Reduced graphene oxide-based materials for electrochemical energy conversion reactions

There have been ever-growing demands to develop advanced electrocatalysts for renewable energy conversion over the past decade.As a promising platform for advanced electrocatalysts,reduced graphene oxide(rGO)has attracted substantial research interests in a variety of electrochemical energy conversion reactions.Its versatile utility is mainly attributed to unique physical and chemical properties,such as high specific surface area,tunable electronic structure,and the feasibility of structural modification and functionalization.Here,a comprehensive discussion is provided upon recent advances in the material preparation,characterization,and the catalytic activity of rGO-based electrocatalysts for various electrochemical energy conversion reactions(water splitting,CO2 reduction reaction,N2 reduction reaction,and O2 reduction reaction).Major advantages of rGO and the related challenges for enhancing their catalytic performance are addressed.

Organic Manures and Crop Residues as Fertilizer Substitutes: Impact on Nitrous Oxide Emission, Plant Growth and Grain Yield in Pre-Monsoon Rice Cropping System

It has been previously argued that application of organic residues added in soils has a great impact on soil quality, grain productivity as well as greenhouse gas emissions. Substitution of chemical fertilizers has become a common practice in agricultural systems which consequently affect the greenhouse gas emissions from agricultural fields. To observe the effects of organic manures and crop residues amendments, five fertilizer treatments including conventional inorganic nitrogen fertilizer—NPK, cow manure, rice straw, poultry manure and sugarcane bagasse were applied in the field for two consecutive pre-monsoon rice seasons. Addition of rice straw, poultry manure and sugarcane bagasse decreased the cumulative N2O emissions by 14% and 31%, and by 1% and 7% and 5% and 3% in 2012 and 2013 respectively when compared with conventional fertilizer treatment (NPK) in both the seasons. Yield differences were not significant (p > 0.005) amongst the treatments, however, a slight increase was observed due to rice straw amendment over control. Soil organic carbon decreased by 11% - 17% under the application of organic residues which might have contributed to lower N2O emissions from the plots. Results of carbon equivalent emission (CEE) and carbon efficiency ratio (CER) indicated that incorporation of rice straw during pre-monsoon rice season had the potential to reduce the N2O emissions and yield scaled emissions of rice production at lower level than the conventional farmers’ practice of using chemical fertilizers (NPK).

Atmospheric N2O gas detection based on an inter-band cascade laser around 3.939 μm

N2O is a significant atmospheric greenhouse gas that contributes to global warming and climate change.In this work,the high sensitivity detection of atmospheric N2O is achieved using wavelength modulation spectroscopy(WMS)with an inter-band cascade laser operating around 3.939μm.A Lab VIEW-based software signal generator and software lock-in amplifiers are designed to simplify the system.In order to eliminate the interference from water vapor,the detection was performed at a pressure of 0.1 atm(1 atm=1.01325×10^5 Pa)and a drying tube was added to the system.To improve the system performance for long term detection,a novel frequency locking method and 2 f/1 f calibration-free method were employed to lock the laser frequency and calibrate the power fluctuations,respectively.The Allan deviation analysis of the results indicates a detection limit of^20 ppb(1 ppb=1.81205μg/m3)for a 1 s integration time,and the optimal detection limit is^5 ppb for a 40-s integration time.

棉纤维素/N-甲基吗啉-N-氧化物—水合物(NMMO·H_(2)O)溶液的流变性能

利用Instron3211型毛细管流变仪和Instron3325型流变力学谱仪研究了棉纤维素/N-甲基吗啉-N-氧化物一水合物(NMMO·H_2O)溶液流变性能,讨论了剪切速率、温度和溶液中的纤维素的质量分数对棉纤维素/NMMO·H_2O溶液流变性能的影响,计算了不同质量分数溶液的粘流活化能。

Rh_2O_3/mesoporous MO_x-Al_2O_3(M = Mn,Fe,Co,Ni,Cu,Ba)catalysts:Synthesis,characterization,and catalytic applications

Recently,a one-pot self-assembly method was proposed for the synthesis of mesoporous Al2O3 and MOx-Al2O3 composite materials.However,few attempts have been made to use mesoporous MOx-Al2O3 composites to support metal oxides for catalysis.In the present work,mesoporous MOx-Al2O3（M = Mn,Fe,Co,Ni,Cu,Ba）materials were prepared by a one-pot self-assembly method using Pluronic P123 as a structure-directing agent.The obtained mesoporous materials were loaded with Rh2O3 nanoparticles via impregnation with Rh（NO3）3 followed by calcination in air at 500°C.The resulting catalysts were characterized by X-ray diffraction,N2 adsorption-desorption measurements,transmission electron microscopy,inductively coupled plasma optical emission spectrometry,X-ray photoelectron spectroscopy,and their catalytic activity and stability for CO oxidation and N2O decomposition were tested.The Rh2O3 nanoparticles were found to be on the order of1 nm in size and were highly dispersed on the high surface area mesoporous MOx-Al2O3 supports.A number of the Rh2O3/mesoporous MOx-Al2O3 catalysts exhibited higher catalytic activity than the Rh2O3/mesoporous Al2O3 prepared for comparison.

Nitrogen cycling and environmental impacts in upland agricultural soils in North China： A review

The upland agricultural soils in North China are distributed north of a line between the Kunlun Mountains, the Qinling Mountains and the Huaihe River. They occur in arid, semi-arid and semi-humid regions and crop production often depends on rain-fed or irrigation to supplement rainfall. This paper summarizes the characteristics of gross nitrogen（N） transformation, the fate of N fertilizer and soil N as well as the N loss pathway, and makes suggestions for proper N management in the region. The soils of the region are characterized by strong N mineralization and nitrification, and weak immobilization and denitrification ability, which lead to the production and accumulation of nitrate in the soil profile. Large amounts of accumulated nitrate have been observed in the vadose-zone in soils due to excess N fertilization in the past three decades, and this nitrate is subject to occasional leaching which leads to groundwater nitrate contamination. Under farmer＇s conventional high N fertilization practice in the winter wheat-summer maize rotation system（N application rate was approximately 600 kg ha–1 yr–1）, crop N uptake, soil residual N, NH_3 volatilization, NO_3~– leaching, and denitrification loss accounted for around 27, 30, 23, 18 and 2% of the applied fertilizer N, respectively. NH_3 volatilization and NO_3~– leaching were the most important N loss pathways while soil residual N was an important fate of N fertilizer for replenishing soil N depletion from crop production. The upland agricultural soils in North China are a large source of N_2O and total emissions in this region make up a large proportion（approximately 54%） of Chinese cropland N_2O emissions. The “non-coupled strong ammonia oxidation” process is an important mechanism of N_2O production. Slowing down ammonia oxidation after ammonium-N fertilizer or urea application and avoiding transient high soil NH4＋ concentrations are key measures for reducing N_2O emissions in this region. Further N management should aim to minimize N losses from crop and livestock production, and increase the recycling of manure and straw back to cropland. We also recommend adoption of the 4 R（Right soure, Right rate, Right time, Right place） fertilization techniques to realize proper N fertilizer management, and improving application methods or modifying fertilizer types to reduce NH_3 volatilization, improving water management to reduce NO_3~– leaching, and controlling the strong ammonia oxidation process to abate N_2O emission. Future research should focus on the study of the trade-off effects among different N loss pathways under different N application methods or fertilizer products.

Advanced glycation end products induce neural tube defects through elevating oxidative stress in mice

Our previous study showed an association between advanced glycation end products （AGEs） and neural tube defects （NTDs）. To understand the molecular mechanisms underlying the effect of AGEs on neural tube development, C57BL/6 female mice were fed for 4 weeks with com- mercial food containing 3% advanced glycation end product bovine serum albumin （AGE-BSA） or 3% bovine serum albumin （BSA） as a control. After mating mice, oxidative stress markers including malondialdehyde and H202 were measured at embryonic day 7.5 （E7.5） of ges- tation, and the level of intracellular reactive oxygen species （ROS） in embryonic cells was determined at E8.5. In addition to evaluating NTDs, an enzyme-linked immunosorbent assay was used to determine the effect of embryonic protein administration on the N-（carboxymethyl） lysine reactivity of acid and carboxyethyl lysine antibodies at E10.5. The results showed a remarkable increase in the incidence of NTDs at El0.5 in embryos of mice fed with AGE-BSA （no hyperglycemia） compared with control mice. Moreover, embryonic protein administration resulted in a noticeable increase in the reactivity of N-（carboxymethyl） lysine and N（ε）-（carboxyethyl） lysine antibodies. Malondialdehyde and H2O2 levels in embryonic cells were increased at E7.5, followed by increased intracellular ROS levels at E8.5. Vitamin E supplementation could partially recover these phenomena. Collectively, these results suggest that AGE-BSA could induce NTDs in the absence of hyperglycemia by an underlying mechanism that is at least partially associated with its capacity to increase embryonic oxidative stress levels.

Methylprednisolone exerts neuroprotective effects by regulating autophagy and apoptosis

Methylprednisolone markedly reduces autophagy and apoptosis after secondary spinal cord injury. Here, we investigated whether pretreatment of cells with methylprednisolone would protect neuron-like cells from subsequent oxidative damage via suppression of autophagy and apoptosis. Cultured N2 a cells were pretreated with 10 μM methylprednisolone for 30 minutes, then exposed to 100 μM H2O2 for 24 hours. Inverted phase contrast microscope images, MTT assay, flow cytometry and western blot results showed that, compared to cells exposed to 100 μM H2O2 alone, cells pretreated with methylprednisolone had a significantly lower percentage of apoptotic cells, maintained a healthy morphology, and showed downregulation of autophagic protein light chain 3B and Beclin-1 protein expression. These findings indicate that methylprednisolone exerted neuroprotective effects against oxidative damage by suppressing autophagy and apoptosis.

Plasma Post Oxidation of Plasma Nitrocarburized SKD 61 Steel

Plasma nitrocarburizing and plasma oxidizing treatments were performed to improve the wear and corrosion resistance of SKD 61 steel.Plasma nitrocarburizing was conducted for 12 h at 540℃in the nitrogen, hydrogen and methane atmosphere to produce theε-Fe-（2-3）（N,C） phase.The compound layer produced by plasma nitrocarburising was predominantly composed ofε-phase,with a small proportion ofγ′-Fe-4 （N,C） phase. The thickness of the compound layer and the diffusion layer are about 10μm and about 200μm,respectively. Plasma post oxidation was performed on the nitrocarburized samples with various oxygen/hydrogen ratio at constant temperature of 500℃for 1 h.The very thin magnetite （Fe-3O-4） layer of 1-2μm in thickness on top of the compound layer was obtained.Anodic polarization test revealed that plasma nitrocarburizing process contributed a significant improvement of corrosion resistance of SKD 61 steel.However,the corrosion characteristics of the nitrocarburized compound layer was deteriorated by oxidation treatment.

A Process-based Model of N_2O Emission from a Rice-Winter Wheat Rotation Agro-Ecosystem:Structure,Validation and Sensitivity

In order to numerically simulate daily nitrous oxide （N2O） emission from a rice-winter wheat rotation cropping system, a process-based site model was developed （referred to as IAP-N-GAS） to track the movement and transformation of several forms of nitrogen in the agro-eeosystem, which is affected by climate, soil, crop growth and management practices. The simulation of daily N2O fluxes, along with key daily environmental variables, was validated with three-year observations conducted in East China. The validation demonstrated that the model simulated well daily solar radiation, soil temperature and moisture, and also captured the dynamics and magnitude of accumulated rice aboveground biomass and mineral nitrogen in the soil. The simulated daily N2O emissions over all three years investigated were generally in good agreement with field observations. Particularly well simulated were the peak N2O emissions induced by fertilizations, rainfall events or mid-season drainages. The model simulation also represented closely the inter-annuM variation in N2O emission. These validations imply that the model has the capability to capture the general characteristics of N2O emission from a typical rice-wheat rotation agro-ecosystem. Sensitivity analyses revealed that the simulated N2O emission is most sensitive to the fertilizer application rate and the soil organic matter content, but it is much less sensitive to variations in soil pH and texture, temperature, precipitation and crop residue incorporation rate under local conditions.

Fabricating GeO_2 passivation layer by N_2O plasma oxidation for Ge NMOSFETs application

In this paper, oxidation of Ge surface by N2O plasma is presented and experimentally demonstrated. Results show that 1.0-nm GeO2 is achieved after 120-s N20 plasma oxidation at 300 ℃. The GeO2/Ge interface is atomically smooth. The interface state density of Ge surface after N20 plasma passivation is about - 3 × 1011 cm-2.eV-1. With GeO2 passivation, the hysteresis of metal-oxide-semiconductor （MOS） capacitor with A1203 serving as gate dielectric is reduced to - 50 mV, compared with - 130 mV of the untreated one. The Fermi-level at GeO2/Ge interface is unpinned, and the surface potential is effectively modulated by the gate voltage.

Effect of Substitution Degree and the Calcination Temperature on the N₂O Decomposition over Zinc Cobaltite Catalysts

In this paper, a series of zinc cobaltite catalysts with the general formula Znx-Co1-xCo2O4 (x = 0.25, 0.50, 0.75 and 1.0) has been prepared using the co-precipitation method. Thermal analyzes (TGA and DTA) were used to follow up the thermal events accompanying the heat treatment of the parent mixture. Based on these results, the various parent mixtures were calcined at 500℃. The obtained solid catalysts were characterized by using XRD, FT-IR and N2-adsorption. The catalytic decomposition of N2O to N2 and O2 was carried out on the zinc-cobaltite catalysts. It was found that partial replacement of Co2+ by Zn2+ in Co3O4 spinel oxide led to a significant improvement in their N2O decomposition activity. Moreover, the catalytic activity was found to be depended on the calcination temperature utilized.

Plasma post oxidation of nitrocarburized AISI 4140 steel

Plasma nitrocarburizing and plasma oxidizing treatments were performed to improve the wear and corrosion resistance of AISI 4140 steel. Plasma nitrocarburizing was conducted for 3 h at 570 ℃ in the nitrogen, hydrogen and methane atmosphere to produce the ε-Fe2-3(N,C) phase. It was found that the compound layer produced by plasma nitrocarburising was predominantly composed of ε-phase, with a small proportion of γ′-Fe4(N,C) phase. The thickness of the compound layer was about 10 μm and the diffusion layer was about 300 μm in thickness, respectively. Plasma post oxidation was performed on the nitrocarburized samples with various oxygen/hydrogen ratio at a constant temperature of 500 ℃ for 1 h. The very thin magnetite (Fe3O4) layer 1-2 μm in thickness on top of the compound layer was obtained by plasma post oxidation. It was confirmed that the corrosion characteristics of the nitrocarburized compound layer can be further improved by the application of the superficial magnetite layer.

Rh_2O_3/monoclinic CePO_4 composite catalysts for N_2O decomposition and CO oxidation

CePO4 （in particular, monoclinic CePO4） has been rarely used to make supported catalysts. Herein, monoclinic CeP04 nanoparticles were prepared by calcining hexagonal CePO4 nanomds （prepared by precipitation） in air at 900 ℃. Monoclinic CePO4 nanowires were prepared by calcining hexagonal CePO4 nanowires （prepared by hydrothermal synthesis at 150 ℃） in air at 900 ℃. Both monoclinic CePO4 materials were used to support Rh2O3 by impregnation using Rh（NO3）3 as a precursor （followed by calcination）. The catalytic performance of Rh2O3/monoclinic CePO4 composite materials in N2O decomposition and CO oxidation was investigated. It was found that Rh2O3 supported on monoclinic CePO4 nanowims was much more active than Rh2O3 supported on monoclinic CePO4 nanoparticles. The stability of catalysts as a function of reaction time on stream was studied in both reactions. The influence of co-fed CO2, O2, and H2O on the catalytic activity in N20 decomposition was also studied. These catalysts were characterized by employing N2 adsorption-desorption, ICP-OES, XRD, TEM, XPS, H2-TPR, O2-TPD, and CO2-TPD. The correlation between physicochemical properties and catalytic properties was discussed.

Water regime-nitrogen fertilizer incorporation interaction：Field study on methane and nitrous oxide emissions from a rice agroecosystem in Harbin, China

Water regime and nitrogen（N） fertilizer are two important factors impacting greenhouse gases（GHG） emission from paddy field, whereas their effects have not been well studied in cold region. In this study, we conducted a two-year field experiment to study the impacts of water regime and N fertilizer on rice yields and GHG emissions in Harbin, China, a cold region located in high latitudes. Our results showed that intermittent irrigation significantly decreased methane（CH4） emission compared with continuous flooding, however,the decrement was far lower than the global average level. The N2O emissions were very small when flooded but peaked at the beginning of the disappearance of floodwater. The N fertilizer treatments increased CH4 emissions at low level（75 kg N/ha）. But both CH4 and N2O emissions were uninfluenced at the levels of 150 kg N/ha and 225 kg N/ha. Rice yields increased under intermittent irrigation and were highest at the level of 150 kg N/ha. From our results, we recommended that the intermittent irrigation and 150 kg N/ha as the ideal water regime-nitrogen fertilizer incorporation for this area to achieve low GHG emissions without impacting rice yields.

Adsorption of nitrous oxide on the(6,0) magnesium oxide nanotube

Nitrous oxide adsorption on the pristine （6,0） magnesium oxide nanotube was studied by using density functional theory calculations. We present the nature of the N2O interaction in selected sites of the nanotube. Adsorption energies corresponding to adsorption of the N2O on the nanotube were calculated to be in the range - 11.67 to -22.21 kJ mol- 1. Our results indicate that the N2O molecule has a weak physical adsorption on the pristine models due to weak Van der Waals interaction between the nanotubes and N2O molecule. The important results can be useful in production of the N2O sensors.

不同生境下氮沉降对土壤N_(2)O通量影响的整合分析

基于在我国开展的66个野外氮沉降模拟试验的290组数据,采用整合分析方法,探究实验样地特征(气候因子、土壤性质)和施氮因素对施氮后土壤N_(2)O通量变化的影响。结果表明:样地的年均降水量、年均温、自然氮沉降量和土壤C/N与施氮后N_(2)O通量增幅呈显著正相关,土壤pH与施氮后N_(2)O通量增幅呈显著负相关。湿地生态系统土壤对施氮最敏感,森林生态系统次之,草原生态系统最小。所有的样地因子中,土壤pH和C/N对施氮后N_(2)O通量变化幅度的影响最大。施加硝态氮后土壤N_(2)O通量增幅最大,施加尿素与铵态氮后N_(2)O通量增幅相当,而施加硝酸铵后N_(2)O通量增幅最小。综上,在准确评估和预测土壤N_(2)O通量对氮沉降的响应时,应综合考虑样地特征及氮源种类的影响。

The performance of nitrate-reducing Fe(Ⅱ)oxidation processes under variable initial Fe/N ratios:The fate of nitrogen and iron species

The Fe/N ratio is an important control on nitrate-reducing Fe(Ⅱ)oxidation processes that occur both in the aquatic environment and in wastewater treatment systems.The response of nitrate reduction,Fe oxidation,and mineral production to different initial Fe/N molar ratios in the presence of Paracoccus denitrificans was investigated in 132 h incubation experiments.A decrease in the nitrate reduction rate at 12 h occurred as the Fe/N ratio increased.Accumulated nitrite concentration at Fe/N ratios of 2–10 peaked at 12–84 h,and then decreased continuously to less than 0.1 mmol/L at the end of incubation.N_(2)O emission was promoted by high Fe/N ratios.Maximum production of N_(2) occurred at a Fe/N ratio of 6,in parallel with the highest mole proportion of N_(2) resulting from the reduction of nitrate(81.2%).XRD analysis and sequential extraction demonstrated that the main Fe minerals obtained from Fe(Ⅱ)oxidation were easily reducible oxides such as ferrihydrite(at Fe/N ratios of 1–2),and easily reducible oxides and reducible oxides(at Fe/N ratios of 3–10).The results suggest that Fe/N ratio potentially plays a critical role in regulating N_(2),N_(2)O emissions and Fe mineral formation in nitrate-reducing Fe(II)oxidation processes.