Efficient immobilization and detoxification of gaseous elemental mercury by nanoflower/rod WSe2/halloysite composite: Performance and mechanisms.

Gaseous mercury pollution control technologies with low stability and high releasing risks always face with great challenges. Herein, we developed one halloysite nanotubes (HNTs)-supported tungsten diselenide (WSe2) composite (WSe2/HNTs) by one-pot solvothermal approach, curing Hg0 from complicated flue gas (CFG) and reducing second environment risks. WSe2 as a monolayer with nano-flower structure and HNTs with rod shapes in the as-prepared sorbent exhibited outstanding synergy efficiency, resulting in exceptional performance for Hg0 removal with high capture capacity of 30.6 mg·g-1 and rate of 9.09 µg·g-1·min-1, which benefited from the high affinity of selenium and mercury (1 ×1045) and the adequate exposure of Se-terminated. The adsorbent showed beneficial tolerance to high amount of NOx and SOx. An online lab-built thermal decomposition system (TPD-AFS) was employed to explore Hg species on the used-sorbent, finding that the adsorbed-mercury species were principally mercury selenide (HgSe). Density functional theory calculations indicated that the hollow-sites were the major adsorption sites and exhibited excellent selectivity for Hg0, as well as HgSe generation needed to overcome the 0.32 eV energy barrier. The adsorbed mercury displayed high environmental stability after the leaching toxicity test, which significantly decreased its secondary environmental risks. With these advantages, WSe2/HNTs possess enormous potential to achieve the effective and permanent immobilization of gaseous mercury from CFG in the future.

Identification of mercury species in coal combustion by-products from power plants using thermal desorption-atomic fluorescence spectrometry on-line coupling system.

Along with the environmental protection policies becoming strict in China, the air pollution control devices (especially selective catalytic reduction (SCR)) are widely equipped in coal-fired power plants. The installation and run of these devices will inevitably affect mercury (Hg) species distribution in coal fired by-products such like fly ash (FA) and gypsum. In this work, a new on-line coupling system based on atomic fluorescence spectrometry (AFS) with a home-made chromatographic workstation was successfully developed to identify Hg species through thermal programmed desorption (TPD). The influences of matrix, furnace temperature, and carrier gas flow on analytical performance were investigated and the parameters were optimized. The FA and gypsum samples from coal-fired power plants equipped with SCR were collected and the mercury species were analyzed by the developed coupling system. HgCl2 and HgO were the main species in FA, while Hg2Cl2 and HgO were the main species in gypsum. All of Hg species in the studied FA and gypsum samples were released below 400 °C. A sequential extraction procedure was applied to further verify the operational Hg species including mobile and non-mobile fractions in FA and gypsum samples. This study demonstrated that AFS coupled with TPD procedure was an effective method to analyze Hg species in coal combustion by-products from power plants.

Simultaneous removal of arsenate and arsenite in water using a novel functional halloysite nanotube composite.

This work aims at exploring a novel environment-friendly nanomaterial based on natural clay minerals for arsenic removal in aqueous samples. Halloysite nanotubes (HNTs) were selected as the substrate with Mn oxides loaded on the surface to enhance its arsenic adsorption ability and then grafted onto the SiO2-coated Fe3O4 microsphere to get a just enough magnetic performance facilitating the material's post-treatment. The prepared composite (Fe3O4@SiO2@Mn-HNTs) was extensively characterized by various instruments including Fourier transform infrared spectroscope (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TG), vibrating sample magnetometer (VSM), X-ray photoelectron spectroscope (XPS), and X-ray diffraction (XRD). Batch experiments were carried out to get the optimum test conditions for arsenic adsorption by the composite, including pH, loading amount of Mn oxides, adsorbent dosage, and the co-existing ions. The adsorption of AsIII and AsV on Fe3O4@SiO2@Mn-HNTs were both well fitted with the pseudo-second-order kinetic model as well as the Langmuir adsorption isotherm model revealing the chemisorption between arsenic and Fe3O4@SiO2@Mn-HNTs. The adsorption process of AsIII and AsV were both endothermic and spontaneous displayed by the thermodynamic study. The capacities of the prepared composite are 3.28 mg g-1 for AsIII and 3.52 mg g-1 for AsV, respectively, which are comparable or better than those of many reported materials in the references. Toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) tests were carried out to access the secondary environmental risk of the composite and showed that it was quite environmentally stable and can be safely disposed. The composite was successfully applied in environmental water samples indicating its great potential applicability in future.

Gaseous Arsenic Capture in Flue Gas by CuCl2-Modified Halloysite Nanotube Composites with High-Temperature NOx and SOx Resistance.

Gaseous arsenic emitted from coal combustion flue gas (CCFG) causes not only severe contamination of the environment but also the failure of selective catalytic reduction (SCR) catalysts in power plants. Development of inexpensive and effective adsorbents or techniques for the removal of arsenic from high-temperature CCFG is crucial. In this study, halloysite nanotubes (HNTs) at low price were modified with CuCl2 (CuCl2-HNTs) through ultrasound assistance and applied for capturing As2O3(g) in simulated flue gas (SFG). Experiments on arsenic adsorption performance, adsorption mechanism, and adsorption energy based on density functional theory were performed. Modification with CuCl2 clearly enhanced the arsenic uptake capacity (approximately 12.3 mg/g) at 600 °C for SFG. The adsorbent exhibited favorable tolerance to high concentrations of NOx and SOx. The As2O3(III) was oxidized and transformed into As2O5(V) on the CuCl2-HNTs. The Al-O bridge had the highest adsorption energy for the O end of the As-O group (-2.986 eV), and the combination formed between arsenic-containing groups and aluminum was stable. In addition, the captured arsenic could be stabilized in the sorbent at high temperature, making it possible to use the sorbent before the SCR system. This demonstrates that CuCl2-HNTs is a promising sorbent for arsenic oxidation and removal from CCFG.

Microwave-assisted continuous flow phytosynthesis of silver nanoparticle/reduced graphene oxide composites and related visible light catalytic performance.

The creation of an environmentally friendly synthesis method for silver nanomaterials (AgNPs) is an urgent concern for sustainable nanotechnology development. In the present study, a novel straightforward and green method for the preparation of silver nanoparticle/reduced graphene oxide (AgNP/rGO) composites was successfully developed through the combination of phytosynthesis, continuous flow synthesis and microwave-assistance. Oriental persimmon (Diospyros kaki Thunb.) extracts were used as both plant reducing and capping agents for fast online synthesis of AgNP/rGO composites. The experimental parameters were optimized and the morphologies of the prepared materials were investigated. The characterization results reveal that spherical AgNPs were quickly synthesized and uniformly dispersed on rGO sheets using the proposed online system. Fourier transform infrared spectroscopy analysis confirmed that phenols, flavonoids, and other substances in the plant extracts played a decisive role in the synthesis of AgNP/rGO composites. Using sodium borohydride (NaBH4) degradation of p-nitrophenol (4-NP) as a model, the catalytic activity of the prepared AgNP/rGO materials was evaluated. The complete degradation of 4-NP was achieved within 12 min through the use of AgNP/rGO materials, and the composite had a much better catalytic activity than the bare AgNPs and rGO had. Compared with the conventional chemical method, our online method is facile, fast, cost-efficient, and environmentally friendly.

Structures and impact strength variation of chemically crosslinked high-density polyethylene: effect of crosslinking density.

Impact strength of high-density polyethylene (HDPE), especially at low temperature, is crucial for its applications outdoors because of its poor impact strength. In order to improve the impact strength of HDPE, crosslinked HDPE was prepared by the addition of a peroxide crosslink agent, bis(tert-butyldioxyisopropyl)benzenehexane, and the effect of the crosslinking density on the microstructures and mechanical properties, especially impact strength between -60 °C and 23 °C, were investigated. The results show that the crosslinking density is controlled by varying the content of the crosslinking agent. It is found that, at room temperature, with increase in the content of crosslink agent from 0% to 0.5-0.7%, the impact strength increases from 4 kJ m-2 to about 80 kJ m-2 and the elongation at break increases from 20% to about 550%. With further increase in the content of crosslink agent to 1.5%, the impact strength and the elongation at break reduce to 64 kJ m-2 and 360% respectively. With increase in crosslink agent, the flexural modulus, yield strength, crystallinity, mean lamellar thickness, crystal size and spherulitic size and the brittle-ductile transition temperature (BDTT) decrease, and the gel content, impact strength of the HDPE at low temperature, intensity of ß transition increase significantly. In considering both the room temperature mechanical properties and low temperature impact strength, the optimized content of the crosslink agent is about 0.7%. Overall, crosslinking significantly improves the toughness and impact strength of HDPE and extends its application, especially at low temperature.

Synergistic effects of Fe-Mn binary oxide for gaseous arsenic removal in flue gas.

High-efficient and economic sorbents are highly desired for arsenic (As) emission control in flue gas from coal-fired power plant. A series of Fe-Mn binary oxides were prepared by a facile method, and their behaviors for gaseous arsenic removal in flue gas were investigated. The binary oxide exhibited a remarkable synergistic effect for arsenic removal compared with Mn or Fe monometallic oxide. The possible effects of CO2, NO, SO2, and O2 on the removal performance were also studied. The adsorption ability was excellent and stable in simulated flue gas conditions. X-ray photoelectron spectroscopy (XPS) and high-performance liquid chromatography atomic fluorescence spectroscopy (HPLC-AFS) coupling system were applied to analyze the species of surface-adsorbed arsenicals and soluble arsenicals. It was confirmed that the good sorption performance resulted from oxidation of As2O3 (As(III)) to As2O5 (As(V)) by Mn oxide and followed by efficient adsorption of As(V) on Fe oxide. Considering the toxicity of pentavalent arsenicals is lower than trivalent arsenicals, the oxidation of arsenic compounds can not only enhance its removal capacity but also decrease the toxicity of arsenicals after capture.

Preparation of halloysite nanotubes-encapsulated magnetic microspheres for elemental mercury removal from coal-fired flue gas.

Halloysite nanotubes (HNTs) as a natural and inexpensive clay mineral with hollow nanotubular structures, good biocompatibility and active surfaces have been ubiquitously applied in many fields. In this work, a novel multifunctional core-shell sorbent based on HNTs, CuCl2-HNTs encapsulated magnetic microspheres (SiO2@Fe3O4), was successfully fabricated and applied for Hg0 removal from flue gas with good performance for the first time. The core-shell structure prevented the composites from aggregating but kept their magnetism, which enabled the adsorbents being easily separated for reuse by an external magnetic field. In addition, the special structure also significantly enhanced the adsorption capacity of the composites by dispersing the CuCl2 modified HNTs on the prepared magnetic microspheres. The adsorption performance was comprehensively investigated and fitted by dynamic models. The adsorption followed surface adsorption, particle diffusion and chemisorption with very good SO2 tolerance. The Cu+, Cl- and lattice oxygen were the crucial components for Hg0 removal. In order to further understand the possible mechanism, an online home-made coupling system of temperature-programmed decomposition (TPD) was used to investigate the mercury species on the spent adsorbent in addition to X-ray photoelectron spectroscopy analysis. The results confirmed the mercury species adsorbed were primarily Hg0, HgO and HgCl2.

Elimination of elemental mercury in flue gas by Arachis hypogaea Linn. shell generated activated carbon.

It is very necessary to produce bio-activated carbon for special use with easy procedure and low cost. One kind of huge surface area microporous bio-material was successfully prepared from agricultural residues (peanut shell, Arachis hypogaea Linn.) and beneficially applied to control elemental mercury (Hg0) in simulated coal-fired flue gas in this study. The possible effects of experimental factors including activator, reaction temperature, and flue components were investigated. The physicochemical properties of the prepared adsorbents were characterized by Brunauer-Emmett-Teller (BET), scanning electron microscopy with energy-dispersive X-ray spectrometry (SEM-EDX), and X-ray photoelectron spectroscopy (XPS). The results indicated that the peanut shell activated carbon presented excellent Hg0 removal efficiency near 90% at 150 °C. The characterization analysis indicated that the removal characteristics were governed by both physical adsorption and chemical adsorption. The chemisorbed mercury on the activated carbon was mainly distinguished into mercuric chloride (HgCl2) and mercuric oxide (HgO). The presence of C-Cl and O* promoted Hg0 into HgCl2 and HgO. Zinc chloride could not only improve the micropore quantity of activated carbon but also have remarkably positive effects on the elemental mercury removal. This study provided a practical and easy preparation method of bio-activated carbon for Hg0 removal with low cost. Graphical Abstract.