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.

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.

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.

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.

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.

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.

Small-sized tungsten nitride anchoring into a 3D CNT- rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions

The application of direct methanol fuel cells （DMFC） is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride （WN） nanoparticles （NPs）, of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework （CNT-rGO） using an assembly route. After depositing Pt, the contacted and strongly coupled Pt-WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt-WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction （MOR） and oxygen reduction reaction （ORR）. In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA.mgpt-1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C（JM） catalysts, respectively. The catalyst also exhibited a more positive onset potential （1.03 V）, higher mass activity （151.3 mA.mgpt-1）, and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt-WN can enhance the catalytic activity and CO-tolerance of Pt. Pt-WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.

Electrocatalytic reduction of NO to NH_(3) in ionic liquids by P-doped TiO_(2) nanotubes

Designing advanced and cost-effective electrocatalytic system for nitric oxide(NO)reduction reaction(NORR)is vital for sustainable NH_(3) production and NO removal,yet it is a challenging task.Herein,it is shown that phosphorus(P)-doped titania(TiO_(2))nanotubes can be adopted as highly efficient catalyst for NORR.The catalyst demonstrates impressive performance in ionic liquid(IL)-based electrolyte with a remarkable high Faradaic efficiency of 89%and NH3 yield rate of 425μg·h^(−1)·mg_(cat).^(−1),being close to the best-reported results.Noteworthy,the obtained performance metrics are significantly larger than those for N_(2) reduction reaction.It also shows good durability with negligible activity decay even after 10 cycles.Theoretical simulations reveal that the introduction of P dopants tunes the electronic structure of Ti active sites,thereby enhancing the NO adsorption and facilitating the desorption of ^(*)NH_(3).Moreover,the utilization of IL further suppresses the competitive hydrogen evolution reaction.This study highlights the advantage of the catalyst−electrolyte engineering strategy for producing NH_(3) at a high efficiency and rate.

Characterization of iron diagenesis in marine sediments using refined iron speciation and quantized iron(Ⅲ)-oxide reactivity:a case study in the Jiaozhou Bay,China

As a case study, refined iron（Fe） speciation and quantitative characterization of the reductive reactivity of Fe（Ⅲ）oxides are combined to investigate Fe diagenetic processes in a core sediment from the eutrophic Jiaozhou Bay.The results show that a combination of the two methods can trace Fe transformation in more detail and offer nuanced information on Fe diagenesis from multiple perspectives. This methodology may be used to enhance our understanding of the complex biogeochemical cycling of Fe and sulfur in other studies. Microbial iron reduction（MIR） plays an important role in Fe（Ⅲ） reduction over the upper sediments, while a chemical reduction by reaction with dissolved sulfide is the main process at a deeper（〉 12 cm） layer. The most bioavailable amorphous Fe（Ⅲ） oxides [Fe（Ⅲ）am] are the main source of the MIR, followed by poorly crystalline Fe（Ⅲ） oxides [Fe（Ⅲ）pc）]and magnetite. Well crystalline Fe（Ⅲ） oxides [Fe（Ⅲ）wc] have barely participated in Fe diagenesis. The importance of the MIR over the upper layer may be a combined result of the high availability of highly reactive Fe oxides and low availability of labile organic matter, and the latter is also the ultimate factor limiting sulfate reduction and sulfide accumulation in the sediments. Microbially reducible Fe（Ⅲ） [MR-Fe（Ⅲ）], which is quantified by kinetics of Fe（II）-oxide reduction, mainly consists of the most reactive Fe（Ⅲ）am and less reactive Fe（Ⅲ）pc. The bulk reactivity of the MR-Fe（Ⅲ） pool is equivalent to aged ferrihydrite, and shows down-core decrease due to preferential reduction of highly reactive phases of Fe oxides.

Effective fabrication of porous Au-Ag alloy nanorods for in situ Raman monitoring catalytic oxidation and reduction reactions

Porous metal nanostructures exhibit excellent catalytic properties due to their high surface-to-volume ratios and abundant catalytic active sites. However, it is still challenging to control nanopores density and structural features in a facile route and the preparation of porous alloy nanorods for catalytic application has not been well explored. In this work, we demonstrate a synthetic strategy to fabricate highly porous Au–Ag alloy nanorods(P-Au Ag NRs) by critically dealloying Ag atoms from homogeneous solid Au–Ag alloy nanorods(Au Ag NRs). Combining the merits of the tunable plasmonic properties of noble metal nanorods, excellent stabilities of alloys, and superior catalytic activities of porous structures, we use the P-Au Ag NRs as a Raman probe for the in situ monitoring of the catalytic oxidation of 3,3',5,5' tetramethylbenzidine(TMB) and reduction of 4-nitrothiophenol(4-NTP). We also compare their compositiondependent catalytic activities. The results show that P-Au Ag NRs possess superior chemical stability and higher catalytic activity than those of core-shell structures due to synergistic structural and chemical mechanisms. This strategy provides a predictive design approach for the next-generation alloy catalysts with high-performance.

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.

Estimation of the Postmortem Interval by Measuring Blood Oxidation‑reduction Potential Values

Accurate estimation of the postmortem interval(PMI)is an important task in forensic practice.In the last half-century,the use of postmortem biochemistry has become an important ancillary method in determining the time of death.The present study was carried out to determine the correlation between blood oxidation-reduction potential(ORP)values and PMIs,and to develop a three-dimensional surface equation to estimate the PMI under various temperature conditions.A total of 48 rabbits were placed into six groups and sacrificed by air embolism.Blood was obtained from the right ventricle of each rabbit,and specimens were stored at 10℃,15℃,20℃,25℃,30℃,and 35℃.At different PMIs(once every 4 h),the blood ORP values were measured using a PB-21 electrochemical analyzer.Statistical analysis and curve fitting of the data yielded cubic polynomial regression equations and a surface equation at different temperatures.Result:The results showed that there was a strong positive correlation between the blood ORP values at different temperatures and the PMI.This study provides another example of using a three-dimensional surface equation as a tool to estimate the PMI at various temperature conditions.

Development of an in-situ H_(2)reduction and moderate oxidation method for 3,5-dimethylpyridine hydrogenation in trickle bed reactor

The Ru/C catalyst prepared by impregnation method was used for hydrogenation of 3,5-dimethylpyridine in a trickle bed reactor.Under the same reduction conditions(300°C in H_(2)),the catalytic activity of the non-in-situ reduced Ru/C-n catalyst was higher than that of the in-situ reduced Ru/C-y catalyst.Therefore,an in-situ H_(2)reduction and moderate oxidation method was developed to increase the catalyst activity.Moreover,the influence of oxidation temperature on the developed method was investigated.The catalysts were characterized by Brunauer–Emmett–Teller method,hydrogen temperature programmed reduction H_(2)-TPR,hydrogen temperature-programmed dispersion(H_(2)-TPD),X-ray diffraction,energy dispersive spectroscopy,X-ray photoelectron spectroscopy,Raman spectroscopy,O2 chemisorption and oxygen temperature-programmed dispersion(O2-TPD)analyses.The results showed that there existed an optimal Ru/RuO_(x)ratio for the catalyst,and the highest 3,5-dimethylpyridine conversion was obtained for the Ru/C-i1 catalyst prepared by in-situ H_(2)reduction and moderate oxidation(oxidized at 100°C).Excessive oxidation(200°C)resulted in a significant decrease in the Ru/RuO_(x)ratio of the in-situ H_(2)reduction and moderate oxidized Ru/C-i2 catalyst,the interaction between RuO_(x)species and the support changed,and the hard-to-reduce RuO_(x)species was formed,leading to a significant decrease in catalyst activity.The developed in-situ H_(2)reduction and moderate oxidation method eliminated the step of the non-in-situ reduction of catalyst outside the trickle bed reactor.

Ultrafast metal oxide reduction at Pd/PdO_(2) interface enables onesecond hydrogen gas detection under ambient conditions

Here,we report a Pd/PdO_(x) sensing material that achieves 1-s detection of 4% H_(2) gas(i.e.,the lower explosive limit concentration for H_(2))at room temperature in air.The Pd/PdO_(x) material is a network of interconnected nanoscopic domains of Pd,PdO,and PdO_(2).Upon exposure to 4% H_(2),PdO and PdO_(2) in the Pd/PdO_(x) are immediately reduced to metallic Pd,generating over a>90% drop in electrical resistance.The mechanistic study reveals that the Pd/PdO_(2) interface in Pd/PdOx is responsible for the ultrafast PdO_(x) reduction.Metallic Pd at the Pd/PdO_(2) interface enables fast H_(2) dissociation to adsorbed H atoms,significantly lowering the PdO2 reduction barrier.In addition,control experiments suggest that the interconnectivity of Pd,PdO,and PdO2 in our Pd/PdO_(x) sensing material further facilitates the reduction of PdO,which would otherwise not occur.The 1-s response time of Pd/PdO_(x) under ambient conditions makes it an excellent alarm for the timely detection of hydrogen gas leaks.