The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are u...The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.展开更多
A bench-scale anaerobic/anoxic/aerobic process-biological aerated filter （A^2/O-BAF） combined system was carded out to treat wastewater with lower C/N and C/P ratios. The A^2/O process was operated in a short aerobi...A bench-scale anaerobic/anoxic/aerobic process-biological aerated filter （A^2/O-BAF） combined system was carded out to treat wastewater with lower C/N and C/P ratios. The A^2/O process was operated in a short aerobic sludge retention time （SRT） for organic pollutants and phosphorus removal, and denitrification. The subsequent BAF process was mainly used for nitrification. The BAF effluent was partially returned to anoxic zone of the A^2/O process to provide electron acceptors for denitrification and anoxic P uptake. This unique system formed an environment for reproducing the denitdfying phosphate-accumulating organisms （DPAOs）. The ratio of DPAOs to phosphorus accumulating organisms （PAOs） could be maintained at 28% by optimizing the organic loads in the anaerobic zone and the nitrate loads into the anoxic zone in the A^2/O process. The aerobic phosphorus over-uptake and discharge of excess activated sludge was the main mechanism of phosphorus removal in the combined system. The aerobic SRT of the A^2/O process should meet the demands for the development of aerobic PAOs and the restraint on the nitrifiers growth, and the contact time in the aerobic zone of the A^2/O process should be longer than 30 min, which ensured efficient phosphorus removal in the combined system. The adequate BAF effluent return rates should be controlled with 1--4 mg/L nitrate nitrogen in the anoxic zone effluent of A^2/O process to achieve the optimal nitrogen and phosphorus removal efficiencies.展开更多
A lab-incubation experiment was conducted to investigate the effects of different forms of nitrogen application （ammonium, NH4＋-N; nitrate, NO3--N; and amide-N, NH2-N） and different concentrations （40, 200 and 800...A lab-incubation experiment was conducted to investigate the effects of different forms of nitrogen application （ammonium, NH4＋-N; nitrate, NO3--N; and amide-N, NH2-N） and different concentrations （40, 200 and 800 mg L-1） on N2O emission from the fluvo-aquic soil subjected to a freezing-thawing cycling. N2O emission sharply decreased at the start of soil freezing, and then showed a smooth line with soil freezing. In subject to soil thawing, N2O emission increased and reached a peak at the initial thawing stage. The average N2O emissions with addition of NH4＋-N, NO3 -N and NH2-N are 119.01, 611.61 and 148. 22 ug m-2 h-1, respectively, at the concentration of 40 mg L-1; 205.28, 1 084.40 and 106.13 ug m2 h-1 at the concentration of 200 mg L-1; and 693.95, 1 820.02 and 49.74 ug m-2 h4 at the concentration of 800 mg L-1. The control is only 100.35 ug m-2 h-1. N2O emissions with addition of NH4＋-N and NO3--N increased with increasing concentration, by ranging from 17.49 to 425.67% for NH4＋-N, and from 563.38 to 1458.6% for NO3--N compared with control. There was a timelag for N2O emission to reach a steady state with an increase of concentration. In contrast, by adding NH2-N to soil, N2O emission decreased with increasing concentration. In sum, NH4＋-N or NO3--N fertilizer incorporated in soil enhanced the cumulative N2O emission from the fluvo-aquic soil relative to amide-N. This study suggested that ammonium and nitrate concentration in overwintering water should be less than 200 and 40 mg L-1 in order to reduce N2O emissions from soil, regardless of amide-N.展开更多
A two-dimensional （2D） fluid model is presented to study the behavior of silicon plasma mixed with SiH4 , N2 , and NH3 in a radio-frequency capacitively coupled plasma （CCP） reactor. The plasma–wall interaction ...A two-dimensional （2D） fluid model is presented to study the behavior of silicon plasma mixed with SiH4 , N2 , and NH3 in a radio-frequency capacitively coupled plasma （CCP） reactor. The plasma–wall interaction （including the deposition） is modeled by using surface reaction coefficients. In the present paper we try to identify, by numerical simulations, the effect of variations of the process parameters on the plasma properties. It is found from our simulations that by increasing the gas pressure and the discharge gap, the electron density profile shape changes continuously from an edge-high to a center-high, thus the thin films become more uniform. Moreover, as the N2 /NH3 ratio increases from 6/13 to 10/9, the hydrogen content can be significantly decreased, without decreasing the electron density significantly.展开更多
以丙二腈为原料,采用4个连续反应,得到3-氨基-4-氨基肟基呋咱(Ⅰ),经Sandmeyer反应生成3-氨基-4-酰氯肟基呋咱(Ⅱ),再与3-氯-4-氟苯胺反应得到吲哚胺2,3-双加氧酶抑制剂4-氨基-N-(3-氯-4-氟苯基)-N'-羟基-1,2,5-口恶二唑-3-甲脒(INC...以丙二腈为原料,采用4个连续反应,得到3-氨基-4-氨基肟基呋咱(Ⅰ),经Sandmeyer反应生成3-氨基-4-酰氯肟基呋咱(Ⅱ),再与3-氯-4-氟苯胺反应得到吲哚胺2,3-双加氧酶抑制剂4-氨基-N-(3-氯-4-氟苯基)-N'-羟基-1,2,5-口恶二唑-3-甲脒(INCB024360)。Ⅱ的工艺优化路线:在0℃下,加入化合物Ⅰ2.0 g,浓盐酸6.5 m L,Na NO20.96 g,Cu Cl 2.87 g,水8 m L,反应时间5 h;INCB024360的工艺优化路线:25℃下,加入反应物Ⅱ1.0 g,3-氯-4-氟苯胺1.58 g,三乙胺0.17 m L,无水乙醇25 m L,反应时间5 h。总产率从10.0%提高到43.1%,HPLC纯度为99.6%,其结构经1HMOL/LR,13CMOL/LR,MS表征。展开更多
基金Y.C.and J.C.are contributed equally to the paper.Project supported by the National Natural Science Foundation of China (U19A2017)the Fundamental Research Funds for the Central South University and the Australian Research Council (DP180100731 and DP180100568)。
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.
文摘A bench-scale anaerobic/anoxic/aerobic process-biological aerated filter （A^2/O-BAF） combined system was carded out to treat wastewater with lower C/N and C/P ratios. The A^2/O process was operated in a short aerobic sludge retention time （SRT） for organic pollutants and phosphorus removal, and denitrification. The subsequent BAF process was mainly used for nitrification. The BAF effluent was partially returned to anoxic zone of the A^2/O process to provide electron acceptors for denitrification and anoxic P uptake. This unique system formed an environment for reproducing the denitdfying phosphate-accumulating organisms （DPAOs）. The ratio of DPAOs to phosphorus accumulating organisms （PAOs） could be maintained at 28% by optimizing the organic loads in the anaerobic zone and the nitrate loads into the anoxic zone in the A^2/O process. The aerobic phosphorus over-uptake and discharge of excess activated sludge was the main mechanism of phosphorus removal in the combined system. The aerobic SRT of the A^2/O process should meet the demands for the development of aerobic PAOs and the restraint on the nitrifiers growth, and the contact time in the aerobic zone of the A^2/O process should be longer than 30 min, which ensured efficient phosphorus removal in the combined system. The adequate BAF effluent return rates should be controlled with 1--4 mg/L nitrate nitrogen in the anoxic zone effluent of A^2/O process to achieve the optimal nitrogen and phosphorus removal efficiencies.
基金supported by the Key Tech-nologies R&D Program of China during the 11th Five-Year Plan period (2006BAD17B02)Central Public Research Institutes Basic Funds for Research and Development (Institute of Agro-Environmental Protection,Ministry of Agriculture), China
文摘A lab-incubation experiment was conducted to investigate the effects of different forms of nitrogen application （ammonium, NH4＋-N; nitrate, NO3--N; and amide-N, NH2-N） and different concentrations （40, 200 and 800 mg L-1） on N2O emission from the fluvo-aquic soil subjected to a freezing-thawing cycling. N2O emission sharply decreased at the start of soil freezing, and then showed a smooth line with soil freezing. In subject to soil thawing, N2O emission increased and reached a peak at the initial thawing stage. The average N2O emissions with addition of NH4＋-N, NO3 -N and NH2-N are 119.01, 611.61 and 148. 22 ug m-2 h-1, respectively, at the concentration of 40 mg L-1; 205.28, 1 084.40 and 106.13 ug m2 h-1 at the concentration of 200 mg L-1; and 693.95, 1 820.02 and 49.74 ug m-2 h4 at the concentration of 800 mg L-1. The control is only 100.35 ug m-2 h-1. N2O emissions with addition of NH4＋-N and NO3--N increased with increasing concentration, by ranging from 17.49 to 425.67% for NH4＋-N, and from 563.38 to 1458.6% for NO3--N compared with control. There was a timelag for N2O emission to reach a steady state with an increase of concentration. In contrast, by adding NH2-N to soil, N2O emission decreased with increasing concentration. In sum, NH4＋-N or NO3--N fertilizer incorporated in soil enhanced the cumulative N2O emission from the fluvo-aquic soil relative to amide-N. This study suggested that ammonium and nitrate concentration in overwintering water should be less than 200 and 40 mg L-1 in order to reduce N2O emissions from soil, regardless of amide-N.
基金Project supported by the China Postdoctoral Science Foundation (Grant No. 2012M511603)the National Natural Science Foundation of China (Grant Nos. 11105057 and 10775025)+1 种基金the Natural Science Foundation of Hubei Province of China (Grant No. 2007ABA035)the Program for New Century Excellent Talents in University of China (Grant No. NCET-08-0073)
文摘A two-dimensional （2D） fluid model is presented to study the behavior of silicon plasma mixed with SiH4 , N2 , and NH3 in a radio-frequency capacitively coupled plasma （CCP） reactor. The plasma–wall interaction （including the deposition） is modeled by using surface reaction coefficients. In the present paper we try to identify, by numerical simulations, the effect of variations of the process parameters on the plasma properties. It is found from our simulations that by increasing the gas pressure and the discharge gap, the electron density profile shape changes continuously from an edge-high to a center-high, thus the thin films become more uniform. Moreover, as the N2 /NH3 ratio increases from 6/13 to 10/9, the hydrogen content can be significantly decreased, without decreasing the electron density significantly.
文摘以丙二腈为原料,采用4个连续反应,得到3-氨基-4-氨基肟基呋咱(Ⅰ),经Sandmeyer反应生成3-氨基-4-酰氯肟基呋咱(Ⅱ),再与3-氯-4-氟苯胺反应得到吲哚胺2,3-双加氧酶抑制剂4-氨基-N-(3-氯-4-氟苯基)-N'-羟基-1,2,5-口恶二唑-3-甲脒(INCB024360)。Ⅱ的工艺优化路线:在0℃下,加入化合物Ⅰ2.0 g,浓盐酸6.5 m L,Na NO20.96 g,Cu Cl 2.87 g,水8 m L,反应时间5 h;INCB024360的工艺优化路线:25℃下,加入反应物Ⅱ1.0 g,3-氯-4-氟苯胺1.58 g,三乙胺0.17 m L,无水乙醇25 m L,反应时间5 h。总产率从10.0%提高到43.1%,HPLC纯度为99.6%,其结构经1HMOL/LR,13CMOL/LR,MS表征。
