Constructing High-performance Cobalt-based Environmental Catalysts from Spent Lithium-Ion Batteries: Unveiling Overlooked Roles of Copper and Aluminum from Current Collectors.

Converting spent lithium-ion batteries (LIBs) cathode materials into environmental catalysts has drawn more and more attention. Herein, we fabricated a Co3O4-based catalyst from spent LiCoO2 LIBs (Co3O4-LIBs) and found that the role of Al and Cu from current collectors on its performance is nonnegligible. The density functional theory calculations confirmed that the doping of Al and/or Cu upshifts the d-band center of Co. A Fenton-like reaction based on peroxymonosulfate (PMS) activation was adopted to evaluate its activity. Interestingly, Al doping strengthened chemisorption for PMS (from -2.615 eV to -2.623 eV) and shortened Co-O bond length (from 2.540 Å to 2.344 Å) between them, whereas Cu doping reduced interfacial charge-transfer resistance (from 28.347 kΩ to 6.689 kΩ) excepting for the enhancement of the above characteristics. As expected, the degradation activity toward bisphenol A of Co3O4-LIBs (0.523 min-1) was superior to that of Co3O4 prepared from commercial CoC2O4 (0.287 min-1). Simultaneously, the reasons for improved activity were further verified by comparing activity with catalysts doped Al and/or Cu into Co3O4. This work reveals the role of elements from current collectors on the performance of functional materials from spent LIBs, which is beneficial to the sustainable utilization of spent LIBs.

Scalable and Consolidated Microbial Platform for Rare Earth Element Leaching and Recovery from Waste Sources.

Chemical methods for the extraction and refinement of technologically critical rare earth elements (REEs) are energy-intensive, hazardous, and environmentally destructive. Current biobased extraction systems rely on extremophilic organisms and generate many of the same detrimental effects as chemical methodologies. The mesophilic methylotrophic bacterium Methylobacterium extorquens AM1 was previously shown to grow using electronic waste by naturally acquiring REEs to power methanol metabolism. Here we show that growth using electronic waste as a sole REE source is scalable up to 10 L with consistent metal yields without the use of harsh acids or high temperatures. The addition of organic acids increases REE leaching in a nonspecific manner. REE-specific bioleaching can be engineered through the overproduction of REE-binding ligands (called lanthanophores) and pyrroloquinoline quinone. REE bioaccumulation increases with the leachate concentration and is highly specific. REEs are stored intracellularly in polyphosphate granules, and genetic engineering to eliminate exopolyphosphatase activity increases metal accumulation, confirming the link between phosphate metabolism and biological REE use. Finally, we report the innate ability of M. extorquens to grow using other complex REE sources, including pulverized smartphones, demonstrating the flexibility and potential for use as a recovery platform for these critical metals.

Emerging catalysts for the ambient synthesis of ethylene glycol from CO2 and its derivatives.

Ethylene glycol (EG), a useful chemical raw material, has been widely applied in many aspects of modern society. The conventional preparation of ethylene glycol mainly uses the petroleum route at high temperatures and pressure. More and more approaches have been developed to synthesize EG from CO2 and its derivatives under mild conditions. In this review, the ambient synthesis of EG from thermocatalysis, photocatalysis, and electrocatalysis is highlighted. The coal-to-ethylene glycol technology, one of the typical thermal catalysis routes for EG preparation, is relatively mature. However, it still faces some problems to be solved in industrialization. The recent progress in the development of coal-to-ethylene glycol technology is introduced. The main focus is on how to realize the preparation of EG under mild conditions. The strategies include doping promoters, modification of supports, design of catalysts with special structures, etc. Furthermore, the emerging technological progress of photocatalytic and electrocatalytic ethylene glycol synthesis under ambient conditions is introduced. Compared with the thermal catalytic reaction, the reaction conditions are milder. However, there are still many problems in large-scale production. Finally, we propose future development issues and related prospects for the ambient synthesis of EG using different catalytic routes.

Core-Shell Covalently Linked Graphitic Carbon Nitride-Melamine-Resorcinol-Formaldehyde Microsphere Polymers for Efficient Photocatalytic CO2 Reduction to Methanol.

Photocatalytic reduction of CO2 with light and H2O to form CH3OH is a promising route to mitigate carbon emissions and climate changes. Although semiconducting metal oxides are potential photocatalysts for this reaction, low photon efficiency and leaching of environmentally unfriendly toxic metals limit their applicability. Here, we report metal-free, core-shell photocatalysts consisting of graphitic carbon nitride (g-C3N4, CN) covalently linked to melamine-resorcinol-formaldehyde (MRF) microsphere polymers for this reaction. Covalent linkage enabled efficient separation of photo-generated carriers and photocatalysis. Using 100 mg of a photocatalyst containing 15 wt % CN, a CH3OH yield of 0.99 µmol·h-1 was achieved at a reaction temperature of 80 °C and 0.5 MPa with external quantum efficiencies ranging from 5.5% at 380 nm to 1.7% at 550 nm. The yield was about 20 and 10 times higher than that of its components CN and MRF, respectively. Characterization with X-ray photoelectron spectroscopy, transmission electron microscopy, and bulk and surface elemental analyses supported the formation of a core-shell structure and the charge transfer in the C-N bond at the CN-MRF interface between the methoxy group in the 2,4-dihydroxylmethyl-1,3-diphenol part of MRF and the terminal amino groups in CN. This enhanced ligand-to-ligand charge transfer resulted in 67% of the photo-excited internal charge transferred from CN to the hydroxymethylamino group in MRF, whose amino group was the catalytic site for the CO2 photocatalytic reduction to CH3OH. This study provides a series of new metal-free photocatalyst designs and insights into the molecular-level structure-mediated photocatalytic response.

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst.

Direct synthesis of dimethyl ether (DME) by CO2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods: co-precipitation, sol-gel, and solid grinding to produce mixed Cu, ZnO, ZrO2 catalysts that were physically mixed with a commercial ferrierite (FER) zeolite. The catalysts were characterized by N2 physisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption of CO2 (CO2-TPD), temperature programmed desorption of NH3 (NH3-TPD), and temperature programmed H2 reduction (H2-TPR). The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases, higher surface area, and lower reduction temperature are all favorable for catalytic activity. The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Methanol appears to be formed via the bidentate-formate (b-HCOO) species undergoing stepwise hydrogenation, while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.

Catalyst-TiO(OH)2 could drastically reduce the energy consumption of CO2 capture.

Implementing Paris Climate Accord is inhibited by the high energy consumption of the state-of-the-art CO2 capture technologies due to the notoriously slow kinetics in CO2 desorption step of CO2 capture. To address the challenge, here we report that nanostructured TiO(OH)2 as a catalyst is capable of drastically increasing the rates of CO2 desorption from spent monoethanolamine (MEA) by over 4500%. This discovery makes CO2 capture successful at much lower temperatures, which not only dramatically reduces energy consumption but also amine losses and prevents emission of carcinogenic amine-decomposition byproducts. The catalytic effect of TiO(OH)2 is observed with Raman characterization. The stabilities of the catalyst and MEA are confirmed with 50 cyclic CO2 sorption and sorption. A possible mechanism is proposed for the TiO(OH)2-catalyzed CO2 capture. TiO(OH)2 could be a key to the future success of Paris Climat e Accord.

Visual Assay of Glutathione in Vegetables and Fruits Using Quantum Dot Ratiometric Hybrid Probes.

Future food safety monitoring with simple, fast, and visual methods has become increasingly important. Accordingly, this work was designed to construct a new-style dual-emission ratiometric fluorescent probe (CdSe@SiO2@CdTe) for visual assay of glutathione (GSH) with a "turn on" strategy. After adding Hg2+, the red fluorescence of the outer CdTe quantum dots (QDs) was quenched through both electron transfer and ion-binding processes. Upon the addition of GSH, the red fluorescence occurred again owing to the strong affinity between GSH and Hg2+, whereas the inner green fluorescence of CdSe QDs was unchanged, leading to a clearly recognizable fluorescence color change (from green to orange-red). In the concentration range from 0.1 to 10 µM, the relative fluorescence intensity ratios ( I619/ I535) showed an excellent linear correlation with the concentration of GSH, and the detection limit was as low as 42 nM under optimal conditions. Meanwhile, the ratiometric hybrid probes were successfully applied for direct visual sensing GSH in real vegetable and fruit samples.

A Self-Supported λ-MnO2 Film Electrode used for Electrochemical Lithium Recovery from Brines.

Lithium recovery from an aqueous resource was accelerated by electrochemically driving the transformation of MnIV /MnIII with a spinel λ-MnO2 film electrode. A λ-MnO2 electrode without binders or conductive additives is preferred for achieving a large capacity at high current density and long-term cycling capability. In this study, a film of Mn(OH)2 was first deposited on the surface of Pt or graphite substrates owing to alkalization near the cathode, then it was oxidized to a Mn3 O4 film by air, followed by being hydrothermally lithiated to LiMn2 O4 spinel and, finally, it was turned into the λ-MnO2 film electrode through potentiostatic delithiation. The results show that the charging/discharging electric capacity of the fabricated λ-MnO2 film electrode was up to ≈100 mAh g-1 at a current density of 50 mA g-1 in 30 mm Li+ aqueous solution, twice that of the λ-MnO2 powder electrode. Also, 82.3 % lithium capacity remained after 100 cycles of an electrochemically assisted lithium recovery process, indicating high availability and good stability of the λ-MnO2 spinel on the electrode. The energy consumption for each cycle is estimated to be approximately 1.55±0.09 J, implying that only 4.14 Wh is required for recovery of one mole of lithium ions by this method.

Selective denitrification of flue gas by O3 and ethanol mixtures in a duct: Investigation of processes and mechanisms.

A novel selective denitrification process, referred as O3-ethanol oxidation method, was developed by injecting O3 and ethanol mixtures into the simulated flue gas duct. The organic radicals, generated through the ethanol oxidation by O3, can oxidize NO into NO2, and finally into important industrial raw, namely, nitrate organics or aqueous nitrate acids. The residual ethanol in the tail can be recycled. The CO3(2-), HCO3(-) and SO2 in the flue gas hardly exhibit any effect on the NOX removal. Compared to the conventional O3 oxidation method, the present method shows higher selective oxidation of NO, higher NO(X) removal and less O3 consumption as well as proves lower initial investment and operating costs with more compact equipment.

Abatement of SO2-NOx binary gas mixtures using a ferruginous active absorbent: Part I. Synergistic effects and mechanism.

A novel ferruginous active absorbent, prepared by fly ash, industrial lime and the additive Fe(VI), was introduced for synchronous abatement of binary mixtures of SO2-NOx from simulated coal-fired flue gas. The synergistic action of various factors on the absorption of SO2 and NOx was investigated. The results show that a strong synergistic effect exists between Fe(VI) dose and reaction temperature for the desulfurization. It was observed that in the denitration process, the synergy of Fe(VI) dose and Ca/(S+N) had the most significant impact on the removal of NO, followed by the synergy of Fe(VI) and reaction temperature, and then the synergy of reaction temperature and flue gas humidity. A scanning electron microscope (SEM) and an accessory X-ray energy spectrometer (EDS) were used to observe the surface characteristics of the raw and spent absorbent as well as fly ash. A reaction mechanism was proposed based on chemical analysis of sulfur and nitrogen species concentrations in the spent absorbent. The Gibbs free energy, equilibrium constants and partial pressures of the SO2-NOx binary system were determined by thermodynamics.

Charge-reversal polyamidoamine dendrimer for cascade nuclear drug delivery.

AIMS: Polyamidoamine (PAMAM) dendrimers with primary amine termini have been extensively explored as drug and gene carriers owing to their unique properties, but their amine-carried cationic charges cause nonspecific cellular uptakes, systemic toxicity and other severe problems in in vivo applications. METHOD: In this article, we report a charge-reversal approach that latently deactivates PAMAM's primary amines to negatively charged acid-labile amides in order to inhibit its nonspecific interaction with cells, but regenerates the active PAMAM once in acidic environments. RESULTS: A cascade cancer cell nuclear drug delivery was achieved using the latently amidized PAMAM as the carrier conjugated with folic acid as the targeting group and a DNA-toxin drug camptothecin. The conjugate had low nonspecific interactions with cells, but easily entered cancer cells overexpressing folate receptors via receptor-mediated endocytosis. Subsequently, the endocytosed conjugate was transferred to acidic lysosomes, wherein the active PAMAM carrier was regenerated, escaped from the lysosome and then entered the nucleus for drug release. CONCLUSION: This reversible deactivation/activation makes PAMAM dendrimers useful nanocarriers for in vivo cancer cell nuclear-targeted drug delivery.

Prodrugs forming high drug loading multifunctional nanocapsules for intracellular cancer drug delivery.

Anticancer drugs embedded in or conjugated with inert nanocarriers, referred to as nanomedicines, show many therapeutic advantages over free drugs, but the inert carrier materials are the major component (generally more than 90%) in nanomedicines, causing low drug loading contents and thus excessive uses of parenteral excipients. Herein, we demonstrate a new concept directly using drug molecules to fabricate nanocarriers in order to minimize use of inert materials, substantially increase the drug loading content, and suppress premature burst release. Taking advantage of the strong hydrophobicity of the anticancer drug camptothecin (CPT), one or two CPT molecule(s) were conjugated to a very short oligomer chain of ethylene glycol (OEG), forming amphiphilic phospholipid-mimicking prodrugs, OEG-CPT or OEG-DiCPT. The prodrugs formed stable liposome-like nanocapsules with a CPT loading content as high as 40 or 58 wt % with no burst release in aqueous solution. OEG-DiCPT released CPT once inside cells, which showed high in vitro and in vivo antitumor activity. Meanwhile, the resulting nanocapsules can be loaded with a water-soluble drug-doxorubicin salt (DOX.HCl)-with a high loading efficiency. The DOX.HCl-loaded nanocapsules simultaneously delivered two anticancer drugs, leading to a synergetic cytotoxicity to cancer cells. The concept directly using drugs as part of a carrier is applicable to fabricating other highly efficient nanocarriers with a substantially reduced use of inert carrier materials and increased drug loading content without premature burst release.

Chemical degradation of drinking water disinfection byproducts by millimeter-sized particles of iron-silicon and magnesium-aluminum alloys.

The candidature of Fe-Si and Mg-Al alloys at millimeter-scale particle sizes for chemical degradation of disinfection byproducts (DBPs) in drinking water systems was substantiated by their enhanced corrosion resistance and catalytic effect on the degradation. The Mg-Al particles supplied electrons for reductive degradation, and the Fe-Si particles acted as a catalyst and provided the sites for the reaction. The alloy particles are obtained by mechanical milling and stable under ambient conditions. The proposed method for chemical degradation of DBPs possesses the advantages of relatively constant degradation performance, long-term durability, no secondary contamination, and ease of handling, storage and maintenance in comparison with nanoparticle systems.

Facile synthesis of polyester dendrimers from sequential click coupling of asymmetrical monomers.

Polyester dendrimers are attractive for in vivo delivery of bioactive molecules due to their biodegradability, but their synthesis generally requires multistep reactions with intensive purifications. A highly efficient approach to the synthesis of dendrimers by simply "sticking" generation by generation together is achieved by combining kinetic or mechanistic chemoselectivity with click reactions between the monomers. In each generation, the targeted molecules are the major reaction product as detected by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The only separation needed is to remove the little unreacted monomer by simple precipitation or washing. This simple clicklike process without complicated purification is particularly suitable for the synthesis of custom-made polyester dendrimers.

An organic-reagent-free method for determination of chromium(VI) in steel alloys, sewage sludge and wastewater.

One of the active areas of green chemistry research and development is in the development of new analytical methods and techniques that reduce and eliminate the use and generation of hazardous substances. In this work, a rapid and organic-reagent-free method was developed for the determination of chromium(VI) by sequential injection analysis (SIA). The method was based on the detection of a blue unstable intermediate compound resulting from the reaction of Cr(VI) with hydrogen peroxide (H(2)O(2)) in acidic medium. H(2)O(2) and its reaction products were environmentally friendly, and chromogenic reagents and organic solvents were not used in the proposed method. Different SIA parameters have been optimized and used to obtain the analytical figures of merit. Under the optimum experimental conditions, the linear range for Cr(VI) was 0.5-100.0 microg mL(-1), and the detection limit was 0.16 microg mL(-1). The sample throughput was 80 h(-1), and the total volume of only 145 microL was consumed in each determination of Cr(VI). The method was applied for the determination of Cr(VI) in seven real samples, including alloy steel, sewage sludge and wastewater samples, and the results were compared with those obtained by atomic absorption spectrometry as well as with the certified value of Cr(VI) in standard reference material. Statistical analysis revealed that there was no significant difference at 95% confidence level.

Rapid decolorization of azo dye methyl orange in aqueous solution by nanoscale zerovalent iron particles.

Azo dyes are recalcitrant and refractory pollutants that constitute a significant burden on the environment. The report here is focused on the decolorization treatment of water soluble azo dye methyl orange (MO) by chemically synthesized nanoscale zerovalent iron (NZVI) particles. Experimental variables such as initial dye concentration, iron dosage, solution pH and temperature were studied systematically. Batch experiments suggest that the decolorization efficiency was enhanced with the increase of NZVI dosage and reaction temperature, but decreased with increasing initial dye concentration and initial solution pH. Further studies indicated that existence of inorganic salt (Na(2)SO(4)) could inhibit the decolorization of MO. Kinetic analyses based on the experimental data elucidated that the decolorization process followed a first order exponential decay kinetics model. The activation energy was determined to be 35.9 kJ/mol.

Production of a new wastewater treatment coagulant from fly ash with concomitant flue gas scrubbing.

The research focused on the production of a complex wastewater coagulant containing polymeric sulfates of aluminum and iron from fly ash. At the same time, SO(2) in the simulated flu gas was removed by absorption in a fly ash slurry and oxidized with sodium chlorate. Extraction efficiency of iron and aluminum oxides from fly ash was affected greatly by reaction temperature and time. The extraction efficiency increases as temperature increases. Removal efficiency of SO(2) was influenced by temperature, SO(2) feed concentration and feed gas dispersing method. The produced complex coagulant containing both polymeric ferric sulfate (PFS) and polymeric aluminum sulfate (PAS) was proven to be effective in removing total suspended solids (TSS) and turbidity in wastewater. The complex coagulant is more effective than conventional iron and aluminum sulfates in turbidity removal.

Breakthrough adsorption study of migratory nickel in fine-grained soil.

The present study was conducted to evaluate the breakthrough curve for nickel adsorption in fine-grained soil from a nearby ash pond site of a thermal power plant. Nickel was found to be the major polluting solute in the ash sluicing wastewater. The adsorption of nickel by vertical soil column batch test and horizontal migration test was carried out in the laboratory. Field investigation was conducted also, by installing test wells around the ash pond site. Experimental results showed a good adsorptive capacity of soil for nickel ions. The breakthrough curves showed a reasonable fitting with a one-dimensional mathematical model. The breakthrough curves yielded from field test results showed good agreement with a two-dimensional mathematical model.

Effect of competing solutes on arsenic(V) adsorption using iron and aluminum oxides.

The study focused on the effect of several typical competing solutes on removal of arsenic with Fe2O3 and Al2O3. The test results indicate that chloride, nitrate and sulfate did not have detectable effects, and that selenium(IV) (Se(IV)) and vanadium(V) (V(V)) showed slight effects on the adsorption of As(V) with Fe2O3. The results also showed that adsorption of As(V) on Al2O3 was not affected by chloride and nitrate anions, but slightly by Se(IV) and V(V) ions. Unlike the adsorption of As(V) with Fe2O3, that with Fe2O3 was affected by the presence of sulfate in water solutions. Both phosphate and silica have significant adverse effects on the adsorption of As(V) adsorption with Fe2O3 and Al2O3. Compared to the other tested anions, phosphate anion was found to be the most prominent solute affecting the As(V) adsorption with Fe2O3 and Al2O3. In general, Fe2O3 has a better performance than Al2O3 in removal of As(V) within a water environment where multi competing solutes are present.

Adsorbents for capturing mercury in coal-fired boiler flue gas.

This paper reviews recent advances in the research and development of sorbents used to capture mercury from coal-fired utility boiler flue gas. Mercury emissions are the source of serious health concerns. Worldwide mercury emissions from human activities are estimated to be 1000 to 6000 t/annum. Mercury emissions from coal-fired power plants are believed to be the largest source of anthropogenic mercury emissions. Mercury emissions from coal-fired utility boilers vary in total amount and speciation, depending on coal types, boiler operating conditions, and configurations of air pollution control devices (APCDs). The APCDs, such as fabric filter (FF) bag house, electrostatic precipitator (ESP), and wet flue gas desulfurization (FGD), can remove some particulate-bound and oxidized forms of mercury. Elemental mercury often escapes from these devices. Activated carbon injection upstream of a particulate control device has been shown to have the best potential to remove both elemental and oxidized mercury from the flue gas. For this paper, NORIT FGD activated carbon was extensively studied for its mercury adsorption behavior. Results from bench-, pilot- and field-scale studies, mercury adsorption by coal chars, and a case of lignite-burned mercury control were reviewed. Studies of brominated carbon, sulfur-impregnated carbon and chloride-impregnated carbon were also reviewed. Carbon substitutes, such as calcium sorbents, petroleum coke, zeolites and fly ash were analyzed for their mercury-adsorption performance. At this time, brominated activated carbon appears to be the best-performing mercury sorbent. A non-injection regenerable sorbent technology is briefly introduced herein, and the issue of mercury leachability is briefly covered. Future research directions are suggested.