Low and high-concentration nitric wastewater can induce stable nitrite accumulation and realize the nitrification system, with the nitrite accumulation rate between 50% and 90%. In the low-concentration nitrite nitrif...Low and high-concentration nitric wastewater can induce stable nitrite accumulation and realize the nitrification system, with the nitrite accumulation rate between 50% and 90%. In the low-concentration nitrite nitrification system, the average FA concentrations during the period of stable nitrite accumulation remained at 7 to 10 mg/L. In the high-concentration nitrite nitrification system, the nitrogen oxidation activity will not be affected by biomass, the nitrite oxidation activity is related to the system biomass, it is recommended to be measured by FA/MLSS. Keeping the FA sludge load below 0.1 is the precondition of making good nitrite accumulation and nitrogen degradation rate. Nitrite oxidation bacteria cannot be totally eliminated or washed out from the system.展开更多
The short-term effects of temperature and free ammonia (FA) on ammonium oxidization were investigated in this study by operating several batch tests with two different partial nitrification aggregates, formed as eithe...The short-term effects of temperature and free ammonia (FA) on ammonium oxidization were investigated in this study by operating several batch tests with two different partial nitrification aggregates, formed as either granules or flocs. The results showed that the rate of ammonium oxidation in both cultures increased significantly as temperature increased from 10 to 30 °C. The specific ammonium oxidation rate with the granules was 2-3 times higher than that with flocs at the same temperature. Nitrification at various FA concentrations and temperatures combination exhibited obvious inhibition in ammonium oxidation rate when FA was 90 mg·L 1 and tempera- ture dropped to 10 °C in the two systems. However, the increase in substrate oxidation rate of ammonia at 30 °C was observed. The results suggested that higher reaction temperature was helpful to reduce the toxicity of FA. Granules appeared to be more tolerant to FA attributed to the much fraction of ammonia oxidizing bacteria (AOB) and higher resistance to the transfer of ammonia into the bacterial aggregates, whereas in the floc system, the bacteria distributed throughout the entire aggregate. These results may contribute to the applicability of the nitrifying granules in wastewater treatment operated at high ammonium concentration.展开更多
Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium c...Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium chloride solution containing lithium was illustrated based on the experimental results, and the effect of lithium on the crystallization of magnesium was clarified. The results of X-ray diffraction（XRD）, scanning election microscope（SEM）, Fourier transform infrared spectroscopy（FTIR）, thermogravimetry analysis（TGA） and laser particle size analysis indicate that the effect of lithium is not obvious on the crystal phase and morphology of the products. But the XRD relative intensity of（001） surface of magnesium hydroxide declines, the specific surface area reduces apparently and the additive mass of lithium affects the heat loss rates of precipitations obviously. Quantum chemical calculations on the interactional systems of Mg（H2O）2＋6 and Li（H2O）＋4 were performed using B3LYP/6-311 G basis set. The results show that when the distance of Mg2＋ and Li＋ is 7-10 , the interaction energy is high and the trend of solvation is strong, which would make hydroxide ions easier to combine with hydrogen ions in ammonia precipitation process. And the absolute value of solvation free energy reduces significantly in MgCl2 solution（1 mol/L） containing lithium ion.展开更多
Electrocatalytic ammonia synthesis under mild conditions is an attractive and challenging process in the earth’s nitrogen cycle,which requires efficient and stable catalysts to reduce the overpotential.The N2 activat...Electrocatalytic ammonia synthesis under mild conditions is an attractive and challenging process in the earth’s nitrogen cycle,which requires efficient and stable catalysts to reduce the overpotential.The N2 activation and reduction overpotential of different Ti3C2O2-supported transition metal(TM)(Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Mo,Ru,Rh,Pd,Ag,Cd,and Au)single-atom catalysts have been analyzed in terms of the Gibbs free energies calculated using the density functional theory(DFT).The end-on N2 adsorption was more energetically favorable,and the negative free energies represented good N2 activation performance,especially in the presence Fe/Ti3C2O2(﹣0.75 eV).The overpotentials of Fe/Ti3C2O2,Co/Ti3C2O2,Ru/Ti3C2O2,and Rh/Ti3C2O2 were 0.92,0.89,1.16,and 0.84 eV,respectively.The potential required for ammonia synthesis was different for different TMs and ranged from 0.68 to 2.33 eV.Two possible potential-limiting steps may be involved in the process:(i)hydrogenation of N2 to*NNH and(ii)hydrogenation of*NH2 to ammonia.These catalysts can change the reaction pathway and avoid the traditional N–N bond-breaking barrier.It also simplifies the understanding of the relationship between the Gibbs free energy and overpotential,which is a significant factor in the rational designing and large-scale screening of catalysts for the electrocatalytic ammonia synthesis.展开更多
The nitrogen reduction reaction(NRR)using new and efficient electrocatalysts is a promising al‐ternative to the traditional Haber‐Bosch process.Nevertheless,it remains a challenge to design efficient catalysts with ...The nitrogen reduction reaction(NRR)using new and efficient electrocatalysts is a promising al‐ternative to the traditional Haber‐Bosch process.Nevertheless,it remains a challenge to design efficient catalysts with improved catalytic performance.Herein,various O‐functional MXenes were investigated as NRR catalysts by a combination of density functional theory calculations and least absolute shrinkage and selection operator(LASSO)regression.Nb_(3)C_(2)O_(X) has been regarded as a promising catalyst for the NRR because of its stability,activity,and selectivity.The poten‐tial‐determining step is*NH_(2) hydrogenation to*NH3 with a limiting potential of-0.45 V.Further‐more,via LASSO regression,the descriptors and equations fitting the relationship between the properties of O‐functional MXenes and NRR activity have been proposed.This work not only pro‐vides a rational design strategy for catalysts but also provides machine learning data for further investigation.展开更多
The influence of preparation conditions （e.g. H2-N2 ratios, final nitriding temperatures） on the performance of MoNx/SBA-15 catalysts for ammonia decomposition was investigated. The variation of catalytic activity w...The influence of preparation conditions （e.g. H2-N2 ratios, final nitriding temperatures） on the performance of MoNx/SBA-15 catalysts for ammonia decomposition was investigated. The variation of catalytic activity with H2-N2 ratios may be attributed to the variation of surface compositions and particle sizes of the active components. The variation of nitriding temperatures leads to the formation of molybdenum nitride domains of varying compositions, which are responsible for the difference in their catalytic performance with respect to ammonia decomposition. At 923 K, ammonia could be completely decomposed using 15800 ml/h·gcat of GHSVNH3, which shows high performance for the catalytic decomposition of ammonia.展开更多
基金supported by Guizhou Science and Technology Fund Project 2008-2236the Scientific and Technological Project under Science and Technology Department of Guizhou Province [SZ(2008)3073]Guizhou University’s Scientific Research Personnel Introduction Pro-gram 2008-029
文摘Low and high-concentration nitric wastewater can induce stable nitrite accumulation and realize the nitrification system, with the nitrite accumulation rate between 50% and 90%. In the low-concentration nitrite nitrification system, the average FA concentrations during the period of stable nitrite accumulation remained at 7 to 10 mg/L. In the high-concentration nitrite nitrification system, the nitrogen oxidation activity will not be affected by biomass, the nitrite oxidation activity is related to the system biomass, it is recommended to be measured by FA/MLSS. Keeping the FA sludge load below 0.1 is the precondition of making good nitrite accumulation and nitrogen degradation rate. Nitrite oxidation bacteria cannot be totally eliminated or washed out from the system.
基金Supported by the Project of Scientific Research Base and Scientific Innovation Platform of Beijing Municipal Education CommissionNational Key Science and Technology Special Projects
文摘The short-term effects of temperature and free ammonia (FA) on ammonium oxidization were investigated in this study by operating several batch tests with two different partial nitrification aggregates, formed as either granules or flocs. The results showed that the rate of ammonium oxidation in both cultures increased significantly as temperature increased from 10 to 30 °C. The specific ammonium oxidation rate with the granules was 2-3 times higher than that with flocs at the same temperature. Nitrification at various FA concentrations and temperatures combination exhibited obvious inhibition in ammonium oxidation rate when FA was 90 mg·L 1 and tempera- ture dropped to 10 °C in the two systems. However, the increase in substrate oxidation rate of ammonia at 30 °C was observed. The results suggested that higher reaction temperature was helpful to reduce the toxicity of FA. Granules appeared to be more tolerant to FA attributed to the much fraction of ammonia oxidizing bacteria (AOB) and higher resistance to the transfer of ammonia into the bacterial aggregates, whereas in the floc system, the bacteria distributed throughout the entire aggregate. These results may contribute to the applicability of the nitrifying granules in wastewater treatment operated at high ammonium concentration.
基金Projects(51104185,51134007)supported by the National Natural Science Foundation of ChinaProject(2010QZZD003)supported by the Key Project of Central South University of Fundamental Research Funds for the Central Universities of China
文摘Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium chloride solution containing lithium was illustrated based on the experimental results, and the effect of lithium on the crystallization of magnesium was clarified. The results of X-ray diffraction（XRD）, scanning election microscope（SEM）, Fourier transform infrared spectroscopy（FTIR）, thermogravimetry analysis（TGA） and laser particle size analysis indicate that the effect of lithium is not obvious on the crystal phase and morphology of the products. But the XRD relative intensity of（001） surface of magnesium hydroxide declines, the specific surface area reduces apparently and the additive mass of lithium affects the heat loss rates of precipitations obviously. Quantum chemical calculations on the interactional systems of Mg（H2O）2＋6 and Li（H2O）＋4 were performed using B3LYP/6-311 G basis set. The results show that when the distance of Mg2＋ and Li＋ is 7-10 , the interaction energy is high and the trend of solvation is strong, which would make hydroxide ions easier to combine with hydrogen ions in ammonia precipitation process. And the absolute value of solvation free energy reduces significantly in MgCl2 solution（1 mol/L） containing lithium ion.
基金financially supported by the National Natural Science Foundation of China(21625604,21776251,21671172,21706229,21878272)~~
文摘Electrocatalytic ammonia synthesis under mild conditions is an attractive and challenging process in the earth’s nitrogen cycle,which requires efficient and stable catalysts to reduce the overpotential.The N2 activation and reduction overpotential of different Ti3C2O2-supported transition metal(TM)(Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Mo,Ru,Rh,Pd,Ag,Cd,and Au)single-atom catalysts have been analyzed in terms of the Gibbs free energies calculated using the density functional theory(DFT).The end-on N2 adsorption was more energetically favorable,and the negative free energies represented good N2 activation performance,especially in the presence Fe/Ti3C2O2(﹣0.75 eV).The overpotentials of Fe/Ti3C2O2,Co/Ti3C2O2,Ru/Ti3C2O2,and Rh/Ti3C2O2 were 0.92,0.89,1.16,and 0.84 eV,respectively.The potential required for ammonia synthesis was different for different TMs and ranged from 0.68 to 2.33 eV.Two possible potential-limiting steps may be involved in the process:(i)hydrogenation of N2 to*NNH and(ii)hydrogenation of*NH2 to ammonia.These catalysts can change the reaction pathway and avoid the traditional N–N bond-breaking barrier.It also simplifies the understanding of the relationship between the Gibbs free energy and overpotential,which is a significant factor in the rational designing and large-scale screening of catalysts for the electrocatalytic ammonia synthesis.
文摘The nitrogen reduction reaction(NRR)using new and efficient electrocatalysts is a promising al‐ternative to the traditional Haber‐Bosch process.Nevertheless,it remains a challenge to design efficient catalysts with improved catalytic performance.Herein,various O‐functional MXenes were investigated as NRR catalysts by a combination of density functional theory calculations and least absolute shrinkage and selection operator(LASSO)regression.Nb_(3)C_(2)O_(X) has been regarded as a promising catalyst for the NRR because of its stability,activity,and selectivity.The poten‐tial‐determining step is*NH_(2) hydrogenation to*NH3 with a limiting potential of-0.45 V.Further‐more,via LASSO regression,the descriptors and equations fitting the relationship between the properties of O‐functional MXenes and NRR activity have been proposed.This work not only pro‐vides a rational design strategy for catalysts but also provides machine learning data for further investigation.
文摘The influence of preparation conditions （e.g. H2-N2 ratios, final nitriding temperatures） on the performance of MoNx/SBA-15 catalysts for ammonia decomposition was investigated. The variation of catalytic activity with H2-N2 ratios may be attributed to the variation of surface compositions and particle sizes of the active components. The variation of nitriding temperatures leads to the formation of molybdenum nitride domains of varying compositions, which are responsible for the difference in their catalytic performance with respect to ammonia decomposition. At 923 K, ammonia could be completely decomposed using 15800 ml/h·gcat of GHSVNH3, which shows high performance for the catalytic decomposition of ammonia.
