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1.
The ac response of polyaniline thin films on platinum electrodes was measured at different dc potentials during the N2-fixation in methanol + LiClO4 electrolyte with 0.03 mol L−1 H2SO4 for the first time. The optimum film thickness was found to be 1.5 μm, N2-pressure 50 bar and an optimum electrolysis potential of −0.12 V (NHE). The diffusion coefficients for N2 into the polymer film was found to be (5 ± 2)×10−9 cm2 s−1.  相似文献   

2.
The adsorption characteristics of CO2 and N2 in 13X zeolites have been studied by the molecular simulation and N2 adsorption experiment. It is found that the simulation results by Dreiding force fields are in an agreement with the published data. The influence of the σ and ε parameters of OZ and Na+ on the adsorption performance is discussed. Then the optimized force field parameters are obtained. Specific surface area (S B ) is calculated by simulation and experiment. Its relative error is just only 4.3 %. Therefore, it is feasible that S B of 13X zeolites is obtained by the simulation methods. Finally, the impacts of pressure and temperature on adsorption characteristics are investigated. At low pressure, CO2 adsorption in 13X zeolites belongs to the surface adsorption. As the pressure increase, the partial multilayer adsorption appears along with the surface adsorption. N2 adsorption in 13X zeolites is different from that of CO2. At low temperature of 77 K, two primary peaks are caused by the surface adsorption and multilayer adsorption respectively regardless of pressure variation. When the temperature is 273 K, the energy distribution curve appears undulate at low pressures. Then it becomes stable with the pressure increase. The surface adsorption plays an important role at the relative high pressures. The results will help to provide the theory guide for the optimization of force field parameters of adsorbents, and it is very important significance to understand the adsorption performance of zeolites.  相似文献   

3.
Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al2O3/ α-Al2O3 composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO2/N2, CO2/H2 and CH4/H2 systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al2O3 support and nanoporous unsupport (TPABr templating SiO2/ γ-Al2O3 composite layer without α-Al2O3 support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al2O3 support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO2 and CH4. While the adsorption rates in the unsupport showed in the order of H2> CO2> N2> CH4 at low pressure range, the permeate flux in the membrane was in the order of H2≫N2> CH4> CO2. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO2/H2 and CH4/H2 systems. Although light and non-adsorbable molecules, such as H2, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO2 and CH4, showed a higher separation factor (CO2/H2=5-7, CH4/H2=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.  相似文献   

4.
This paper presents the measurement and simulation data on the thermal and chemical structure of an atmospheric-pressure premixed H2/O2/N2 flame doped with iron pentacarbonyl Fe(CO)5. Soft ionization molecular beam mass spectrometry was used to measure concentration profiles of the combustion products of iron pentacarbonyl: Fe, FeO2, FeOH, and Fe(OH)2. A comparison of experimental and simulated concentration profiles showed that they are in satisfactory agreement for FeO2 and Fe(OH)2 and differ significantly for Fe and FeOH. Thus, the previously proposed kinetic model for the oxidation of iron pentacarbonyl was tested and it was shown that the mechanism needs further elaboration.  相似文献   

5.
Nitrous oxide (N2O) is primarily produced as intermediate in denitrification and, to a lesser extent, through nitrification processes. Nitrous oxide emission and, consequently, its atmospheric impacts depend on the extent to which N2O is reduced to dinitrogen gas (N2) by denitrifiers. Field experiments were conducted from 1998 through 2000 growing seasons at St. Emmanuel, Quebec, Canada, to investigate the combined impact of water table management (WTM) and N fertilization rate on the soil denitrification (N2O + N2) rate, rate of N2O production, and the N2O:N2O + N2 ratio. Water table treatments included subirrigation (SI) with a target water table depth of 0.6 m and free drainage (FD) with open drains. The tile drains (75 mm diameter) were laid at a 1.0 m depth from the soil surface. Nitrogen fertilizer was applied at two rates:120 and 200 kg N ha−1 as ammonium nitrate (34-0-0). The N2O + N2 evolution rates were greater in SI (12.9 kg N ha−1) than in FD (5.8 kg N ha−1) plots. The percentages of N2O relative to overall N2O + N2 evolution were 35 and 11% for 1998, 29 and 8% for 1999, and 37 and 20% for 2000, under FD and SI, respectively. The reduced N2O production under SI was due to a greater reduction of N2O to N2. Results indicate that greater N2O + N2 evolution under shallow water tables are not necessarily accompanied by higher N2O emissions.  相似文献   

6.
Grazed pastures contribute significantly to anthropogenic emissions of N2O but the respective contributions of archaea, bacteria and fungi to codenitrification in such systems is unresolved. This study examined the relative contributions of bacteria and fungi to rates of denitrification and codenitrification under a simulated ruminant urine event. It was hypothesised that fungi would be primarily responsible for both codenitrification and total N2O and N2 emissions. The effects of bacterial (streptomycin), fungal (cycloheximide), and combined inhibitor treatments were measured in a laboratory mesocosm experiment, on soil that had received 15N labelled urea. Soil inorganic-N concentrations, N2O and N2 gas fluxes were measured over 51 days. On Days 42 and 51, when nitrification was actively proceeding in the positive control, the inhibitor treatments inhibited nitrification as evidenced by increased soil NH 4 + -N concentrations and decreased soil NO 2 ? -N and NO 3 ? -N concentrations. Codenitrification was observed to contribute to total fluxes of both N2O (≥ 33%) and N2 (≥ 3%) in urine-amended grassland soils. Cycloheximide inhibition decreased NH 4 + 15N enrichment and reduced N2O fluxes while reducing the contribution of codenitrification to total N2O fluxes by ≥ 66 and ≥ 42%, respectively. Thus, given archaea do not respond to significant urea deposition, it is proposed that fungi, not bacteria, dominated total N2O fluxes, and the codenitrification N2O fluxes, from a simulated urine amended pasture soil.  相似文献   

7.
Controlled tile drainage (CTD) can benefit the environment and crop production. However, CTD has the potential to increase soil greenhouse gas (GHG: CO2, CH4, N2O) emissions by increasing soil water contents and elevating field water levels. A paired-field (CTD and uncontrolled tile drainage (UTD)) approach was used to compare soil GHG emissions for silt loam corn, soybean, and forage fields under CTD and UTD management in eastern Ontario, Canada during a drier and a wetter growing season. A total of five field pairs were examined. Soil GHG emissions directly over tile drains (OT) and between tile drains (BT) in the CTD fields were also assessed. Average soil GHG emissions did not significantly differ (p > 0.05) for CTD and UTD field pairs, except for CO2 emissions (greater emissions from UTD fields) among two field pairs studied (forage in the drier growing season and soybean in the wetter growing season), and N2O emissions from a soybean field pair in the wet growing season (greater emissions from CTD field). Significantly higher soil water contents in the UTD forage field may have augmented CO2 fluxes there. There were some significantly higher N2O (in the wetter growing season) and CO2 emissions (in both growing seasons) BT relative to OT locations in some fields; but these differences were not translated significantly to other BT and OT site comparisons. The wetter growing season examined resulted in greater average daily soil CO2 fluxes overall, but similar CH4 and N2O fluxes for soybean fields compared to soybean fields in the drier growing season. Overall, there were no spatially or temporally systematic differences in GHG emissions among CTD and UTD field pairs, or among BT and OT locations in CTD fields.  相似文献   

8.
The chemical and thermal structure of a Mache-Hebra burner stabilized premixed rich CH4/O2/N2 flame with additives of vapors of triphenylphosphine oxide [(C6H5)3PO], hexabromocyclododecane (C12H18Br6), and ethyl bromide (C2H5Br) was studied experimentally using molecular beam mass spectrometry (MBMS) and a microthermocouple method. The concentration profiles of stable and active species, including atoms and free radicals, and flame temperature pro.les were determined at a pressure of 1 atm. A comparison of the experimental and modeling results on the flame structure shows that MBMS is a suitable method for studying the structure of flames stabilized on a Mache-Hebra burner under near-adiabatic conditions. The relative flame inhibition effectiveness of the added compounds is estimated from changes in the peak concentrations of H and OH radicals in the flame and from changes in the flame propagation velocity. The results of the investigation suggest that place of action of the examined flame retardants is the gas phase. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 5, pp. 12–20, September–October, 2007.  相似文献   

9.
It is difficult to research on the surface structure of amorphous phase in fly ash during leaching reaction due to crystalline phase and complex structure. In the present work, in order to reveal the effects of leaching reaction on the surface structure of amorphous phase in fly ash, the modelling CaO-Fe2O3-Al2O3-SiO2 glass was prepared by the traditional melting methods. The leaching reaction of CaO-Fe2O3-Al2O3-SiO2 glass with 7.5 M KOH was investigated by spectroscopy, spectrophotometer and wet chemical method. The results show that the content of Q 1, Q 2, Q 3 and Q 4 of glass without corrosion was 4.21, 9.51, 23.03 and 52.55%, respectively, which shows that the network polymerization of glass is compact. The leaching reaction of glass can be described by the following equation: dS/dt = k/(r + S 0). Leaching in KOH for various times induces the content of Q 4 and Q 1 to be decreased, and Q 2 and Q 3 increased, resulted in the depolymerization of network and the surface glass dissolved in alkaline solution to form a gel phase. In stage one of leaching reaction, the rate of iron ion leached from glass surface was slow, which resulted in the small slope of straight-line relationship of leaching curve. In the following stage, the leaching rate of iron ion increased with the prolongation of time.  相似文献   

10.
Aluminum terephthalate, MIL-53(Al), metal–organic framework synthesized hydrothermally and purified by solvent extraction method was used as an adsorbent for gas adsorption studies. The synthesized MIL-53(Al) was characterized by powder X-Ray diffraction analysis, surface area measurement using N2 adsorption–desorption at 77 K, FTIR spectroscopy and thermo gravimetric analysis. Adsorption isotherms of CO2, CH4, CO, N2, O2 and Ar were measured at 288 and 303 K. The absolute adsorption capacity was found in the order CO2>CH4>CO>N2>Ar>O2. Henry’s constants, heat of adsorption in the low pressure region and adsorption selectivities for the adsorbate gases were calculated from their adsorption isotherms. The high selectivity and low heat of adsorption for CO2 suggests that MIL-53(Al) is a potential adsorbent material for the separation of CO2 from gas mixtures. The high selectivity for CH4 over O2 and its low heat of adsorption suggests that MIL-53(Al) could also be a compatible adsorbent for the separation of methane from methane–oxygen gas mixtures.  相似文献   

11.
Photocatalytic hydrogen evolution is considered as one of the promising pathways to settle the energy crises and environmental issues by utilizing solar energy. In this paper, noble-metal-free Ni2P was used as cocatalyst to enhance g-C3N4 for photocatalytic hydrogen production under visible light irradiation (λ?>?420 nm). Characterization results indicated that Ni2P nanoparticles were successfully loaded onto g-C3N4, which can significantly contribute to accelerate the separation and transfer of photogenerated electron. The hydrogen evolution rate reached ~?270 µmol h?1 g?1 and the apparent quantum yield (AQY) was ~?2.85% at 420 nm. Meanwhile, there is no obviously decrease of the hydrogen production rate even after 36 h under visible light illumination. In addition, the mechanism of photocatalytic hydrogen evolution was also elaborated in detail.

Graphical Abstract

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12.
Slurry separation using mechanical and chemical methods is one of the options considered to solve problems of slurry management at the farm scale. The fractions obtained with such treatments have distinct compositions, which allow different options for their utilization (composting, direct application, and fertigation). In this study, four fractions of slurry were obtained using a combined treatment system including slurry treatment with a screw press separator (solid and liquid fractions) followed by sedimentation with the addition of Polyacrylamide (PAM) (PAM-Supernatant and PAM-Sediment) to the LF. These fractions were then incorporated into arable soil under controlled laboratory conditions and the organic N degradation from each treatment was followed for 94 days. Total N emissions (N2O + N2) as well as the sources of the N emissions (nitrification or denitrification) were also studied during this period. Results showed that the slurry fractions (SFs) had distinct behavior relative to the whole slurry (WS), namely in terms of N degradation in soil, where N mineralization was observed only in the WS treatment whereas N immobilization occurred in the other treatments. In terms of N2O emissions, higher losses, expressed as a percentage of the total N added, occurred from the LF treatments (liquid, PAM-Supernatant and PAM-Sediment). This work indicates that the slurry treatment by mechanical and chemical separation may be a good option for slurry management at the farm scale since it allows greater utilization of the different fractions with a small effect on N2O emissions after SFs’ application to soil.  相似文献   

13.
MIL-101@g-C3N4 nanocomposite was prepared by solvothermal synthesis and used for CO2 adsorption. The parent materials (MIL-101 and g-C3N4) and the MIL-101@g-C3N4 were characterized by X-ray diffraction, argon adsorption/desorption, Fourier transform infrared spectroscopy, thermal analysis (TG/DTA), transmission electronic microscopy, and Energy-dispersive X-ray spectroscopy. The results confirmed the formation of well-defined MIL-101@g-C3N4 with interesting surface area and pore volume. Furthermore, both MIL-101 and MIL-101@g-C3N4 were accomplished in carbon dioxide capture at different temperatures (280, 288, 273 and 298 K) at lower pressure. The adsorption isotherms show that the nanocomposite has a good CO2 adsorption affinity compared to MIL-101. The best adsorption capacity is about 1.6 mmol g?1 obtained for the nanocomposite material which is two times higher than that of MIL-101, indicating strong interactions between CO2 and MIL-101@g-C3N4. This difference in efficacy is mainly due to the presence of the amine groups dispersed in the nanocomposite. Finally, we have developed a simple route for the preparation of an effective and new adsorbent for the removal of CO2, which can be used as an excellent candidate for gas storage, catalysis, and adsorption.  相似文献   

14.
The hollow TiO2@g-C3N4 composites were synthesized by a facile stirring method. The phase compositions, optical properties, and morphologies of the samples were characterized via X-ray diffraction, scanning electron microscope, transmission electron microscopy, high resolution transmission electron microscopy, fourier transform infrared spectroscopy, N2 adsorption–desorption, UV–Vis diffuse reflectance spectroscopy and Photoluminescence. The photocatalyitc performance was evaluated by reduction carbon dioxide under visible light irradiation. The results indicated that TiO2@g-C3N4 nanocomposites displayed higher photocatalytic activity compared with pure g-C3N4. The increased photocatalytic activity of TiO2@g-C3N4 nanocomposites can be attributed to facilitating the photo-induced electron–hole separation efficiency and enhancing the photo-induced electron migration.

Graphical Abstract

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15.
The glasses, in which oxygen was partially replaced with sulfur, have been synthesized in the Na2O-P2O5-Na2S system. The chemical and chromatographic analyses of the glasses synthesized have been performed. The temperature-concentration dependences of electrical conductivity of the glasses have been studied over a wide temperature range; the glass transition temperatures and the nature of charge carriers have been determined. The IR spectra and Raman spectra have been recorded at room temperature; the density and microhardness of the glasses and ultrasound velocity have been measured. A comparison of the electrical conductivities of the investigated glasses with those of the earlier studied glasses in the Na2O-P2O5 system has shown their fair coincidence. The introduction of sodium sulfide into the Na2O-P2O5 system is accompanied by an approximately threefold increase in electrical conductivity, although the concentrations of charge carriers (sodium ions) in the glasses amount to ∼17 and ∼26 mmol/cm3, respectively. The rise in electrical conductivity has been assumed to be caused by the increase in the degree of dissociation of polar structural chemical units including sulfide ions and by the higher mobility of sodium ions in the oxygen-free matrix.  相似文献   

16.
17.
The objective of this study was to evaluate N2O fluxes from integrated crop-livestock (ICL) and integrated crop-livestock forest (ICLF) systems, continuous pasture and native Cerrado. The experiment was conducted at Embrapa Cerrados, Planaltina-DF, in a Red Oxisol, between February 2012 and April 2014, following the transition of crop to livestock, which began in March 2012, with the sowing of Brachiaria brizantha cv. Piatã, intercropped with sorghum. The experimental design was a randomized block with three replications. The treatments were: cultivated area intercropped with rows of Eucalyptus, spaced 2 × 2 m between plants and 22 m between rows (ICLF); and an area cultivated without tree species (ICL), and also two adjacent reference areas: native Cerrado and continuous pasture. N2O productions were characterized by fluxes below 20 μg N m?2 h?1. The ICL system had the highest cumulative flux with 2.84 kg N ha?1, while the ICLF system obtained cumulative fluxes of 2.05 kg N ha?1. The native Cerrado showed a negative balance, with –0.05 kg N ha?1. The dry season was mostly characterized by low N2O fluxes ranging between 10 μg N m?2 h?1 and negative values, whereas higher N2O fluxes were observed after precipitation events, especially those following a long drought period. The water filled pore space was the factor that best explained N2O fluxes, but higher fluxes were observed after the application of nitrogen fertilizer. There was a positive correlation between microbial biomass carbon and N2O fluxes in the ICL and ICLF systems.  相似文献   

18.
The polytherms of ice melting in sections of the Ca(NO3)2-Mg(NO3)2-CO(NH2)2-H2O system with different component ratios were studied in the temperature interval from 0 to −40°C. A series of nitrate and nitrate-carbonate reagents that are promising for the creation of anti-acing reagents were found, which form eutectics with ice at temperatures from −25 to −39°C. Their properties, viz., melting properties with respect to ice and corrosiveness on metals and alloys, were determined. An effective corrosion inhibitor was selected.  相似文献   

19.
A new compound of (Rb,K)2Cu3(P2O7)2 is obtained by high-temperature reactions from a mixture of RbNO3, KNO3, Cu(NO3)2, and (NH4)4P2O7. The crystal structure was solved by direct methods and refined to R 1 = 0.056 for 5022 independent reflections. The compound belongs to a rhombic crystal system, P212121, Z = 8, a = 9.9410(7) Å, b = 13.4754(6) Å, c = 18.6353 (3) Å, and R = 0.056. The basis of the structure is a complex copper-phosphate skeleton of the composition of [Cu3(P2O7)2]2–, which can be regarded as consisting of two types of heteropolyhedral layers parallel to the (001) plane. The layers are alternated with each other, forming a frame, in the cavities of which the positions of alkali cations are located, statistically populated with K+ and Rb+ ions. Based on the refined populations of the positions of alkali cations, an exact chemical formula of the compound can be written as Rb1.28K0.72Cu3(P2O7)2. The compound is the most complex among those known to this day of the composition of A2 IB3 II(P2O7)2 (A = Li, Na, K, Rb, or Cs; B = Ni, Cu, or Zn).  相似文献   

20.
Two mesoporous material Ni/γ-Al2O3 catalysts were prepared and characterized by ICP-AES, XRD, and TPR. The differences in reaction activity between Ni-in-Al2O3 and Ni-on-Al2O3 were investigated for hydrotreating of crude 2-ethylhexanol. The results show that the Ni species (Ni-on-Al2O3) exhibit excellent hydrogenation activities at a wide range of H2 pressure and space velocity, while the Ni species (Ni-in-Al2O3) exhibit similar activities with those of Ni-on-Al2O3 only at higher H2 pressure and lower space velocity. Due to the presence of extensively exposed Ni species on the Ni-on-Al2O3 catalyst, its hydrogenation performance was increased significantly because of the low interphase mass transfer resistance.  相似文献   

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