Tailoring the Electronic Metal-Support Interactions in Supported Silver Catalysts through Al modification for Efficient Ethylene Epoxidation.

Metal-modified catalysts have attracted extraordinary research attention in heterogeneous catalysis due to their enhanced geometric and electronic structures and outstanding catalytic performances. Silver (Ag) possesses necessary active sites for ethylene epoxidation, but the catalyst activity is usually sacrificed to obtain high selectivity towards ethylene oxide (EO). Herein, we report that using Al can help in tailoring the unoccupied 3d state of Ag on the MnO2 support through strong electronic metal-support interactions (EMSIs), overcoming the activity-selectivity trade-off for ethylene epoxidation and resulting in a very high ethylene conversion rate (~100 %) with 90 % selectivity for EO under mild conditions (170 °C and atmospheric pressure). Structural characterization and theoretical calculations revealed that the EMSIs obtained by the Al modification tailor the unoccupied 3d state of Ag, modulating the adsorption of ethylene (C2H4) and oxygen (O2) and facilitating EO desorption, resulting in high C2H4 conversion. Meanwhile, the increased number of positively charge Ag+ lowers the energy barrier for C2H4(ads) oxidation to produce oxametallacycle (OMC), inducing the unexpectedly high EO selectivity. Such an extraordinary electronic promotion provides new promising pathways for designing advanced metal catalysts with high activity and selectivity in selective oxidation reactions.

Volatile organic compounds (VOCs) emissions from internal floating-roof tank in oil depots in Beijing: Influencing factors and emission reduction strategies analysis.

The internal floating-roof tank is the main type of storage tank for refined oil products. The volatile organic compounds (VOCs) emission from the internal floating-roof tank plays a dominant role in the unorganized emission source of the oil depot. In this study, we selected six typical oil depots in Beijing to investigate VOC emission characteristics from the tank top vent hole using infrared imaging technology and flame ionization detector (FID). The results reveal that infrared thermal imager is efficient in quickly identifying the emission level of the tank discharge point. The ambient temperature and wind speed have a direct effect on sealing loss, the turnover can greatly influence the wall hanging loss, and the concentration of VOCs emitted from the tank top vent hole is negatively correlated with liquid height. Furthermore, the influence of accessories type of the internal floating-roof tank on the concentration of VOCs emission from the top vent hole is also studied when other parameters remain unchanged, and find the floating deck type and sealing mode have a significant influence on their VOCs emissions, of which the combination of pontoon type floating deck and secondary seal are effective in controlling the concentration of VOCs emitted from the tank top vent hole. Finally, based on our experimental results, several feasible emission reduction strategies are proposed in terms of source prevention and process control in order to achieve the fine management of the whole process. This paper provides important technical support and policy thoughts for VOCs emission control during oil storage.

Insight into the crucial reason causing the difference in secondary organic aerosol yields of monocyclic aromatic hydrocarbons with different methyl substituent numbers.

The secondary organic aerosol (SOA) yield of toluene photooxidation was reported to substantially higher than that of trimethylbenzene due to the effect of the number of methyl substituents. However, the intrinsic mechanism for this disparity is not clear enough. In this study, a highly-sensitive thermal-desorption photoinduced associative ionization mass spectrometer (TD-PAI-MS) was used to real-time characterize the molecular composition and its evolution of the SOA generated from the photooxidation of toluene and 1,2,3-trimethylbenzene (1,2,3-TMB) in a smog chamber. In the new particle formation (NPF) stage, toluene generated more variety of nucleation precursors, such as benzaldehyde (MW 106) and benzoic acid (MW 122), resulting in a much higher nucleation rate and SOA number concentration. In the SOA growth/aging stage, the key SOA components of toluene were mainly dialdehydes, e.g., 2-oxopropanedial (MW 86) and 4-oxopent-2-enedial (MW 112), which played an important role in the formation of highly oxidized species (HOS) through oligomerization or cyclization reactions. In contrast, due to the presence of more methyl groups, 1,2,3-TMB was inclined to produce ketones, e.g., 2,3-butanedione (MW 86) and 3-methyl-4-oxopent-2-enal (MW 112), which would be cleaved into high-volatility low molecular compounds, e.g., acetic acid, through fragmentation. Taken together, relative to 1,2,3-TMB, the higher nucleation rate during NPF and the significant oligomerization/functionalization process during SOA growth are thought to be the major reasons resulting in the higher SOA yield of toluene. This work provides a reference for the insight into the different SOA yields of monocyclic aromatic hydrocarbons (MAHs) through further revealing the SOA formation mechanism during toluene and 1,2,3-TMB photooxidation.

Simultaneously Constructing Active Sites and Regulating Mn-O Strength of Ru-Substituted Perovskite for Efficient Oxidation and Hydrolysis Oxidation of Chlorobenzene.

Chlorinated volatile organic compounds (CVOCs) are a class of hazardous pollutants that severely threaten environmental safety and human health. Although the catalytic oxidation technique for CVOCs elimination is effective, enhancing the catalytic efficiency and simultaneously inhibiting the production of organic byproducts is still of great challenge. Herein, Ru-substituted LaMn(Ru)O3+ δ perovskite with Ru-O-Mn structure and weakened Mn-O bond strength has been developed for catalytic oxidation of chlorobenzene (CB). The formed Ru-O-Mn structure serves as favorable sites for CB adsorption and activation, while the weakening of Mn-O bond strength facilitates the formation of active oxygen species and improves oxygen mobility and catalyst reducibility. Therefore, LaMn(Ru)O3+ δ exhibits superior low-temperature activity with the temperature of 90% CB conversion decreasing by over 90 °C compared with pristine perovskite, and the deep oxidation of chlorinated byproducts produced in low temperature is also accelerated. Furthermore, the introduction of water vapor into reaction system triggers the process of hydrolysis oxidation that promotes CB destruction and inhibits the generation of chlorinated byproducts, due to the higher-activity *OOH species generated from the dissociated H2 O reacting with adsorbed oxygen. This work can provide a unique, high-efficiency, and facile strategy for CVOCs degradation and environmental improvement.

A review of whole-process control of industrial volatile organic compounds in China.

Volatile organic compounds (VOCs) play an important role in the formation of ground-level ozone and secondary organic aerosol (SOA), and they have been key issues in current air pollution prevention and control in China. Considerable attention has been paid to industrial activities due to their large and relatively complex VOCs emissions. The present research aims to provide a comprehensive review on whole-process control of industrial VOCs, which mainly includes source reduction, collection enhancement and end-pipe treatments. Lower VOCs materials including water-borne ones are the keys to source substitution in industries related to coating and solvent usage, leak detection and repair (LDAR) should be regarded as an efficient means of source reduction in refining, petrochemical and other chemical industries. Several types of VOCs collection methods such as gas-collecting hoods, airtight partitions and others are discussed, and airtight collection at negative pressure yields the best collection efficiency. Current end-pipe treatments like UV oxidation, low-temperature plasma, activated carbon adsorption, combustion, biodegradation, and adsorption-combustion are discussed in detail. Finally, several recommendations are made for future advanced treatment and policy development in industrial VOCs emission control.

Adsorption and membrane separation for removal and recovery of volatile organic compounds.

Volatile organic compounds (VOCs) are a crucial kind of pollutants in the environment due to their obvious features of severe toxicity, high volatility, and poor degradability. It is particularly urgent to control the emission of VOCs due to the persistent increase of concentration and the stringent regulations. In China, clear directions and requirements for reduction of VOCs have been given in the "national plan on environmental improvement for the 13th Five-Year Plan period". Therefore, the development of efficient technologies for removal and recovery of VOCs is of great significance. Recovery technologies are favored by researchers due to their advantages in both recycling VOCs and reducing carbon emissions. Among them, adsorption and membrane separation processes have been extensively studied due to their remarkable industrial prospects. This overview was to provide an up-to-date progress of adsorption and membrane separation for removal and recovery of VOCs. Firstly, adsorption and membrane separation were found to be the research hotspots through bibliometric analysis. Then, a comprehensive understanding of their mechanisms, factors, and current application statuses was discussed. Finally, the challenges and perspectives in this emerging field were briefly highlighted.

Emission characteristics, risk assessment and scale effective control of VOCs from automobile repair industry in Beijing.

Automobile repair is regarded as a typical domestic source of VOCs in China characterized by numerous sites, wide dispersion and intermittent VOCs emissions. It is of great importance to study and control VOCs from such activities. In this research, emission characteristics, risk assessment and scale effective control of VOCs from automobile repair in Beijing were studied. Results showed that coating spraying and baking were the main processes of VOCs and the major species determined were mostly oxygen-containing VOCs and aromatic hydrocarbons in the case of solvent-based coating usage. Meanwhile, alkanes were determined and accounted for 40 % of total VOCs emissions during the water-based coating spraying and baking. Generally, the total determined VOCs during the automobile repair processes were 1.06-1.27 mg/m3 and 2.93-53.46 mg/m3 for the usage of water-based and solvent-based paint, respectively. Health risk assessments indicated that the residents in the region about 30 m high within a radius of 20 m around the automobile repair plants might suffer from both serious non-carcinogenic and carcinogenic risk threats in the case of solvent-based coating usage in that the values of total hazard index (HI) represented by dichloropropane and acrolein were higher than 1 and the value of lifetime cancer risk (LCR) represented by dichloroethane was higher than 10-5. Besides, those in the region about 30 m high and within a wider radius of 340 m might suffer from carcinogenic risk threat with a certain probability (LCR > 10-6) no matter either solvent-based or water-based coatings were used. As for the scale control of VOCs from automobile repair, independent adsorption by activated carbon combined with mobile regeneration by catalytic combustion was also proposed as an efficient way.

Visible Light Accelerates Cr(III) Release and Oxidation in Cr-Fe Chromite Residues: An Overlooked Risk of Cr(VI) Reoccurrence.

The reduced chromite ore processing residue (rCOPR) deposited in environments is susceptible to surrounding factors and causes reoccurrence of Cr(VI). However, the impact of natural sunlight on the stability of rCOPR is still unexplored. Herein, we investigated the dissolution and transformation behaviors of Cr(III)-Fe(III) hydroxide, a typical Cr(III)-containing component in rCOPR, under visible light. At acidic conditions, the release rate of Cr(III) under illumination markedly increased, up to 7 times higher than that in the dark, yet no Cr(VI) was produced. While at basic conditions, only Cr(VI) was obtained by photo-oxidation, with an oxidation rate of ∼7 times higher than that by δ-MnO2 under dark conditions at pH 10, but no reactive oxygen species was generated. X-ray absorption near-edge structure and density functional theory analyses reveal that coexisting Fe in the solid plays a critical role in the pH-dependent release and transformation of Cr(III), where photogenerated Fe(II) accelerates Cr(III) produced at acidic conditions. Meanwhile, at basic conditions, the production of intermediate Cr(III)-Fe(III) clusters by light leads to the oxidation of Cr(III) into Cr(VI) through the nonradical "metal-to-metal charge transfer" mechanism. Our study provides a new insight into Cr(VI) reoccurrence in rCOPR and helps in predicting its environmental risk in nature.

Hierarchical Core-Shell Co2 N/CoP Embedded in N, P-doped Carbon Nanotubes as Efficient Oxygen Reduction Reaction Catalysts for Zn-air Batteries.

Projecting a cost-effective and highly efficient electrocatalyst for the oxygen reaction reduction (ORR) counts a great deal for Zn-air batteries. Herein, a hierarchical core-shell ORR catalyst (Co2 N/CoP@PNCNTs) is developed by embedding cobalt phosphides and/or cobalt nitrides as the core into N, P-doped carbon nanotubes (PNCNTs) as the shell via one-step carbonization, nitridation, and phosphorization of pyrolyzing Co-MOF precursor. The globally N, P-doped structure of Co2 N/CoP@PNCNTs demonstrates an outstanding electrocatalytic activity in the alkaline solution with the onset and half-wave potentials of 1.07 and 0.85 V respectively. Moreover, a Zn-air battery assembled from Co2 N/CoP@PNCNTs as the air cathode delivers an open circuit potential of 1.49 V, a maximum power density of 151.1 mW cm-2 and a specific capacity of 823.8 mAh kg-1 . It is reflected that Co2 N/CoP@PNCNTs provides a long-term durability with a slight decline of 15 h in the chronoamperometry measurement and an excellent charge-discharge stability with negligible voltage decay for 150 h at 10 mA cm-2 in Zn-air batteries. The results reveal that Co2 N/CoP@PNCNTs has superiority over most Co-Nx -C or Cox P@C catalysts reported so far. The excellent catalytic properties and stability of Co2 N/CoP@PNCNTs derive from synergistic effects between Co2 N/CoP and mesoporous N, P-doped carbon nanotubes.

Study of heterogeneous reaction of dimethyl sulfide on atmospheric-like particulate TiO2.

Dimethyl sulfide (DMS) related to solar radiation and greenhouse effect is one of the most important volatile sulfides and its' oxidation products are also important contributors to acid rain. It is of great importance to study the consumption and reactions of DMS in the atmosphere. In this work, atmospheric-like particulate TiO2 was selected to study the reaction mechanism of DMS on TiO2 with the purpose to explore the possible heterogeneous oxidation of DMS. The results showed that the heterogeneous reaction of DMS with TiO2 occurred under the condition of illumination, which is a first-order-like reaction with the rate constant K = 2.83 × 10-4/s, the initial reaction uptake coefficient and the steady reaction uptake coefficient indicated the occupation of products and by-products on the surface of TiO2. The heterogeneous reaction mechanism of DMS studied by aerosol time-of-flight mass spectrometry (ATOFMS) suggested that DMS underwent a series of complex chemical reactions with sulfate and various sulfur-containing gas products, in which hydroxyl radicals might play an important role.

Unraveling the adsorption and diffusion properties of hexamethyldisiloxane on zeolites by static gravimetric analysis.

Utilization of biogas from wastewater treatment plants (WWTPs) as a kind of renewable energy can effectively alleviate the escalating energy crisis. However, volatile methylsiloxanes (VMS) exist in biogas as impurities and hinder its efficient use. Adsorption is the main technology to achieve high-efficiency purification of VMS currently, yet studies on the adsorption processes and mechanisms are quite insufficient. Here, we use the static vapor adsorption method to investigate the adsorption performances and mechanisms of four typical zeolite adsorbents (Hbeta, SBA-15, MOR and MCM-41) towards hexamethyldisiloxane (L2), which is a representative of VMS. Results suggest the adsorption interaction of L2 and zeolite is closely related to the pore size of zeolite and follows the order of Hbeta > MCM-41 > SBA-15 > MOR. The adsorption rate constants of L2 on MCM-41 are larger than the others in the most relative pressure ranges. Besides, cyclic adsorption/desorption performances of L2 on MCM-41, SBA-15 and Hbeta show their super recycling properties. These studies would provide important information on designing an effective zeolite-L2 adsorption system, and are helpful to understand the deeper adsorption mechanisms of VMS on zeolites.

Effects of mesoporous silica particle size and pore structure on the performance of polymer-mesoporous silica mixed matrix membranes.

The fabrication of mixed matrix membranes (MMMs) has been regarded as an effective and economic approach to enhance the gas permeability and selectivity properties of conventional polymeric membranes for gas separation applications. However, the poor compatibility between polymeric matrix and inorganic filler in MMMs could lead to the generation of interfacial defects resulting in reduced gas selectivity. In this work, with the aim of studying the effect of particle size and pore structure of the filler on the performance of the resultant MMMs, nano/micro sized spherical mesoporous silicas with 2D/3D pore structure (MCM-41 and MCM-48) were synthesized and selected as fillers for the preparation of polydimethylsiloxane (PDMS)-based MMMs. The separation properties of the membranes prepared were characterized by permeability measurements for nitrogen and organic vapors (C3H6 and n-C4H10). Compared with microsized particles, nanosized fillers have better dispersion in the polymer matrix which could minimize the formation of non-selective microvoids around the particles, leading to higher vapor/N2 ideal selectivities of the MMMs, even at the high loading (15 wt%). Moreover, due to the conventional random packing orientation of the particles in the polymer, vapor permeation was severely hindered in the MMMs fabricated from mesoporous silica with 2D pore channels. The interface morphologies and gas diffusion paths in the MMMs have also been proposed. With an optimum loading of nanosized MCM-48 (3D pore structure), the vapor permeabilities and vapor/N2 ideal selectivities of the MMMs were shown to increase simultaneously, compared with the neat polymer membrane.

Influence of oxygen and water content on the formation of polychlorinated organic by-products from catalytic degradation of 1,2-dichlorobenzene over a Pd/ZSM-5 catalyst.

Understanding the generation and influence mechanism of polychlorinated organic by-products during the catalytic degradation of chlorinated volatile organic compounds (CVOCs) is essential to the safe and environmentally friendly treatment of those pollutants. In this study, a systematic investigation of the catalytic oxidation of 1,2-dichlorobenzene (1,2-DCB) was conducted using various oxygen and water contents over a Pd/ZSM-5(25) catalyst. It was found that decreasing the oxygen content and increasing the water content resulted in the improvement of the 1,2-DCB catalytic activity, while the amount and variety of polychlorinated organic by-products decreased. More importantly, when water was the sole oxidant, the Pd/ZSM-5(25) catalyst also demonstrated high activity towards 1,2-DCB catalytic degradation. Only chlorobenzene and 1,3-dichlorobenzene were detected as by-products. X-ray photoelectron spectra (XPS) and UV-vis DRS spectra results indicated that the polychlorinated organic by-products were suppressed mainly due to inhibition of the chlorination of the palladium species by regulating the oxygen and water content in the reaction atmosphere. Similar surface species were formed under aerobic and anaerobic atmospheres via the study of the in situ FTIR spectra. We therefore proposed that 1,2-DCB undergoes similar catalytic degradation reaction mechanisms under both aerobic and anaerobic conditions.

Study on emissions of volatile organic compounds from a typical coking chemical plant in China.

Coking chemical industry associated with high energy consumption and high pollution emits significant amount of volatile organic compounds (VOCs) to atmosphere, but is often ignored. This article reports a new study on emissions of VOCs from a typical coking chemical plant. Results show that about 70 species of VOCs including alkanes, alkenes, alkynes, aromatic hydrocarbons, halogenated hydrocarbons and oxygenates are detected, naphthalene and benzene could be used as the emission markers. Compared to coking stage, gas purifying stage is found to have 4 times more total concentrations of VOCs, in which condensing and blasting process is found to be the largest contributor with 77% ozone formation potential (OFP) contribution. Emission control measures currently used are insufficient and inefficient to reduce VOCs to meet regulatory emission standards. Further, by using a proposed integrated emission factor of 2.652 g/kg coke, the coking chemical industry in China was estimated to account for about 7.8-20% of total historical industrial VOCs emissions, and about 1241 Gg of VOCs were emitted in 2019. A large proportion is emitted from the northern China with a distinctive spatial distribution. Shanxi, Hebei, Shandong, and Shannxi provinces are the top four emitters. It is suggested that more stringent and efficient measures should be taken on the coking chemical industry, not just on the coking processes, but also on the gas purifying processes.

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine.

In this work, a series of Cu-ZSM-5 catalysts with different SiO2/Al2O3 ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N2, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N2 selectivity was impacted by the Brønsted acidity and the isolated Cu2+ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.

Gaseous adsorption of hexamethyldisiloxane on carbons: Isotherms, isosteric heats and kinetics.

Volatile methylsiloxanes (VMS) are a special kind of impurity that exist in biogas and seriously hamper its utilization; therefore, their removal has attracted great attention in recent years. Adsorption is the only technology that is currently capable of industrial-scale removal of VMS. In this research, three carbons with various porous structures, including ordered mesoporous carbon (OMC), activated carbon fiber (ACF) and granular activated carbon (GAC), were selected as potential adsorbents to investigate their adsorption properties toward hexamethyldisiloxane (L2), which is a typical linear VMS pollutant. The adsorption isotherms and kinetics of L2 on the three carbons were studied, and the isosteric heats of adsorption were calculated in accordance with the isotherms under different temperatures by using the Van't Hoff equation. Additionally, the influences of the topological structures of the carbons on the adsorption kinetics were compared. Generally, adsorption isotherms of the three carbons can be well-fitted by the Dubinin-Astakhov equation, and the variation of the isosteric heats and adsorption kinetics are presumed to be closely related to the pore sizes of the carbons. These new findings reveal the adsorption mechanisms of L2 on carbons and make it possible that the proper adsorption system is set up to fulfill higher removal efficiency.

Insight into structure defects and catalytic mechanism for NO oxidation over Ce0.6Mn0.4Ox solid solutions catalysts: Effect of manganese precursors.

The effects of Mn precursors on structure defects and NO catalytic mechanism over Ce0·6Mn0.4Ox catalysts were fully investigated. The Ce0·6Mn0.4Ox-Ac catalyst, synthesized by using MnAc2 as a Mn precursor, showed the best catalytic activity for NO conversion (86.9%) at 250 °C under high space velocity (40,000 mL g-1 h-1). Detailed structure-activity relationship reveals that the abundant oxygen vacancies and the highly migratory oxygen species formed on Ce0·6Mn0.4Ox are the crucial factors that leading to the better NO oxidation activity than that of the other Ce0·6Mn0.4Ox-Y (YNO3, SO4, Cl) catalysts. In situ DRIFTS technique confirms that the differences in formation mode and desorption ability of N-based (nitrates, nitrites, and dimer nitroso) intermediate species are the vital factors for NO high-efficiency catalytic oxidation. The highly reactive surface intermediate species, like monodentate nitrates, were observed particularly on Ce0·6Mn0.4Ox-Ac catalyst, so that the NO oxidation performance on Ce0·6Mn0.4Ox-Ac catalyst was more active comparing with other Ce0·6Mn0.4Ox-Y catalysts. This study can broaden the horizons for understanding NO catalytic oxidation mechanism on serial Ce0·6Mn0.4Ox catalysts and serve as a reference guide in design of structure defects for functional materials by modulating precursor species.

Interfacial Force-Assisted In-Situ Fabrication of Graphene Oxide Membrane for Desalination.

Graphene-based membranes have shown great potential application prospects in many fields, especially for water purification. Except for the current relatively low salt rejection rate, another main factor restricting application of such membranes is the lack of applicable preparation processes. In this work, a facile and cost-effective method was developed that can be used to in situ fabricate a graphene oxide (GO)-based membrane inside a filtration apparatus. Novel partial reduction and cross-linking was employed to adjust the surface properties and interlayer distance of GO membranes at the subnanometer range. A simple compacting process was applied to promote the integrity and compactness of the GO-based membranes by making full use of the interfacial tensions of gas/liquid/solid, which enables the in-situ fabrication. The as-prepared PrGO membranes show good water permeability (17.2-86.5 L m-2 h-1 MPa-1), reasonable desalination rates (27.7-62.6% for NaCl and 68.4-86.1% for Na2SO4), and good rejection rates of 92.3-96.8% for methyl orange. The method is appropriate for large-scale preparation and is theoretically not restricted by the shape or texture of the basement membrane, which represents another step forward in the fabrication of GO-based membranes toward wide-ranging applications.

Insight into mineralizer modified and tailored scorodite crystal characteristics and leachability for arsenic-rich smelter wastewater stabilization.

Arsenic-rich non-ferrous smelter wastewater has the potential to cause harm to the environment and human health. The use of mineralizer modified and tailored scorodite crystals, a secondary As-bearing mineral, is considered to be the most promising strategy for arsenic stabilization. In this work, firstly, the mechanisms influencing the scorodite crystal characteristics for arsenic stabilization were investigated, and the results indicated that the scorodite stability was greatly influenced by the scorodite crystal shape and particle size. The crystal shape changes that the scorodite solids undergo during the aging period were observed, from a laminar structure to a polyhedron to a standard octahedral structure, and meanwhile, the As-concentration decreased from 10.2 mg L-1 to 3.7 mg L-1, with the relative particle size value (RPS) increasing from 1.50 to 2.64. Secondly, the addition of a mineralizer to further improve the scorodite crystal stability was investigated. It was meaningful to observe that the lowest As-concentration of 0.39 mg L-1 could be attained when trace NaF was employed, and it was of great significance to apply this strategy for the disposal of As and F-containing wastewater due to the electrostatic interaction between scorodite and sodium fluoride. However, the scorodite crystal stability was weakened when other mineralizers (Na2SiO3·9H2O and Al(NO3)3·9H2O) were added. This indicated that these mineralizers play different roles in influencing the crystal phase, shapes and sizes of the solid precipitate (mainly scorodite). Finally, the mechanisms of the scorodite crystal evolution and the arsenic leachability characteristics were analyzed. In conclusion, the addition of appropriate mineralizers is a potentially effective strategy for the control of crystal growth, and could be used in the disposal and stabilization of arsenic-rich non-ferrous effluents.

Hybrids of NiCo2O4 nanorods and nanobundles with graphene as promising electrode materials for supercapacitors.

High dispersion of NiCo2O4 nanorods and porous NiCo2O4 nanobundles decorated on RGO have been synthesized by a facile hydrothermal method, followed by calcination in one step. By adjusting the starting metal sources to realize the synthesis of different morphologies of NiCo2O4. The morphology and the microstructure of the as-prepared composites were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM) techniques. Among them, the porous RGO/NiCo2O4 nanobundles gives a higher specific capacitance of 1278F/g at 1A/g and 719F/g at 20A/g, showing a remarkable rate capability. The excellent electrochemical performances could ascribed to the unique structural feature with higher surface area. It could be anticipated that the synthesized electrode material will gain promising applications in supercapacitors and other devices because of their outstanding characteristics of controllable capacitance and facilely synthesized.