and development of high-performance carbon-based adsorbent materials.
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Alcoholes , Grafito , Aguas Residuales , Contaminantes Químicos del Agua , Grafito/química , Adsorción , Aguas Residuales/química , Contaminantes Químicos del Agua/química , Alcoholes/química , Eliminación de Residuos Líquidos/métodos , Modelos Químicos , Ácidos/químicaRESUMEN
Nano zero-valent iron (nZVI) is a promising phosphate adsorbent for advanced phosphate removal. However, the rapid passivation of nZVI and the low activity of adsorption sites seriously limit its phosphate removal performance, accounting for its inapplicability to meet the emission criteria of 0.1 mg P/L phosphate. In this study, we report that the oxalate modification can inhibit the passivation of nZVI and alter the multi-stage phosphate adsorption mechanism by changing the adsorption sites. As expected, the stronger anti-passivation ability of oxalate modified nZVI (OX-nZVI) strongly favored its phosphate adsorption. Interestingly, the oxalate modification endowed the surface Fe(III) sites with the lowest chemisorption energy and the fastest phosphate adsorption ability than the other adsorption sites, by in situ forming a Fe(III)-phosphate-oxalate ternary complex, therefore enabling an advanced phosphate removal process. At an initial phosphate concentration of 1.00 mg P/L, pH of 6.0 and a dosage of 0.3 g/L of adsorbents, OX-nZVI exhibited faster phosphate removal rate (0.11 g/mg/min) and lower residual phosphate level (0.02 mg P/L) than nZVI (0.055 g/mg/min and 0.19 mg P/L). This study sheds light on the importance of site manipulation in the development of high-performance adsorbents, and offers a facile surface modification strategy to prepare superior iron-based materials for advanced phosphate removal.
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Hierro , Oxalatos , Fosfatos , Contaminantes Químicos del Agua , Fosfatos/química , Adsorción , Hierro/química , Contaminantes Químicos del Agua/química , Oxalatos/química , Purificación del Agua/métodos , Modelos QuímicosRESUMEN
Perfluoroalkyl substances (PFASs) are typical persistent organic pollutants, and their removal is urgently required but challenging. Photocatalysis has shown potential in PFASs degradation due to the redox capabilities of photoinduced charge carriers in photocatalysts. Herein, hexagonal ZnIn2S4 (ZIS) nanosheets were synthesized by a one-pot oil bath method and were well characterized by a series of techniques. In the degradation of sodium p-perfluorous nonenoxybenzenesulfonate (OBS), one kind of representative PFASs, the as-synthesized ZIS showed activity superior to P25 TiO2 under both simulated sunlight and visible-light irradiation. The good photocatalytic performance was attributed to the enhanced light absorption and facilitated charge separation. The pH conditions were found crucial in the photocatalytic process by influencing the OBS adsorption on the ZIS surface. Photogenerated e- and h+ were the main active species involved in OBS degradation in the ZIS system. This work confirmed the feasibility and could provide mechanistic insights into the degradation and defluorination of PFASs by visible-light photocatalysis.
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Fluorocarburos , Luz , Fotólisis , Fluorocarburos/química , Nanoestructuras/química , Catálisis , Contaminantes Químicos del Agua/química , Zinc/química , Indio/química , Modelos QuímicosRESUMEN
Naphthenic acids, NAs, are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters, OSPW. Using activated carbon adsorbents are an attractive option given their low cost of fabrication and implementation. A deeper evaluation of the effect NA structural differences have on uptake affinity is warranted. Here we provide an in-depth exploration of NA adsorption including many more model NA species than have been assessed previously with evaluation of adsorption kinetics and isotherms at the relevant alkaline pH of OSPW using several different carbon adsorbents with pH buffering to simulate the behaviour of real OSPW. Uptake for the NA varied considerably regardless of the activated carbon used, ranging from 350 mg/g to near zero highlighting recalcitrant NAs. The equilibrium data was explored to identify structural features of these species and key physiochemical properties that influence adsorption. We found that certain NA will be resistant to adsorption when hydrophobic adsorbents are used. Adsorption isotherm modelling helped explore interactions occurring at the interface between NA and adsorbent surfaces. We identified the importance of NA hydrophobicity for activated carbon uptake. Evidence is also presented that indicates favorable hydrogen bonding between certain NA and surface site hydroxyl groups, demonstrating the importance of adsorbent surface functionality for NA uptake. This research highlights the challenges associated with removing NAs from OSPW through adsorption and also identifies how adsorbent surface chemistry modification can be used to increase the removal efficiency of recalcitrant NA species.
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Ácidos Carboxílicos , Contaminantes Químicos del Agua , Adsorción , Ácidos Carboxílicos/química , Contaminantes Químicos del Agua/química , Carbón Orgánico/química , Modelos Químicos , Cinética , Concentración de Iones de HidrógenoRESUMEN
Heterogeneous oxidation by gas-phase oxidants is an important chemical transformation pathway of secondary organic aerosol (SOA) and plays an important role in controlling the abundance, properties, as well as climate and health impacts of aerosols. However, our knowledge on this heterogeneous chemistry remains inadequate. In this study, the heterogeneous oxidation of α-pinene ozonolysis SOA by hydroxyl (OH) radicals was investigated under both low and high relative humidity (RH) conditions, with an emphasis on the evolution of molecular composition of SOA and its RH dependence. It is found that the heterogeneous oxidation of SOA at an OH exposure level equivalent to 12 hr of atmospheric aging leads to particle mass loss of 60% at 25% RH and 95% at 90% RH. The heterogeneous oxidation strongly changes the molecular composition of SOA. The dimer-to-monomer signal ratios increase dramatically with rising OH exposure, in particular under high RH conditions, suggesting that aerosol water stimulates the reaction of monomers with OH radicals more than that of dimers. In addition, the typical SOA tracer compounds such as pinic acid, pinonic acid, hydroxy pinonic acid and dimer esters (e.g., C17H26O8 and C19H28O7) have lifetimes of several hours against heterogeneous OH oxidation under typical atmospheric conditions, which highlights the need for the consideration of their heterogeneous loss in the estimation of monoterpene SOA concentrations using tracer-based methods. Our study sheds lights on the heterogeneous oxidation chemistry of monoterpene SOA and would help to understand their evolution and impacts in the atmosphere.