Selective sulfur conversion with surface engineering of electrocatalysts in a lithium-sulfur battery

The sluggish kinetics of multiphase sulfur conversion with homogeneous and heterogeneous electrochemical processes,causing the“shuttle effect”of soluble polysulfide species(PSs),is the challenges in terms of lithium-sulfur batteries(LSBs).In this paper,a Mn_(3)O_(4-x) catalyst,which has much higher activity for heterogeneous reactions than for homogeneous reactions(namely,preferentialactivity catalysts),is designed by surface engineering with rational oxygen vacancies.Due to the rational design of the electronic structure,the Mn_(3)O_(4-x) catalyst prefers to accelerate the conversion of Li2S4 into Li_(2)S_(2)/Li_(2)S and optimize Li_(2)S deposition,reducing the accumulation of PSs and thus suppressing the“shuttle effect.”Both density functional theory calculations and in situ X-ray diffraction measurements are used to probe the catalytic mechanism and identify the reaction intermediates of MnS and Li_(y)Mn_(z)O_(4-x) for fundamental understanding.The cell with Mn_(3)O_(4-x) delivers an ultralow attenuation rate of 0.028% per cycle over 2000 cycles at 2.5 C.Even with sulfur loadings of 4.93 and 7.10mg cm^(-2) in a lean electrolyte(8.4μL mg s^(-1)),the cell still shows an initial areal capacity of 7.3mAh cm^(-2).This study may provide a new way to develop preferential-activity heterogeneous-reaction catalysts to suppress the“shuttle effect”of the soluble PSs generated during the redox process of LSBs.

Fe_3O_4@UiO-66-NH_2 core–shell nanohybrid as stable heterogeneous catalyst for Knoevenagel condensation

separation is an attractive alternative to filtration or centrifugation for separating solid catalysts from a liquid phase, Here, core-shell Fe3O4@UiO-66-NH2 nanohybrids with well-defined structures were constructed by dispersing magnets in a dimethylformamide （DMF） solution con- taining two metal-organic framework （MOF） precursors, namely ZrCI4 and 2-aminobenzenetricar- boxylic acid. This method is simpler and more efficient than previously reported step-by-step method in which magnets were consecutively dispersed in DMF solutions each containing one MOF precursor, and the obtained Fe304@UiO-66-NH2 with three assembly cycles has a higher degree of crystallinity and porosiW. The core-shell Fe3O4@UiO-66-NH2 is highly active and selective in Knoevenagel condensations because of the bifunctionality of UiO-66-NH2 and better mass transfer in the nano-sized shells. It also has good recycling stability, and can be recovered magnetically and reused at least four times without significant loss of catalytic activity and framework integrity. The effects of substitution on the reactivity of benzaldehyde and of substrate size were also investigated.

Enhanced production of glycyrrhetic acid 3-O-mono-β-D-glucuronide by fed-batch fermentation using p H and dissolved oxygen as feedback parameters

Glycyrrhetic acid 3-O-mono-β-D-glucuronide （GAMG）, the major functional ingredient in licorice, has widespread applications in food, pharmacy and cosmetics industry. The production of GAMG through Penicillium purpurogenum Li-3 cultivation was for the first time performed through both batch and fed-batch processes in bioreactors. In batch process, under optimal conditions （pH 5.0, temperature 32℃, agitation speed 100 r. rain 1）, 3.55 g. L^-1 GAMG was obtained in a 2.5 L fermentor. To further enhance GAMG production, a fine fed-batch process was developed by using pH and DO as feedback parameters. Starting from 48 h, 100 m190 g-L 1 substrate Glycyrrhizin （GL） was fed each time when pH increased to above 5.0 and DO was increased to above 80%. This strategy can significantly enhance GAMG production： the achieved GL conversion was 95.34% with GAMG yield of 95.15%, and GAMG concentration was 16.62 g. L^-1 which was 5 times higher than that of batch. Then, a two-step separation strat- egy was established to separate GAMG from fermentation broth by crude extraction of 15 ml column packed with D10I resin followed by fine purification with preparative C18 chromatography. The obtained GAMG purity was 95.79%. This study provides a new insight into the industrial bioprocess of high-level GAMG production.

γ-Fe_2O_3:A magnetic separable catalyst for synthesis of 5-substituted 1H-tetrazoles from nitriles and sodium azide

An efficient route for the synthesis of 5-substituted 1H-tetrazole via[2＋3]cycloaddition of nitriles and sodium azide is reported usingγ-Fe2O3 nanoparticles as a magnetic separable catalyst.Under optimized conditions,the moderate to good yields（71-95%） can be obtained.The catalyst can be easily separated by a magnet and reused for several circles.

Surface magnetization of siderite mineral

Surface self-magnetization of siderite is achieved by generating ferromagnetic substance on the surface of siderite by adjusting slurry temperature,pH value,stirring rate and reaction time.No addition of any iron-containing reagent is required.The temperature of 60 ℃,NaOH concentration of 0.10 mol/L;stirring rate of 900 r/min and the reaction time of 10 min are the optimal conditions.The results show that the siderite recovery in magnetic separation increased from 26.9% to 88.8% after surface magnetization.Magnetization kinetic equation is expressed as 1 [1(e0.269)]1/3 = Kt.Activation energy for the magnetization reaction is 4.30 kJ/mol.VSM,SEM and XPS were used to characterize the siderite,and results show that the saturated magnetization(rs) of siderite increased from 0.652 to 2.569Am2 /kg,the magnetic hysteresis was detected with a coercive force of 0.976 A/m after magnetization;Fe2P3/2 electron binding energy changed which reflects the valence alteration in iron on the surface and the formation of ferromagnetic Fe3O4.

Mixed-conducting ceramic–carbonate membranes exhibiting high CO2/O2 permeation flux and stability at high temperatures

This investigation demonstrates the feasibility to fabricate high quality ceramic–carbonate membranes based on mixed-conducting ceramics.Specifically,it is reported the simultaneous CO2/O2 permeation and stability properties of membranes constituted by a combination of ceramic and carbonate phases,wherein the microstructure of the ceramic part is composed,in turn,of a mixture of fluorite and perovskite phases.These ceramics showed ionic and electronic conduction,and at the operation temperature,the carbonate phase of the membranes is in liquid state,which allows the transport of CO32-and O2–species via different mechanisms.To fabricate the membranes,the ceramic powders were uniaxially pressed in a disk shape.Then,an incipient sintering treatment was carried out in such a way that a highly porous ceramic was obtained.Afterwards,the piece is densified by the infiltration of molten carbonate.Characterization of the membranes was accomplished by SEM,XRD,and gas permeation techniques among others.Thermal and chemical stability under an atmosphere rich in CO2 was evaluated.CO2/O2 permeation and long-term stability measurements were conducted between 850 and 940℃.The best permeation–separation performance of membranes of about 1 mm thickness,showed a maximum permeance flux of about 4.46×10^–7 mol·m^–2·s^–1·Pa^–1 for CO2 and 2.18×10^–7 mol·m^–2·s^–1·Pa^–1 for O2 at 940℃.Membranes exhibited separation factor values of 150–991 and 49–511 for CO2/N2 and O2/N2 respectively in the studied temperature range.Despite long-term stability test showed certain microstructural changes in the membranes,no significant detriment on the permeation properties was observed along 100 h of continuous operation.

Greenhouse gas emissions from different pig manure management techniques： a critical analysis

Manure management is the primary source of greenhouse gas （GHG） emissions from pig farming, which in turn accounts for 18% of the total global GHG emissions from the livestock industry. In this review, GHG emissions （N20 and CH4 emissions in particular） from individual pig manure （PGM） management practices （European practises in particular） are systematically analyzed and discussed. These manure management practices include manure storage, land application, solid/liquid separation, anaerobic digestion, composting and aerobic wastewater treatment. The potential reduction in net GHG emissions by changing and optimising these techniques is assessed. This review also identifies key research gaps in the literature including the effect of straw covering of liquid PGM storages, the effect of solid/liquid separation, and the effect of dry anaerobic digestion on net GHG emissions from PGM management. In addition to identifying these research gaps, several recommendations including the need to standardize units used to report GHG emissions, to account ~br indirect N20 emissions, and to include a broader research scope by conducting detailed life cycle assessment are also discussed. Overall, anaerobic digestion and compositing to liquid and solid fractions are best PGM management practices with respect to their high GHG mitigation potential.

Synergistic impacts of anthropogenic and biogenic emissions on summer surface O_3 in East Asia

A factor separation technique and an improved regional air quality model （RAQM） were applied to calculate synergistic contributions of anthropogenic volatile organic compounds （AVOCs）,biogenic volatile organic compounds （BVOCs） and nitrogen oxides （NOx） to daily maximum surface O3（O3DM） concentrations in East Asia in summer （June to August 2000）.The summer averaged synergistic impacts of AVOCs and NOx are dominant in most areas of North China,with a maximum of 60 ppbv,while those of BVOCs and NOx are notable only in some limited areas with high BVOC emissions in South China,with a maximum of 25 ppbv.This result implies that BVOCs contribute much less to summer averaged O3DM concentrations than AVOCs in most areas of East Asia at a coarse spatial resolution （1×1） although global emissions of BVOCs are much greater than those of AVOCs.Daily maximum total contributions of BVOCs can approach 20 ppbv in North China,but they can reach 40 ppbv in South China,approaching or exceeding those in some developed countries in Europe and North America.BVOC emissions in such special areas should be considered when O3 control measures are taken.Synergistic contributions among AVOCs,BVOCs and NOx significantly enhance O3 concentrations in the Beijing-Tianjin-Tangshan region and decrease them in some areas in South China.Thus,the total contributions of BVOCs to O3DM vary significantly from day to day and from location to location.This result suggests that O3 control measures obtained from episodic studies could be limited for long-term applications.

Covering α-Fe2O3 protection layer on the surface of p-Si micropillar array for enhanced photoelectrochemical performance

The spontaneous oxidation process of pristine silicon （Si） limits its application as photocatalyst or electrode in aqueous solution or moist air. Covering a protection layer on Si surface is an effective approach to overcome this disadvantage. In this paper, α-Fe2O3 is demonstrated to be an excellent alternative as a protection material, α-Fe2O3 layer was deposited around each p-type Si micropillar （SiMP） in well-ordered array by chemical bath ＂deposition ＂method. The diameter of SiMP was 3 μm and the thickness of α-Fe2O3 layer was about 20 nm. The photoeletrochemical stability of SiMP/α-Fe2O3 was proved by 10 circles cyclic voltammetr7 testing. Compared with SiMP, its optical absorption and photocurrent density improved 2 times and 4 times, respectively, and its onset potential for hydrogen evolution moved positively about 0.4 V. These improved performances could be ascribed to the enhanced photogenemted-charge-separation efficiency deriving from built-in electric field at the interface between Si and α-Fe2O3. The above results show an effective strategy to utilize Si material as photocatalyst or electrode in aqueous solution or moist air.

Synthesis of novel magnetic sulfur-doped Fe_3O_4 nanoparticles for efficient removal of Pb(Ⅱ)

In this work, we report the synthesis of magnetic sulfur-doped Fe_3O_4 nanoparticles (Fe_3O_4:S NPs) with a novel simple strategy,which includes low temperature multicomponent mixing and high temperature sintering. The prepared Fe_3O_4:S NPs exhibit a much better adsorption performance towards Pb(Ⅱ) than bare Fe_3O_4 nanoparticles. FTIR, XPS, and XRD analyses suggested that the removal mechanisms of Pb(Ⅱ) by Fe_3O_4:S NPs were associated with the process of precipitation (formation of PbS), hydrolysis,and surface adsorption. The kinetic studies showed that the adsorption data were described well by a pseudo second-order kinetic model, and the adsorption isotherms could be presented by Freundlich isotherm model. Moreover, the adsorption was not significantly affected by the coexisting ions, and the adsorbent could be easily separated from water by an external magnetic field after Pb(Ⅱ) adsorption. Thus, Fe_3O_4:S NPs are supposed to be a good adsorbents for Pb(Ⅱ) ions in environmental remediation.