Nitrogen oxides(NO_(x))are crucial in tropospheric photochemical ozone(O_(3))production and oxidation capacity.Currently,the widely used NO_(x)measurement technique is chemiluminescence(CL)(CL-NO_(x)),which tends to o...Nitrogen oxides(NO_(x))are crucial in tropospheric photochemical ozone(O_(3))production and oxidation capacity.Currently,the widely used NO_(x)measurement technique is chemiluminescence(CL)(CL-NO_(x)),which tends to overestimate NO_(2)due to atmospheric oxidation products of NO_(x)(i.e.,NO_(z)).We developed and characterized a NO_(x)measurement system using the cavity attenuated phase shift(CAPS)technique(CAPS-NO_(x)),which is free from interferences with nitrogen-containing species.The NO_(x)measured by the CAPS-NO_(x)and CL-NO_(x)analyzers were compared.Results show that both analyzers showed consistent measurement results for NO,but the NO_(2)measured by the CAPS-NO_(x)analyzer(NO_(2)_CAPS)was mostly lower than that measured by the CL-NO_(x)analyzer(NO_(2)_CL),which led to the deviations in O_(3)formation sensitivity regime and O_(x)(=O_(3)+NO_(2))sources(i.e.,regional background and photochemically produced O_(x))determined by the ozone production efficiencies(OPE)calculated from NO_(2)_CL and NO_(2)_CAPS.Overall,OPE_CL exceeded OPE_CAPS by 18.9%,which shifted 3 out of 13 observation days from the VOCs-limited to the transition regime when judging using OPE_CL,as compared to calculations using OPE_CAPS.During the observation period,days dominated by regional background O_(x)accounted for 46%and 62%when determined using NO_(2)_CL and NO_(2)_CAPS,respectively.These findings suggest that the use of the CL-NO_(x)analyzer tends to underestimate both the VOCs-limited regime and the regional background O_(x)dominated days.The newly built CAPS-NO_(x)analyzer here can promote the accurate measurement of NO_(2),which is meaningful for diagnosing O_(3)formation regimes and O_(x)sources.展开更多
The electrochemical nitrogen reduction reaction(NRR)under ambient conditions presents a promising approach for the eco-friendly and sustainable synthesis of ammonia,with a continuous emergence of potential electrocata...The electrochemical nitrogen reduction reaction(NRR)under ambient conditions presents a promising approach for the eco-friendly and sustainable synthesis of ammonia,with a continuous emergence of potential electrocatalysts.However,the low solubility and limited diffusion of N_(2)significantly hinder the achievement of satisfactory performance.In this context,we report an effective strategy to enhance NRR activity by introducing a metal-organic framework(MOF)membrane,specifically MIL-53(Al),onto a perovskite oxide(LiNbO_(3)),denoted as LN@MIL-X(X=0.2,0.4 and 0.6).The MIL-53(Al)membrane selectively recognizes and concentrates N_(2)at the catalyst interface while simultaneously repelling water molecules,thereby inhibiting the hydrogen evolution reaction(HER).This ultrathin nanostructure significantly improves the NRR performance of LN@MIL-X compared to pristine LiNbO_(3).Notably,LN@MIL-0.4 exhibits a maximum NH_(3)yield of 45.25 mg h^(-1)mg_(cat.)^(-1)with an impressive Faradaic efficiency(FE)of 86.41%at-0.45 V versus RHE in 0.1 mol L^(-1)Na_(2)SO_(4).This work provides a universal strategy for the design and synthesis of perovskite oxide electrocatalysts,facilitating high-efficiency ammonia synthesis.展开更多
Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and re...Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.展开更多
In order to improve the total-dose radiation har dness of the buried oxides(BOX) in the structure of separation-by-implanted-oxygen(SIMOX) silicon-on-insulator(SOI),nitrogen ions are implanted into the buried oxides w...In order to improve the total-dose radiation har dness of the buried oxides(BOX) in the structure of separation-by-implanted-oxygen(SIMOX) silicon-on-insulator(SOI),nitrogen ions are implanted into the buried oxides with two different doses,2×10 15 and 3×10 15 cm -2 ,respectively.The experimental results show that the radiation hardness of the buried oxides is very sensitive to the doses of nitrogen implantation for a lower dose of irradiation with a Co-60 source.Despite the small difference between the doses of nitrogen implantation,the nitrogen-implanted 2×10 15 cm -2 BOX has a much higher hardness than the control sample (i.e.the buried oxide without receiving nitrogen implantation) for a total-dose irradiation of 5×104rad(Si),whereas the nitrogen-implanted 3×10 15 cm -2 BOX has a lower hardness than uhe control sample.However,this sensitivity of radiation hardness to the doses of nitrogen implantation reduces with the increasing total-dose of irradiation (from 5×104 to 5×105rad (Si)).The radiation hardness of BOX is characterized by MOS high-frequency (HF) capacitance-voltage (C-V) technique after the top silicon layers are removed.In addition,the abnormal HF C-V curve of the metal-silicon-BOX-silicon(MSOS) structure is observed and explained.展开更多
A series of meso‐microporous copper‐supporting chabazite molecular sieve（CuSAPO‐34） catalysts with excellent performance in low‐temperature ammonia selective catalytic reduction（NH3‐SCR）have been synthesized ...A series of meso‐microporous copper‐supporting chabazite molecular sieve（CuSAPO‐34） catalysts with excellent performance in low‐temperature ammonia selective catalytic reduction（NH3‐SCR）have been synthesized via a one‐pot hydrothermal crystallization method. The physicochemical properties of the catalysts were characterized by scanning electron microscopy, transmission electron microscopy, N2 adsorption‐desorption measurements, X‐ray diffraction, 27 Al magic angle spinning nuclear magnetic resonance, diffuse reflectance ultraviolet‐visible spectroscopy, inductively coupled plasma‐atomic emission spectroscopy, X‐ray photoelectron spectroscopy, temperature‐programmed reduction measurements, and electron paramagnetic resonance analysis. The formation of micro‐mesopores in the Cu‐SAPO‐34 catalysts decreases diffusion resistance and greatly improves the accessibility of reactants to catalytic active sites. The main active sites for NH3‐SCR reaction are the isolated Cu^2＋ species displaced into the ellipsoidal cavity of the Cu‐SAPO‐34 catalysts.展开更多
Dielectric barrier discharge （DBD） plasma was utilized to oxidize NO contained in the exhaust gas to NO2, ultimately improve the selective catalytic reduction of nitrogen oxides （NOx）. In the one case, DBD was cre...Dielectric barrier discharge （DBD） plasma was utilized to oxidize NO contained in the exhaust gas to NO2, ultimately improve the selective catalytic reduction of nitrogen oxides （NOx）. In the one case, DBD was created directly in the exhaust gas （direct application）, and in the an other case, ozone produced by DBD was injected into the exhaust gas （indirect application）. A comparative study between such direct and indirect applications of DBD plasma was made in terms of the NOx removal efficiency and the energy consumption. The NO2 content in the exhaust gas was changed by the voltage applied to the DBD device （for direct application） or by the amount of ozone added to the exhaust gas （for indirect application）. In both cases, NO was easily oxidized to NO2, and the change in NO2 content largely affected the NOx removal performance of the catalytic reactor placed downstream, where both NO and NO2 were reduced to N2 in the presence of ammonia as the reducing agent. The experiments were primarily concerned with the effect of reaction temperature on the catalytic NOx reduction at various NO2 contents. The direct and indirect applications of DBD were found to remarkably improve the catalytic NOx reduction, especially at low temperatures.展开更多
A single-stage plasma-catalytic reactor in which catalytic materials werepacked was used to remove nitrogen oxides. The packing material was scoria being made of variousmetal oxides including Al_2O_3, MgO, TiO_2, etc....A single-stage plasma-catalytic reactor in which catalytic materials werepacked was used to remove nitrogen oxides. The packing material was scoria being made of variousmetal oxides including Al_2O_3, MgO, TiO_2, etc. Scoria was able to act not only as dielectricpellets but also as a catalyst in the presence of reducing agent such as ethylene and ammonia.Without plasma discharge, scoria did not work well as a catalyst in the temperature range of 100 ℃to 200 ℃, showing less than 10% of NOx removal efficiency. When plasma is produced inside thereactor, the NOx removal efficiency could be increased to 60% in this temperature range.展开更多
The potential of using denitrifying and nitrifying concurrent biofilters for the removal of nitrogen oxides from synthetic gas streams was studied under the condition of high oxygen concentration. It was found that ...The potential of using denitrifying and nitrifying concurrent biofilters for the removal of nitrogen oxides from synthetic gas streams was studied under the condition of high oxygen concentration. It was found that more than 85% of nitric oxide was removed from synthetic combustion gas-streams which contained 20% oxygen and 350 μL/L NO, with a residence time of 60 seconds. In the process, it was found that the existing of oxygen showed no evident negative effect on the efficiency of nitrogen removal.展开更多
This paper reports the studies conducted on removal of oxides ofnitrogen (NOx) from diesel engine exhaust using electrical dischargeplasma combined with adsorbing materials such as molecular sieves.This study is being...This paper reports the studies conducted on removal of oxides ofnitrogen (NOx) from diesel engine exhaust using electrical dischargeplasma combined with adsorbing materials such as molecular sieves.This study is being reported for the first time. The exhaust is takenfrom a diesel engine of 6 kW under no load conditions. Thecharacteristic behavior of a pulse energized dielectric barrierdischarge reactor in the diesel exhaust treatment is reported. TheNOx removal was not significant (36/100) when the reactor without anypacking was used.展开更多
Nitrogen oxides（NOx：NO,NO2）are a concern due to their adverse health effects.Diesel engine transport sector is the major emitter of NOx.The regulations have been strengthened and to comply with them,one of the two ...Nitrogen oxides（NOx：NO,NO2）are a concern due to their adverse health effects.Diesel engine transport sector is the major emitter of NOx.The regulations have been strengthened and to comply with them,one of the two methods commonly used is the selective catalytic reduction of NOxby NH3（NH3-SCR）,NH3being supplied by the in-situ hydrolysis of urea.Efficiency and durability of the catalyst for this process are highly required.Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800℃.In this study,very active catalysts for the NH3-SCR of NOxwere prepared by using a silicoaluminophosphate commercial zeolite as copper host structure.Characterizations by X-ray diffraction（XRD）,scanning electron microscopy（SEM）and temperature programmed desorption of ammonia（NH3-TPD）showed that this commercial zeolite was hydrothermally stable up to 850℃ and,was able to retain some structural properties up to950℃.After hydrothermal treatment at 850℃,the NOxreduction efficiency into NH3-SCR depends on the copper content.The catalyst with a copper content of 1.25 wt.%was the most active.The difference in activity was much more important when using NO than the fast NO/NO2reaction mixture.展开更多
Based on observational data of ozone （O3） and nitrogen oxide （NOx） mixing ratios on the ground and at high altitude in urban areas of Beijing during a period of six days in November 2011, the temporal and spatial ...Based on observational data of ozone （O3） and nitrogen oxide （NOx） mixing ratios on the ground and at high altitude in urban areas of Beijing during a period of six days in November 2011, the temporal and spatial characteristics of mixing ratios were analyzed. The major findings include： urban O3 mixing ratios are low and NOx mixing ratios are always high near the road in November. Vertical variations of the gases are significantly different in and above the planetary boundary layer. The mixing ratio of O3 is negatively correlated with that of NOx and they are positively correlated with air temperature, which is the main factor directly causing vertical variation of O3 and NOx mixing ratios at 600-2100 m altitude. The NOx mixing ratios elevated during the heating period, while the O3 mixing ratios decreased： these phenomena are more significant at high altitudes compared to lower altitudes. During November, air masses in the urban areas of Beijing are brought by northwesterly winds, which transport O3 and NOx at low mixing ratios. Due to Beijing＇s natural geographical location, northwest air currents arc beneficial to the dilution and dispersion of pollutants, which can result in lower O3 and NOx background values in the Beijing urban area.展开更多
Nitrogen oxides(NO_2 and NO)are absorbed by tributyl phosphorate(TBP)to fom a new complex mixture of TBP-NO_x. which is used as a selective oddizing agent to oxidize benzylalcohols to corresponding sldehydes or ketone...Nitrogen oxides(NO_2 and NO)are absorbed by tributyl phosphorate(TBP)to fom a new complex mixture of TBP-NO_x. which is used as a selective oddizing agent to oxidize benzylalcohols to corresponding sldehydes or ketones In high yield. In the reaction process, nitrogen oxides are llberated mildly and mainly reduced to nitrogen, while tributyl phosphorate is recovered end recycled.展开更多
A series of nanosized ion-doped TiO2 catalysts with different ion content （between 0.1 at.% and 1.0 at.%） have been prepared by wet impregnation method and investigated with respect to their behavior for UV photocat...A series of nanosized ion-doped TiO2 catalysts with different ion content （between 0.1 at.% and 1.0 at.%） have been prepared by wet impregnation method and investigated with respect to their behavior for UV photocatalytic oxidation of nitric oxide. The catalytic activity was correlated with structural, electronic and surface examinations of the catalysts using X-ray diffraction analysis （XRD）, ultraviolet-visible （UV-Vis） absorption spectroscopy, transmission electron microscopy （TEM）, energy disperse spectrometer （EDS） and high resolution-transmission electron microscopy （HR-TEM） techniques. An enhancement of the photocatalytic activity was observed for Zn2＋ doping catalyst ranged from 0.1 at.% to 1.0 at.% which was attributed to the lengthened lifetime of electrons and holes. The improvement in photocatalytic activity could be also observed with the low doping concentration of Cr^3＋ （0.1 at.%）. However, the doping of Fe^3＋, Mo^6＋, Mn^2＋ and the high doping concentration of Cr^3＋ had no contribution to photocatalytic activity of nitric oxide.展开更多
Mn-Ni oxides with different compositions were prepared using standard co-precipitation(CP) and urea hydrolysis-precipitation(UH) methods and optimized for the selective catalytic reduction of nitrogen oxides(NOx) by N...Mn-Ni oxides with different compositions were prepared using standard co-precipitation(CP) and urea hydrolysis-precipitation(UH) methods and optimized for the selective catalytic reduction of nitrogen oxides(NOx) by NH3 at low temperature.Mn((2))Ni(1)Ox-CP and Mn(2)Ni(1)Ox-UH(with Mn:Ni molar ratio of 2:1) catalysts showed almost identical selective catalytic reduction(SCR) catalytic activity,with about 96% NOx conversion at 750 C and-99%in the temperature range from 100 to 250℃.X-ray diffraction(XRD) results showed that Mn(2)Ni(1)Ox-CP and Mn(2)Ni(1)Ox-UH catalysts crystallized in the form of Mn2NiO4 and MnO2-Mn2NiO4 spinel,respectively.The latter gave relatively good selectivity to N2,which might be due to the presence of the MnO2 phase and high metal-O binding energy,resulting in low dehydrogenation ability.According to the results of various characterization methods,it was found that a high density of surface chemisorbed oxygen species and efficient electron transfer between Mn and Ni in the crystal structure of Mn2NiO4 spinel played important roles in the high-efficiency SCR activity of these catalysts.Mn(2)Ni(1)Ox catalysts presented good resistance to H2O or/and SO2 with stable activity,which benefited from the Mn2NiO4 spinel structure and Eley-Rideal mechanism,with only slight effects from SO2.展开更多
An electric discharge plasma reactor combined with a catalytic reactor wasstudied for removing nitrogen oxides. To understand the combined process thoroughly, dischargeplasma and catalytic process were separately stud...An electric discharge plasma reactor combined with a catalytic reactor wasstudied for removing nitrogen oxides. To understand the combined process thoroughly, dischargeplasma and catalytic process were separately studied first, and then the two processes were combinedfor the study. The plasma reactor was able to oxidize NO to NO_2 well although the oxidation ratedecreased with temperature. The plasma reactor alone did not reduce the NO_x (NO+NO_2) leveleffectively, but the increase in the ratio of NO_2 to NO as a result of plasma discharge led to theenhancement of NO_x removal efficiency even at lower temperatures over the catalyst surface(V_2O_5-WO_3/TiO_2). At a gas temperature of 100℃, the NO_x removal efficiency obtained using thecombined plasma catalytic process was 88% for an energy input of 36 eV/molecule or 30 J/l.展开更多
We evaluate nitrogen oxides pollution in Takamatsu and Utazu area in Kagawa prefecture, Japan. Annually observations for nitrogen oxides (nitrogen dioxide;NO2, nitric oxide;NO) (1990-2007) were obtained from data base...We evaluate nitrogen oxides pollution in Takamatsu and Utazu area in Kagawa prefecture, Japan. Annually observations for nitrogen oxides (nitrogen dioxide;NO2, nitric oxide;NO) (1990-2007) were obtained from data base of Kagawa prefecture, Japan. Changes in NO2 and NO in Takamatsu and Utazu area were evaluated and compared. In 2007, NO2, NO and NO2 + NO (ppm) in Takamatsu area were higher than those in Utazu area. However, NO2 /NO + NO2 in Takamatsu area was lower than that in Utazu area. From 1990 to 2007, mean of NO2 in a day over the level of 0.06 ppm was 30 days in Takamatsu area and only one day in Utazu area. Mean of NO2, NO and NO2 + NO was significantly higher and NO2/NO + NO2 was lower in Takamatsu area than that in Utazu area. In addition, NO2, NO and NO2 + NO were negatively correlated and NO2/NO + NO2 was positively correlated with years (1990-2007) in Takamatsu area. The level of nitrogen oxides pollution in Utazu area was lower than Takamatsu area. Further observation is required for preventing nitrogen oxides pollution in Kagawa prefecture, Japan.展开更多
V-Pd/γ-Al2O3-TiO2 catalysts with different vanadium contents were prepared by a combined sol-gel and impregnation method. X-ray diffraction （XRD）, N2 adsorption-desorption （BET）, X-ray photoelectron spectroscopy ...V-Pd/γ-Al2O3-TiO2 catalysts with different vanadium contents were prepared by a combined sol-gel and impregnation method. X-ray diffraction （XRD）, N2 adsorption-desorption （BET）, X-ray photoelectron spectroscopy （XPS） and catalytic removal of ethanol, acetaldehyde and nitrogen oxides at low temperature （〈300 ？C） were used to assess the properties of the catalysts. The results showed that the sample with 1wt% vanadium exhibited an excellent catalytic performance for simultaneous removal of ethanol, acetaldehyde and nitrogen oxides. The conversions of ethanol, acetaldehyde and nitrogen oxides at 250 ？C were 100%, 74.4% and 98.7%, respectively. V-Pd/γ-Al2O3-TiO2 catalyst with 1 wt% vanadium showed the largest surface area and higher dispersion of vanadium oxide on the catalyst surface, and possessed a larger mole fraction of V4＋ species and unique PdO species on the surface, which can be attributed to the strong synergistic effect among palladium, vanadium and the carriers. The higher activity of V-Pd/γ-Al2O3-TiO2 catalyst is related to the V4＋ and Pd2＋ species on the surface, which might be favorable for the formation of active sites.展开更多
Outdoor air quality, building materials, HVAC （Heating, Ventilation, Air Conditioning） systems and people activity are important factors in human exposition of polluted indoor air. The degree of signification varies...Outdoor air quality, building materials, HVAC （Heating, Ventilation, Air Conditioning） systems and people activity are important factors in human exposition of polluted indoor air. The degree of signification varies in dependence on pollution character and its sources. Buildings eliminate significantly people exposition of outdoor pollutants, but on the other hand, buildings are significant source of indoor pollution. The contamination of indoor air is largely from the use of gas for heating and cooking appliances. A comprehensive analysis of indoor air pollution by nitrogen oxides shows that the extent of indoor air pollution and consequent exposure varies as a result of many factors mainly the differing dislribution of appliances and their level of use. This study aims to formulate a mathematical model for the production of nitrogen oxides indoors. The physical processes that determine the concentrations of indoor nitrogen oxides as a function of outdoor concentrations, indoor emission rates and building characteristics have been mathematically described. The mathematical model developed has been parameterized for typical Slovak residences. The modeling of the occurrence of indoor nitrogen oxides and verification of the model is presented in this paper.展开更多
The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation ...The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.展开更多
Electrocatalytic production of ammonia from dinitrogen is considered as a sustainable alternative to the energy-demanding and pollutive Haber-Bosch process.A promising class of materials for selective nitrogen reducti...Electrocatalytic production of ammonia from dinitrogen is considered as a sustainable alternative to the energy-demanding and pollutive Haber-Bosch process.A promising class of materials for selective nitrogen reduction(NRR)corresponds to transition-metal oxides given that these electrodes do not show a high activity toward the competing hydrogen evolution reaction.So far,density functional theory calculations have been used to comprehend trends in a class of materials by using the concept of scaling relations and volcano plots.This thermodynamic theory pinpoints that either the formation of the*NNH adsorbate or the formation of ammonia are reconciled with the potential-determining reaction steps.Thus,the development of NRR catalyst has largely focused on the optimization of these two elementary processes.In the present contribution,overpotential and kinetic effects are factored into the volcano plot for the NRR over transition-metal oxides by making use of the recently introduced activity descriptor G_(max)(η).It is illustrated that the thermodynamic volcano picture is too simplistic as the limiting reaction step may alter close to the volcano apex:there,particularly surface reactions may govern the reaction rate.In addition,it is demonstrated how to include the formation of hydrazine as a competing side reaction into the volcano plot,which is of importance for weak binding*NNH catalysts where the formation of hydrazine may compete with the formation of ammonia.Given that the outlined methodology in this manuscript is universal and not restricted to the class of transition-metal oxides,the presented kinetic volcano picture may contribute to the development of NRR catalysts for nitrogen fixation.展开更多
基金supported by the Natural Science Foundation of Guangdong Province(No.2020A1515110526)the Key-Area Research and Development Programof Guangdong Province(No.2020B1111360003)the National Natural Science Foundation of China(No.42305096).
文摘Nitrogen oxides(NO_(x))are crucial in tropospheric photochemical ozone(O_(3))production and oxidation capacity.Currently,the widely used NO_(x)measurement technique is chemiluminescence(CL)(CL-NO_(x)),which tends to overestimate NO_(2)due to atmospheric oxidation products of NO_(x)(i.e.,NO_(z)).We developed and characterized a NO_(x)measurement system using the cavity attenuated phase shift(CAPS)technique(CAPS-NO_(x)),which is free from interferences with nitrogen-containing species.The NO_(x)measured by the CAPS-NO_(x)and CL-NO_(x)analyzers were compared.Results show that both analyzers showed consistent measurement results for NO,but the NO_(2)measured by the CAPS-NO_(x)analyzer(NO_(2)_CAPS)was mostly lower than that measured by the CL-NO_(x)analyzer(NO_(2)_CL),which led to the deviations in O_(3)formation sensitivity regime and O_(x)(=O_(3)+NO_(2))sources(i.e.,regional background and photochemically produced O_(x))determined by the ozone production efficiencies(OPE)calculated from NO_(2)_CL and NO_(2)_CAPS.Overall,OPE_CL exceeded OPE_CAPS by 18.9%,which shifted 3 out of 13 observation days from the VOCs-limited to the transition regime when judging using OPE_CL,as compared to calculations using OPE_CAPS.During the observation period,days dominated by regional background O_(x)accounted for 46%and 62%when determined using NO_(2)_CL and NO_(2)_CAPS,respectively.These findings suggest that the use of the CL-NO_(x)analyzer tends to underestimate both the VOCs-limited regime and the regional background O_(x)dominated days.The newly built CAPS-NO_(x)analyzer here can promote the accurate measurement of NO_(2),which is meaningful for diagnosing O_(3)formation regimes and O_(x)sources.
基金supported by the National Natural Science Foundation of China(No.U22A20418,22075196)the Research Project Supported by Shanxi Scholarship Council of China(2022–050).
文摘The electrochemical nitrogen reduction reaction(NRR)under ambient conditions presents a promising approach for the eco-friendly and sustainable synthesis of ammonia,with a continuous emergence of potential electrocatalysts.However,the low solubility and limited diffusion of N_(2)significantly hinder the achievement of satisfactory performance.In this context,we report an effective strategy to enhance NRR activity by introducing a metal-organic framework(MOF)membrane,specifically MIL-53(Al),onto a perovskite oxide(LiNbO_(3)),denoted as LN@MIL-X(X=0.2,0.4 and 0.6).The MIL-53(Al)membrane selectively recognizes and concentrates N_(2)at the catalyst interface while simultaneously repelling water molecules,thereby inhibiting the hydrogen evolution reaction(HER).This ultrathin nanostructure significantly improves the NRR performance of LN@MIL-X compared to pristine LiNbO_(3).Notably,LN@MIL-0.4 exhibits a maximum NH_(3)yield of 45.25 mg h^(-1)mg_(cat.)^(-1)with an impressive Faradaic efficiency(FE)of 86.41%at-0.45 V versus RHE in 0.1 mol L^(-1)Na_(2)SO_(4).This work provides a universal strategy for the design and synthesis of perovskite oxide electrocatalysts,facilitating high-efficiency ammonia synthesis.
基金supported by National Natural Science Fundation of China(Nos.52170086,22308194,U22A20423)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Taishan Scholars Program of Shandong Province(No.tsqn202211012)Shandong Provincial Excellent Youth(No.ZR2022YQ47)。
文摘Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.
文摘In order to improve the total-dose radiation har dness of the buried oxides(BOX) in the structure of separation-by-implanted-oxygen(SIMOX) silicon-on-insulator(SOI),nitrogen ions are implanted into the buried oxides with two different doses,2×10 15 and 3×10 15 cm -2 ,respectively.The experimental results show that the radiation hardness of the buried oxides is very sensitive to the doses of nitrogen implantation for a lower dose of irradiation with a Co-60 source.Despite the small difference between the doses of nitrogen implantation,the nitrogen-implanted 2×10 15 cm -2 BOX has a much higher hardness than the control sample (i.e.the buried oxide without receiving nitrogen implantation) for a total-dose irradiation of 5×104rad(Si),whereas the nitrogen-implanted 3×10 15 cm -2 BOX has a lower hardness than uhe control sample.However,this sensitivity of radiation hardness to the doses of nitrogen implantation reduces with the increasing total-dose of irradiation (from 5×104 to 5×105rad (Si)).The radiation hardness of BOX is characterized by MOS high-frequency (HF) capacitance-voltage (C-V) technique after the top silicon layers are removed.In addition,the abnormal HF C-V curve of the metal-silicon-BOX-silicon(MSOS) structure is observed and explained.
基金supported by the National Natural Science Foundation of China(2137626121173270)+4 种基金the National High Technology Research and Development Program of China(863 Program2015AA034603)the Beijing Natural Science Foundation(2142027)the China University of Petroleum Fund(201300071100072462015QZDX04)~~
文摘A series of meso‐microporous copper‐supporting chabazite molecular sieve（CuSAPO‐34） catalysts with excellent performance in low‐temperature ammonia selective catalytic reduction（NH3‐SCR）have been synthesized via a one‐pot hydrothermal crystallization method. The physicochemical properties of the catalysts were characterized by scanning electron microscopy, transmission electron microscopy, N2 adsorption‐desorption measurements, X‐ray diffraction, 27 Al magic angle spinning nuclear magnetic resonance, diffuse reflectance ultraviolet‐visible spectroscopy, inductively coupled plasma‐atomic emission spectroscopy, X‐ray photoelectron spectroscopy, temperature‐programmed reduction measurements, and electron paramagnetic resonance analysis. The formation of micro‐mesopores in the Cu‐SAPO‐34 catalysts decreases diffusion resistance and greatly improves the accessibility of reactants to catalytic active sites. The main active sites for NH3‐SCR reaction are the isolated Cu^2＋ species displaced into the ellipsoidal cavity of the Cu‐SAPO‐34 catalysts.
文摘Dielectric barrier discharge （DBD） plasma was utilized to oxidize NO contained in the exhaust gas to NO2, ultimately improve the selective catalytic reduction of nitrogen oxides （NOx）. In the one case, DBD was created directly in the exhaust gas （direct application）, and in the an other case, ozone produced by DBD was injected into the exhaust gas （indirect application）. A comparative study between such direct and indirect applications of DBD plasma was made in terms of the NOx removal efficiency and the energy consumption. The NO2 content in the exhaust gas was changed by the voltage applied to the DBD device （for direct application） or by the amount of ozone added to the exhaust gas （for indirect application）. In both cases, NO was easily oxidized to NO2, and the change in NO2 content largely affected the NOx removal performance of the catalytic reactor placed downstream, where both NO and NO2 were reduced to N2 in the presence of ammonia as the reducing agent. The experiments were primarily concerned with the effect of reaction temperature on the catalytic NOx reduction at various NO2 contents. The direct and indirect applications of DBD were found to remarkably improve the catalytic NOx reduction, especially at low temperatures.
基金The project supported by the Basic Research Program of the Korea Science & Engineering Foundation (KOSEF) (No. R05-2001-000-01247-0)
文摘A single-stage plasma-catalytic reactor in which catalytic materials werepacked was used to remove nitrogen oxides. The packing material was scoria being made of variousmetal oxides including Al_2O_3, MgO, TiO_2, etc. Scoria was able to act not only as dielectricpellets but also as a catalyst in the presence of reducing agent such as ethylene and ammonia.Without plasma discharge, scoria did not work well as a catalyst in the temperature range of 100 ℃to 200 ℃, showing less than 10% of NOx removal efficiency. When plasma is produced inside thereactor, the NOx removal efficiency could be increased to 60% in this temperature range.
基金supported by the National Natural Science Foundation of China(Grants No.20277009)
文摘The potential of using denitrifying and nitrifying concurrent biofilters for the removal of nitrogen oxides from synthetic gas streams was studied under the condition of high oxygen concentration. It was found that more than 85% of nitric oxide was removed from synthetic combustion gas-streams which contained 20% oxygen and 350 μL/L NO, with a residence time of 60 seconds. In the process, it was found that the existing of oxygen showed no evident negative effect on the efficiency of nitrogen removal.
文摘This paper reports the studies conducted on removal of oxides ofnitrogen (NOx) from diesel engine exhaust using electrical dischargeplasma combined with adsorbing materials such as molecular sieves.This study is being reported for the first time. The exhaust is takenfrom a diesel engine of 6 kW under no load conditions. Thecharacteristic behavior of a pulse energized dielectric barrierdischarge reactor in the diesel exhaust treatment is reported. TheNOx removal was not significant (36/100) when the reactor without anypacking was used.
基金the UREENOX project (ANR-11-VPTT-002) funded by the French ANR (L'Agence National de la Recherche)the French ANR for financial supportThe Institute of Chemistry of Poitiers (IC2MP) for the management of the UREENOX project
文摘Nitrogen oxides（NOx：NO,NO2）are a concern due to their adverse health effects.Diesel engine transport sector is the major emitter of NOx.The regulations have been strengthened and to comply with them,one of the two methods commonly used is the selective catalytic reduction of NOxby NH3（NH3-SCR）,NH3being supplied by the in-situ hydrolysis of urea.Efficiency and durability of the catalyst for this process are highly required.Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800℃.In this study,very active catalysts for the NH3-SCR of NOxwere prepared by using a silicoaluminophosphate commercial zeolite as copper host structure.Characterizations by X-ray diffraction（XRD）,scanning electron microscopy（SEM）and temperature programmed desorption of ammonia（NH3-TPD）showed that this commercial zeolite was hydrothermally stable up to 850℃ and,was able to retain some structural properties up to950℃.After hydrothermal treatment at 850℃,the NOxreduction efficiency into NH3-SCR depends on the copper content.The catalyst with a copper content of 1.25 wt.%was the most active.The difference in activity was much more important when using NO than the fast NO/NO2reaction mixture.
基金supported by the Beijing Post-Doctoral Work Foundation under Grant (No. 2011ZZ-86)the Beijing Science and Technology Nova Project (No.2010B029)the National Natural Science Foundation of China (No. 40905060)
文摘Based on observational data of ozone （O3） and nitrogen oxide （NOx） mixing ratios on the ground and at high altitude in urban areas of Beijing during a period of six days in November 2011, the temporal and spatial characteristics of mixing ratios were analyzed. The major findings include： urban O3 mixing ratios are low and NOx mixing ratios are always high near the road in November. Vertical variations of the gases are significantly different in and above the planetary boundary layer. The mixing ratio of O3 is negatively correlated with that of NOx and they are positively correlated with air temperature, which is the main factor directly causing vertical variation of O3 and NOx mixing ratios at 600-2100 m altitude. The NOx mixing ratios elevated during the heating period, while the O3 mixing ratios decreased： these phenomena are more significant at high altitudes compared to lower altitudes. During November, air masses in the urban areas of Beijing are brought by northwesterly winds, which transport O3 and NOx at low mixing ratios. Due to Beijing＇s natural geographical location, northwest air currents arc beneficial to the dilution and dispersion of pollutants, which can result in lower O3 and NOx background values in the Beijing urban area.
文摘Nitrogen oxides(NO_2 and NO)are absorbed by tributyl phosphorate(TBP)to fom a new complex mixture of TBP-NO_x. which is used as a selective oddizing agent to oxidize benzylalcohols to corresponding sldehydes or ketones In high yield. In the reaction process, nitrogen oxides are llberated mildly and mainly reduced to nitrogen, while tributyl phosphorate is recovered end recycled.
基金Porject supported by the New Century Excellent Scholar Program of Ministry of Education of China(No.NCET-04-0549)the China Postdoctoral Science Foundation(No.20060401047).
文摘A series of nanosized ion-doped TiO2 catalysts with different ion content （between 0.1 at.% and 1.0 at.%） have been prepared by wet impregnation method and investigated with respect to their behavior for UV photocatalytic oxidation of nitric oxide. The catalytic activity was correlated with structural, electronic and surface examinations of the catalysts using X-ray diffraction analysis （XRD）, ultraviolet-visible （UV-Vis） absorption spectroscopy, transmission electron microscopy （TEM）, energy disperse spectrometer （EDS） and high resolution-transmission electron microscopy （HR-TEM） techniques. An enhancement of the photocatalytic activity was observed for Zn2＋ doping catalyst ranged from 0.1 at.% to 1.0 at.% which was attributed to the lengthened lifetime of electrons and holes. The improvement in photocatalytic activity could be also observed with the low doping concentration of Cr^3＋ （0.1 at.%）. However, the doping of Fe^3＋, Mo^6＋, Mn^2＋ and the high doping concentration of Cr^3＋ had no contribution to photocatalytic activity of nitric oxide.
基金financially supported by the National Key R&D Program of China (No.2017YFC0210303)National Natural Science Foundation of China (Nos.21806009 and 21677010)+1 种基金China Postdoctoral Science Foundation (Nos.2019T120049 and 2018M631344)Fundamental Research Funds for the Central Universities (No.FRF-TP-18-019A1).
文摘Mn-Ni oxides with different compositions were prepared using standard co-precipitation(CP) and urea hydrolysis-precipitation(UH) methods and optimized for the selective catalytic reduction of nitrogen oxides(NOx) by NH3 at low temperature.Mn((2))Ni(1)Ox-CP and Mn(2)Ni(1)Ox-UH(with Mn:Ni molar ratio of 2:1) catalysts showed almost identical selective catalytic reduction(SCR) catalytic activity,with about 96% NOx conversion at 750 C and-99%in the temperature range from 100 to 250℃.X-ray diffraction(XRD) results showed that Mn(2)Ni(1)Ox-CP and Mn(2)Ni(1)Ox-UH catalysts crystallized in the form of Mn2NiO4 and MnO2-Mn2NiO4 spinel,respectively.The latter gave relatively good selectivity to N2,which might be due to the presence of the MnO2 phase and high metal-O binding energy,resulting in low dehydrogenation ability.According to the results of various characterization methods,it was found that a high density of surface chemisorbed oxygen species and efficient electron transfer between Mn and Ni in the crystal structure of Mn2NiO4 spinel played important roles in the high-efficiency SCR activity of these catalysts.Mn(2)Ni(1)Ox catalysts presented good resistance to H2O or/and SO2 with stable activity,which benefited from the Mn2NiO4 spinel structure and Eley-Rideal mechanism,with only slight effects from SO2.
文摘An electric discharge plasma reactor combined with a catalytic reactor wasstudied for removing nitrogen oxides. To understand the combined process thoroughly, dischargeplasma and catalytic process were separately studied first, and then the two processes were combinedfor the study. The plasma reactor was able to oxidize NO to NO_2 well although the oxidation ratedecreased with temperature. The plasma reactor alone did not reduce the NO_x (NO+NO_2) leveleffectively, but the increase in the ratio of NO_2 to NO as a result of plasma discharge led to theenhancement of NO_x removal efficiency even at lower temperatures over the catalyst surface(V_2O_5-WO_3/TiO_2). At a gas temperature of 100℃, the NO_x removal efficiency obtained using thecombined plasma catalytic process was 88% for an energy input of 36 eV/molecule or 30 J/l.
文摘We evaluate nitrogen oxides pollution in Takamatsu and Utazu area in Kagawa prefecture, Japan. Annually observations for nitrogen oxides (nitrogen dioxide;NO2, nitric oxide;NO) (1990-2007) were obtained from data base of Kagawa prefecture, Japan. Changes in NO2 and NO in Takamatsu and Utazu area were evaluated and compared. In 2007, NO2, NO and NO2 + NO (ppm) in Takamatsu area were higher than those in Utazu area. However, NO2 /NO + NO2 in Takamatsu area was lower than that in Utazu area. From 1990 to 2007, mean of NO2 in a day over the level of 0.06 ppm was 30 days in Takamatsu area and only one day in Utazu area. Mean of NO2, NO and NO2 + NO was significantly higher and NO2/NO + NO2 was lower in Takamatsu area than that in Utazu area. In addition, NO2, NO and NO2 + NO were negatively correlated and NO2/NO + NO2 was positively correlated with years (1990-2007) in Takamatsu area. The level of nitrogen oxides pollution in Utazu area was lower than Takamatsu area. Further observation is required for preventing nitrogen oxides pollution in Kagawa prefecture, Japan.
基金supported by the National Natural Science Foundation of China (No. 21073131)the Shanxi Natural Science Foundation(No. 2009011011-3)
文摘V-Pd/γ-Al2O3-TiO2 catalysts with different vanadium contents were prepared by a combined sol-gel and impregnation method. X-ray diffraction （XRD）, N2 adsorption-desorption （BET）, X-ray photoelectron spectroscopy （XPS） and catalytic removal of ethanol, acetaldehyde and nitrogen oxides at low temperature （〈300 ？C） were used to assess the properties of the catalysts. The results showed that the sample with 1wt% vanadium exhibited an excellent catalytic performance for simultaneous removal of ethanol, acetaldehyde and nitrogen oxides. The conversions of ethanol, acetaldehyde and nitrogen oxides at 250 ？C were 100%, 74.4% and 98.7%, respectively. V-Pd/γ-Al2O3-TiO2 catalyst with 1 wt% vanadium showed the largest surface area and higher dispersion of vanadium oxide on the catalyst surface, and possessed a larger mole fraction of V4＋ species and unique PdO species on the surface, which can be attributed to the strong synergistic effect among palladium, vanadium and the carriers. The higher activity of V-Pd/γ-Al2O3-TiO2 catalyst is related to the V4＋ and Pd2＋ species on the surface, which might be favorable for the formation of active sites.
文摘Outdoor air quality, building materials, HVAC （Heating, Ventilation, Air Conditioning） systems and people activity are important factors in human exposition of polluted indoor air. The degree of signification varies in dependence on pollution character and its sources. Buildings eliminate significantly people exposition of outdoor pollutants, but on the other hand, buildings are significant source of indoor pollution. The contamination of indoor air is largely from the use of gas for heating and cooking appliances. A comprehensive analysis of indoor air pollution by nitrogen oxides shows that the extent of indoor air pollution and consequent exposure varies as a result of many factors mainly the differing dislribution of appliances and their level of use. This study aims to formulate a mathematical model for the production of nitrogen oxides indoors. The physical processes that determine the concentrations of indoor nitrogen oxides as a function of outdoor concentrations, indoor emission rates and building characteristics have been mathematically described. The mathematical model developed has been parameterized for typical Slovak residences. The modeling of the occurrence of indoor nitrogen oxides and verification of the model is presented in this paper.
基金supported by Natural Science Foundation of Shandong Province(ZR2021MB075)Fundamental Research Funds for the Central Universities,Ocean University of China(202461021).
文摘The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.
文摘Electrocatalytic production of ammonia from dinitrogen is considered as a sustainable alternative to the energy-demanding and pollutive Haber-Bosch process.A promising class of materials for selective nitrogen reduction(NRR)corresponds to transition-metal oxides given that these electrodes do not show a high activity toward the competing hydrogen evolution reaction.So far,density functional theory calculations have been used to comprehend trends in a class of materials by using the concept of scaling relations and volcano plots.This thermodynamic theory pinpoints that either the formation of the*NNH adsorbate or the formation of ammonia are reconciled with the potential-determining reaction steps.Thus,the development of NRR catalyst has largely focused on the optimization of these two elementary processes.In the present contribution,overpotential and kinetic effects are factored into the volcano plot for the NRR over transition-metal oxides by making use of the recently introduced activity descriptor G_(max)(η).It is illustrated that the thermodynamic volcano picture is too simplistic as the limiting reaction step may alter close to the volcano apex:there,particularly surface reactions may govern the reaction rate.In addition,it is demonstrated how to include the formation of hydrazine as a competing side reaction into the volcano plot,which is of importance for weak binding*NNH catalysts where the formation of hydrazine may compete with the formation of ammonia.Given that the outlined methodology in this manuscript is universal and not restricted to the class of transition-metal oxides,the presented kinetic volcano picture may contribute to the development of NRR catalysts for nitrogen fixation.
