Oxidation Evolution and Activity Origin of N-Doped Carbon in the Oxygen Reduction Reaction

N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.

Synthesis of super high molecular weight copolymer of AM/NaA/AMPS by oxidation–reduction and controlled radical polymerization

Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.

Influences of Microbial Oxidation/Reduction on Mineral Transformation in Sulfide Tailings and Environmental Consequence in Shizishan Cu-Au Mine, Tongling, Eastern China

Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.

The Effect of Oxidation/Reduction Disposing on Optical Properties of Mg:Fe:Mn:LiNbO_3 Crystals

The congruent tri-doped Mg:Mn:Fe:LiNbO 3 crystal has been grown by Czochralski method. Some crystal samples are reduced in Li 2CO 3 powder at 500 ℃ for 24 hours or oxidized for 10 hours at 1100 ℃ in Nb 2O 5 powder. Compared with As-grown Mg:Mn:Fe:LiNbO 3, the absorption edge in UV-Vis. absorption spectrum of the oxidized sample and the reduced shifts to the violet and the red, respectively. Reduction increases the absorption of crystals in visible light region. In two-wave coupling experiments, the writing time, maximum diffraction efficiency and the erasure time of crystal samples in the same conditions are determined. The results indicate that oxidation and reduction disposing has great effect on the holographic recording properties of these crystals. The reduced crystal exhibits the fastest response time of 160 s among the crystal series. The mechanism of post-disposing effect on the holographic recording properties of Mg:Mn:Fe:LiNbO 3 crystals are investigated.

NO reduction by CO over TiO_2-γ-Al_2O_3 supported In/Ag catalyst under lean burn conditions

TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties of the catalysts were studied by N2 adsorption-desorption,X-ray diffraction,transmission electron microscopy,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy,H2 temperature-programmed reduction and Fourier transform infrared spectroscopy.TiO2/γ-Al2O3 supported In/Ag is a good catalyst for the reduction of NO to N2.It displayed high dispersion,large amounts of surface active components and high NO adsorption capacity,which gave good catalytic performance and stability for the reduction of NO with CO under lean burn conditions.The silver species stabilized and improved the dispersion of the indium species.The introduction of TiO2 into the γ-Al2O3 support promoted NO adsorption and improved the dispersion of the indium species and silver species.

Neutral and metallic vs.charged and semiconducting surface layer in acceptor doped CeO_(2)

The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.

Nitrous oxide emission and reduction in a laboratory-incubated paddy soil response to pretreatment of water regime

A laboratory incubation experiment was conducted to investigate nitrous oxide(N 2O) emission and reduction in a paddy soil(Stagnic Anthrosol) response to the pretreatment of water regime. The paddy soil was maintained under either air dried(sample D) or submerged(sample F) conditions for 110 d before the soil was adjusted into soil moisture of 20%, 40%, 60%, 80% and 100% water holding capacity(WHC) respectively, and then incubated with or without 10%(v/v) acetylene for 138 h at 25℃. At lower soil water content (≤60% WHC), N 2O emission from the sample F was 2 29 times higher than that from the sample D( P <0 01). While, N 2O emission from the sample F was only 29 and 14 percent of that from the sample D at the soil moisture of 80% and 100% WHC, respectively( P <0 01). The maximal N 2O emissions observed at soil moisture of 80% WHC were about 24 and 186 times higher than the minima obtained at the soil moisture of 20% WHC for the sample F and D, respectively. But at the soil moisture of 80% and 100% WHC, N 2O emission from the sample F with acetylene(F+ACE) was comparable to that of the sample D with acetylene (D+ACE). The results showed that the F sample produced N 2O ability in denitrification was similar to the sample D, however, the sample F was in the better reduction of N 2O to N 2 than the sample D even after the soil moisture was adjusted into the same level of 80% or 100% WHC. Therefore, the pretreatment of water regime influenced the strength and product composition of denitrification and N 2O emission from the paddy soil.

Recovery of Ferric Oxide from Bayer Red Mud by Reduction Roasting-Magnetic Separation Process

A great amount of red mud generated from alumina production by Bayer process was considered as a low-grade iron ore with a grade of 5wt% to 30wt% iron.We adopted the reduction roastingmagnetic separation process to recover ferric oxide from red mud.The red mud samples were processed by reduction roasting,grinding and magnetic separating respectively.The effects of different parameters on the recovery rate of iron were studied in detail.The optimum techqicalparameters were proposed with 700 ℃roasting for 20 min,as 50wt% carbon and 4wt% additive were added.The experimentalresults indicated that the iron recovery and the grade of totaliron were 91% and 60%,respectively.A novelprocess is applicable to recover ferric oxide from the red mud waste fines.

Hydrogen Reduction of Tungsten Oxides Part Ⅰ:Reduction of WO_(2.90),W_(20)O_(58) and WO_3

The hydrogen reduction of tungsten oxides WO_(2.90),W_(20)O_(58) and WO_3 were directly studied using high temperature X-ray diffraction analysis.The differences between tetragonal WO_(2.90) and monoclinic W_(20)O_(58) were discussed.Pure β-W was obtained from oxide WO_(2.90),while there appears small amount of WO_2 during the reduction of W_(20)O_(58) to β-W.

Hydrogen Reduction of Tungsten Oxides Part Ⅱ:Reduction of WO_(2.72) and WO_2,Transformation of β-W

The hydrogen reduction of tungsten oxides WO_(272)and WO_2 were studied directly using high-temperature X-ray diffraction analysis,The pure β-W was obtained from the reduction of WO_(272)The transformation of β-W to x-W was also studied in both hydrogen and nitrogen.The forming condition of β-W from WO_2 was discussed.Finally.a complete schematic diagram of reduction of tungsten oxides was given in this paper.

Nitric Oxide Reduction Performance of Automotive Palladium Catalysts

Activity of three-way palladium catalyst was examined by means of a pulse-flam-microreactor. The effects of cerium on the catalytic properties of gamma-alumina-supported palladium for the reduction of nitric oxide were studied with X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). The reduction of nitric oxide on palladium catalysts is inhibited significantly by hydrocarbon. However, the reduction of nitric oxide was improved by the addition of cerium to the catalysts. The XPS and TPR studies showed that the presence of cerium provided, palladium oxide in a hard-reduced state and suppressed the chemisorption of hydrocarbons on the palladium oxide. Additionally,cerium could increase surface specific oxygen storage capacity and decrease the apparent activation energy for the rea;ltion CO+NO-->CO2-+-1/2 N-2. So a high conversion of NOx reduction could shift to higher A/F ratio.

Near-infrared H_(2)O_(2)production via dual pathways of O_(2)reduction and H_(2)O oxidation

Hydrogen peroxide(H_(2)O_(2))is a chemical that is widely of interest in both environmental and energy fields.On the one hand,as a clean oxidant,H_(2)O_(2)has been commonly used in the field of bleaching,disinfection,and advanced oxidation processes.On the other hand,H_(2)O_(2)has also been explored as a liquid fuel alternative to H_(2)or fossil fuels in fuel cells due to its high energy density.However,the current industrial production of H_(2)O_(2)relies on the anthraquinone(AO)method that involves palladium-catalyzed hydrogenation-oxidation steps.

Indoor Simulation Study on Nutrient Release of Fishponds Sediment

[Objective] The study aimed to research the nutrients release of ponds sediment.[Method] The sediments which from a new pond(A) and an old one (B) these analyses used to carry out indoor experiment under the anaerobic dark condition for researching on nutrient release. The N(nitrogenous) and P(phosphorous) release were analyzed every two days.[Result] At the prophase, the N release in B was bigger than that in A, while the decline sediment release in A was gentle.[Conclusion] There was no accumulation of organic compound during the breeding time. The NH4-N was the main form of N release; and the P release was correlated with N release, while PO4-P was the main form of P release.

Dealloyed TiCuMn efficiently catalyze the NO reduction and Zn-NO batteries

Electrocatalytic NO reduction reaction offers a sustainable route to achieving environmental protection and NH3 production targets as well.In this work,a class of dealloyed Ti_(60)Cu_(33)Mn_(7)ribbons with enough nanoparticles for the high-efficient NO reduction reaction to NH_(3)is fabricated,reaching an excellent Faradaic efficiency of 93.2%at–0.5 V vs reversible hydrogen electrode and a high NH_(3) synthesis rate of 717.4μmol·h^(-1)·mg_(cat).^(-1) at–0.6 V vs reversible hydrogen electrode.The formed nanoparticles on the surface of the catalyst could facilitate the exposure of active sites and the transportation of various reactive ions and gases.Meanwhile,the Mn content in the TiCuMn ribbons modulates the chemical and physical properties of its surface,such as modifying the electronic structure of the Cu species,optimizing the adsorption energy of N^(*)atoms,decreasing the strength of the NO adsorption,and eliminating the thermodynamic energy barrier,thus improving the NO reduction reaction catalytic performance.Moreover,a Zn-NO battery was fabricated using the catalyst and Zn plates,generating an NH_(3) yield of 129.1µmol·h^(-1)·cm^(-2)while offering a peak power density of 1.45 mW·cm^(-2).

THE EFFECTS OF SHORT CHAIN FATTY ACID ON BIOLOGICAL PHOSPHATE RELEASE AND PHB SYNTHESIS UNDER ANAEROBIC CONDITION

The basic objective of this research is to determine the effects of acetate, propionate and butyrate on the biological phosphate(bio p) release and poly β hydroxybutyrate(PHB) synthesis and to test the effects of different acetate concentrations on the bio p release as well as the effect of butyrate on the bio p release and PHB synthesis in the presence of nitrates. Oxidation reduction potential probes are used to monitor the relative anaerobic and anoxic states of the sewage. The author quantified PHB, PHV in activated sludge by gas liquid chromatography. It has been demonstrated through a series of batch experiments that phosphorus release and PHB synthesis both take place in anaerobic zone of the bio p removal process, and the key factors to the maximization of PHB synthesis are that simple carbon substrates should be added to the anaerobic zone and that the addition of electron acceptors should be avoided.

Modeling, Optimization, and Control of Solution Purification Process in Zinc Hydrometallurgy

The solution purification process is an essential step in zinc hydrometallurgy. The performance of solution purification directly affects the normal functioning and economical benefits of zinc hydrometallurgy. This paper summarizes the authors' recent work on the modeling, optimization, and control of solution purification process. The online measurable property of the oxidation reduction potential(ORP) and the multiple reactors, multiple running statuses characteristic of the solution purification process are extensively utilized in this research. The absence of reliable online equipment for detecting the impurity ion concentration is circumvented by introducing the oxidationreduction potential into the kinetic model. A steady-state multiple reactors gradient optimization, unsteady-state operationalpattern adjustment strategy, and a process evaluation strategy based on the oxidation-reduction potential are proposed. The effectiveness of the proposed research is demonstrated by its industrial experiment.

Kinetics of reductive leaching of manganese oxide ore using cellulose as reductant

The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.

Fabrication of Fe Nanoparticles into N-doped Mesoporous Carbon Nanotube Derived from Rice-Like Fe/N-MOF and Its ORR Catalytic Performance for MFC

The development of non-noble metal oxidation reduction catalysts(ORR)to improve microbial fuel cell(MFC)performance remains extremely challenging.Herein,the nitrogen-doped iron-based porous carbon nanotube Fe/N@MC-T ORR catalysts were derived from Fe/N-MOF by pyrolyzation using acetonitrile as the nitrogen precursor in a low-cost organic solvent.The Fe/N@MC-T catalysts under different pyrolysis temperatures were characterized by SEM,TEM,BET,XRD,and XPS techniques.Fe/N-MOF showed a smooth rice-like structure with a particle size of about 400×50 nm^(2).The Fe species in Fe/N@MC-T mainly exists in the form of zero-valent iron with a small amount of Fe3C.The results of electrochemical tests revealed that the onset and half-wave potentials of Fe/N@MC-700 were 0.89 V and 0.80 V,respectively,which were only slightly lower than those of the commercial Pt/C(0.92 V and 0.82 V).The MFC with Fe/N@MC-700 showed a highest power density of 864.1 mW/m^(2),which was about 2.25 times that of MFC with carbon cloth,and was slightly lower than that of MFC with Pt/C(20%)(1002.0 mW/m^(2)),which demonstrated that the Fe particles wrapped in carbon nanotubes possessed a relatively high ORR activity.

Comparison of different valent iron on anaerobic sludge digestion:Focusing on oxidation reduction potential,dissolved organic nitrogen and microbial community

This study compared effects of three different valent iron(Fe^(0),Fe(II)and Fe(III))on enhanced anaerobic sludge digestion,focusing on the changes of oxidation reduction potential(ORP),dissolved organic nitrogen(DON),and microbial community.Under the same iron dose in range of 0−160 mg/L after an incubation period of 30 days(d),the maximum methane production rate of sludge samples dosed with respective Fe^(0),Fe(II)and Fe(III)at the same concentration showed indiscernible differences at each iron dose,regardless of the different iron valence.Moreover,their behavior in changes of ORP,DON and microbial community was different:(1)the addition of Fe^(0) made the ORP of sludge more negative,and the addition of Fe(II)and Fe(III)made the ORP of sludge less negative.However,whether being more or less negative,the changes of ORP may show unobservable effects on methane yield when it ranged from−278.71 to−379.80 mV;(2)the degradation of dissolved organic nitrogen,particularly proteins,was less efficient in sludge samples dosed with Fe^(0) compared with those dosed with Fe(II)and Fe(III)after an incubation period of 30 d.At the same dose of 160 mg/L iron,more cysteine was noted in sludge samples dosed with Fe(II)(30.74 mg/L)and Fe(III)(27.92 mg/L)compared with that dosed with Fe^(0)(21.75 mg/L);(3)Fe^(0) particularly promoted the enrichment of Geobacter,and it was 6 times higher than those in sludge samples dosed with Fe(II)and Fe(III)at the same dose of 160 mg/L iron.

A method for recovery of iron,titanium,and vanadium from vanadium-bearing titanomagnetite

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures： low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70 wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.