This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature....This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.展开更多
Cation exchange capacity (CEC) is one of the most important properties of soils. The NH<sub>4</sub>OAc (pH = 7.0) exchange method is usually recommended to determine CEC (CEC<sub>1</sub>) of al...Cation exchange capacity (CEC) is one of the most important properties of soils. The NH<sub>4</sub>OAc (pH = 7.0) exchange method is usually recommended to determine CEC (CEC<sub>1</sub>) of all soils with different pH values, particularly for studies on soil taxonomy. But comparatively the BaCl<sub>2</sub>-MgSO<sub>4</sub> forced-exchange method is more authentic in determining CEC (CEC<sub>2</sub>) of tropical and subtropical highly-weathered acid soils. But so far little is known about the difference between CEC<sub>1</sub> and CEC<sub>2</sub>. In this study, the physiochemical data of 114 acid B horizon soils from 112 soil series of tropical and subtropical China were used, CEC<sub>1</sub> and CEC<sub>2</sub> were determined and compared, the influencing factors were analyzed for the difference between CEC<sub>1</sub> and CEC<sub>2</sub>, and then a regression model was established between CEC<sub>1</sub> and CEC<sub>2</sub>. The results showed that CEC<sub>2</sub> was significantly lower than CEC<sub>1</sub> (p < 0.01), CEC<sub>2</sub> was 14.76% - 63.31% with a mean of 36.32% of CEC<sub>1</sub>. In view of the contribution to CEC from other properties, CEC<sub>2</sub> was mainly determined by pH (45.92%), followed by silt (21.05%), free Fe<sub>2</sub>O<sub>3</sub> (17.35%) and clay contents (12.76%), CEC<sub>1</sub> was mainly decided by free Fe<sub>2</sub>O<sub>3</sub> content (40.38%), followed by pH (28.39%) and silt content (27.29%;and the difference between CEC<sub>1</sub> and CEC<sub>2</sub> was mainly affected by free Fe<sub>2</sub>O<sub>3</sub> (50.92%), followed by silt content (26.46%) and pH (21.80%). The acceptable optimal regression model between CEC<sub>2</sub> and CEC<sub>1</sub> was established as CEC<sub>2</sub> = 2.3114 × CEC<sub>1</sub><sup>1.1496</sup> (R<sup>2</sup> = 0.410, P < 0.001, RMSE = 0.15). For the studies on soil taxonomy, the BaCl<sub>2</sub>-MgSO<sub>4</sub> forced-exchange method is recommended in determining CEC of the highly-weathered acid soils in the tropical and subtropical regions.展开更多
The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions f...The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.展开更多
Granular CuO-CeO2-MnOx/γ-Al2O3 catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO2-MnOx/γ-Al2O3 catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. ...Granular CuO-CeO2-MnOx/γ-Al2O3 catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO2-MnOx/γ-Al2O3 catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. Preliminary tests were carried out to analyze the behavior of NH3 and NO over catalyst in the presence of oxygen. The optimum temperature range for SCR over the CuO-CeO2-MnOx/γ-Al2O3 catalysts is 300-400 ℃ . The catalysts maintain nearly 100% NO conversion at 350 ℃. The NH3 oxidation experiments show that both NO and N2O are produced gradually with the increase of temperature. The catalysts in this experiment have a stronger oxidation property on NH3, which improves the denitrification activity at low temperature. The over-oxidation of NH3 at high temperature is the main cause leading to a decrease in the NO conversion. The NH3 and NO desorption experiments show that NH3 and NO can be adsorbed on CuO-CeO2-MnOx/γ-Al2O3 granular catalysts. The transient response of NH3 and NO indicates that the SCR reaction proceeds in accordance with the Eley-Rideal mechanism. The adsorbed NO has little influence on the denitrification activity in SCR process.展开更多
4,4-Dialkyl-2-oxazolin-5-ones are prepared by one step reaction of 2-oxazolin-5-one with the magnesium methyl carbonate(MMC)and alkyIhalides.It is a novel and convenient method for synthesis of α, Υ-disubstitutcd α...4,4-Dialkyl-2-oxazolin-5-ones are prepared by one step reaction of 2-oxazolin-5-one with the magnesium methyl carbonate(MMC)and alkyIhalides.It is a novel and convenient method for synthesis of α, Υ-disubstitutcd α-amino acid by hydrolysis of 4,4-dialkyl-2-oxazolin-5-ones.展开更多
To understand the effect of the doping amount of Cu^2+ on the structure and reactivity of SnO2 in NOx-SCR with NH3, a series of Sn-Cu-O binary oxide catalysts with different Sn/Cu ratios have been prepared and thoroug...To understand the effect of the doping amount of Cu^2+ on the structure and reactivity of SnO2 in NOx-SCR with NH3, a series of Sn-Cu-O binary oxide catalysts with different Sn/Cu ratios have been prepared and thoroughly characterized. Using the XRD extrapolation method, the SnO2 lattice capacity for Cu^2+ cations is determined at 0.10 g Cu O per g of SnO2, equaling a Sn/Cu molar ratio of 84/16. Therefore, in a tetragonal rutile SnO2 lattice, only a maximum of 16% of the Sn4+ cations can be replaced by Cu^2+ to form a stable solid solution structure. If the Cu content is higher, Cu O will form on the catalyst surface, which has a negative effect on the reaction performance. For samples in a pure solid solution phase, the number of surface defects increase with increasing Cu content until it reaches the lattice capacity, as confirmed by Raman spectroscopy. As a result, the amounts of both active oxygen species and acidic sites on the surface, which critically determine the reaction performance, also increase and reach the maximum level for the catalyst with a Cu content close to the lattice capacity. A distinct lattice capacity threshold effect on the structure and reactivity of Sn-Cu binary oxide catalysts has been observed. A Sn-Cu catalyst with the best reaction performance can be obtained by doping the SnO2 matrix with the lattice capacity amount of Cu^2+.展开更多
The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The ...The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The photocatalytic reduction of N_(2)is expected to achieve clean and sustainable NH_(3)production by using clean solar energy.To date,the new photocatalysts for photocatalytic reduction of N_(2)to NH_(3)at room temperature and atmospheric pressure have not been fully developed.The major challenge is to achieve high light-absorption efficiency,conversion efficiency,and stability of photocatalysts.Herein,the methods for measuring produced NH_(3)are compared,and the problems related to possible NH_(3)pollution in photocatalytic systems are mentioned to provide accurate ideas for measuring photocatalytic efficiency.The recent progress of nitrogen reduction reaction(NRR)photocatalysts at ambient temperature and pressure is summarized by introducing charge transfer,migration,and separation in photocatalytic NRR,which provides a guidance for the selection of future photocatalyst.More importantly,we introduce the latest research strategies of photocatalysts in detail,which can guide the preparation and design of photocatalysts with high NRR activity.展开更多
基金supported by the National Natural Science Foundation of China (No. 21507130)the Open Project Program of Beijing National Laboratory for Molecular Sciences (No. 20140142)+3 种基金the Open Project Program of Chongqing Key Laboratory of Environmental Materials and Remediation Technology from Chongqing University of Arts and Sciences (No. CEK1405)the Open Project Program of Jiangsu Key Laboratory of Vehicle Emissions Control (No. OVEC001)the Open Project Program of Chongqing Key Laboratory of Catalysis and Functional Organic Molecules from Chongqing Technology and Business University (1456029)the Chongqing Science & Technology Commission (Nos. cstc2016jcyj A0070, cstc2014pt-gc20002, cstckjcxljrc13)~~
文摘This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.
文摘Cation exchange capacity (CEC) is one of the most important properties of soils. The NH<sub>4</sub>OAc (pH = 7.0) exchange method is usually recommended to determine CEC (CEC<sub>1</sub>) of all soils with different pH values, particularly for studies on soil taxonomy. But comparatively the BaCl<sub>2</sub>-MgSO<sub>4</sub> forced-exchange method is more authentic in determining CEC (CEC<sub>2</sub>) of tropical and subtropical highly-weathered acid soils. But so far little is known about the difference between CEC<sub>1</sub> and CEC<sub>2</sub>. In this study, the physiochemical data of 114 acid B horizon soils from 112 soil series of tropical and subtropical China were used, CEC<sub>1</sub> and CEC<sub>2</sub> were determined and compared, the influencing factors were analyzed for the difference between CEC<sub>1</sub> and CEC<sub>2</sub>, and then a regression model was established between CEC<sub>1</sub> and CEC<sub>2</sub>. The results showed that CEC<sub>2</sub> was significantly lower than CEC<sub>1</sub> (p < 0.01), CEC<sub>2</sub> was 14.76% - 63.31% with a mean of 36.32% of CEC<sub>1</sub>. In view of the contribution to CEC from other properties, CEC<sub>2</sub> was mainly determined by pH (45.92%), followed by silt (21.05%), free Fe<sub>2</sub>O<sub>3</sub> (17.35%) and clay contents (12.76%), CEC<sub>1</sub> was mainly decided by free Fe<sub>2</sub>O<sub>3</sub> content (40.38%), followed by pH (28.39%) and silt content (27.29%;and the difference between CEC<sub>1</sub> and CEC<sub>2</sub> was mainly affected by free Fe<sub>2</sub>O<sub>3</sub> (50.92%), followed by silt content (26.46%) and pH (21.80%). The acceptable optimal regression model between CEC<sub>2</sub> and CEC<sub>1</sub> was established as CEC<sub>2</sub> = 2.3114 × CEC<sub>1</sub><sup>1.1496</sup> (R<sup>2</sup> = 0.410, P < 0.001, RMSE = 0.15). For the studies on soil taxonomy, the BaCl<sub>2</sub>-MgSO<sub>4</sub> forced-exchange method is recommended in determining CEC of the highly-weathered acid soils in the tropical and subtropical regions.
文摘The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.
基金Projects (50776037,50721005) supported by the National Natural Science Foundation of China
文摘Granular CuO-CeO2-MnOx/γ-Al2O3 catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO2-MnOx/γ-Al2O3 catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. Preliminary tests were carried out to analyze the behavior of NH3 and NO over catalyst in the presence of oxygen. The optimum temperature range for SCR over the CuO-CeO2-MnOx/γ-Al2O3 catalysts is 300-400 ℃ . The catalysts maintain nearly 100% NO conversion at 350 ℃. The NH3 oxidation experiments show that both NO and N2O are produced gradually with the increase of temperature. The catalysts in this experiment have a stronger oxidation property on NH3, which improves the denitrification activity at low temperature. The over-oxidation of NH3 at high temperature is the main cause leading to a decrease in the NO conversion. The NH3 and NO desorption experiments show that NH3 and NO can be adsorbed on CuO-CeO2-MnOx/γ-Al2O3 granular catalysts. The transient response of NH3 and NO indicates that the SCR reaction proceeds in accordance with the Eley-Rideal mechanism. The adsorbed NO has little influence on the denitrification activity in SCR process.
文摘4,4-Dialkyl-2-oxazolin-5-ones are prepared by one step reaction of 2-oxazolin-5-one with the magnesium methyl carbonate(MMC)and alkyIhalides.It is a novel and convenient method for synthesis of α, Υ-disubstitutcd α-amino acid by hydrolysis of 4,4-dialkyl-2-oxazolin-5-ones.
文摘To understand the effect of the doping amount of Cu^2+ on the structure and reactivity of SnO2 in NOx-SCR with NH3, a series of Sn-Cu-O binary oxide catalysts with different Sn/Cu ratios have been prepared and thoroughly characterized. Using the XRD extrapolation method, the SnO2 lattice capacity for Cu^2+ cations is determined at 0.10 g Cu O per g of SnO2, equaling a Sn/Cu molar ratio of 84/16. Therefore, in a tetragonal rutile SnO2 lattice, only a maximum of 16% of the Sn4+ cations can be replaced by Cu^2+ to form a stable solid solution structure. If the Cu content is higher, Cu O will form on the catalyst surface, which has a negative effect on the reaction performance. For samples in a pure solid solution phase, the number of surface defects increase with increasing Cu content until it reaches the lattice capacity, as confirmed by Raman spectroscopy. As a result, the amounts of both active oxygen species and acidic sites on the surface, which critically determine the reaction performance, also increase and reach the maximum level for the catalyst with a Cu content close to the lattice capacity. A distinct lattice capacity threshold effect on the structure and reactivity of Sn-Cu binary oxide catalysts has been observed. A Sn-Cu catalyst with the best reaction performance can be obtained by doping the SnO2 matrix with the lattice capacity amount of Cu^2+.
基金Taishan Scholars Program of Shandong Province,Grant/Award Number:tsqn201812068Higher School Youth Innovation Team of Shandong Province,Grant/Award Number:2019KJA013+1 种基金The Opening Fund of State Key Laboratory of Heavy Oil Processing,Grant/Award Number:SKLOP202002006National Natural Science Foundation of China,Grant/Award Number:51872173。
文摘The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The photocatalytic reduction of N_(2)is expected to achieve clean and sustainable NH_(3)production by using clean solar energy.To date,the new photocatalysts for photocatalytic reduction of N_(2)to NH_(3)at room temperature and atmospheric pressure have not been fully developed.The major challenge is to achieve high light-absorption efficiency,conversion efficiency,and stability of photocatalysts.Herein,the methods for measuring produced NH_(3)are compared,and the problems related to possible NH_(3)pollution in photocatalytic systems are mentioned to provide accurate ideas for measuring photocatalytic efficiency.The recent progress of nitrogen reduction reaction(NRR)photocatalysts at ambient temperature and pressure is summarized by introducing charge transfer,migration,and separation in photocatalytic NRR,which provides a guidance for the selection of future photocatalyst.More importantly,we introduce the latest research strategies of photocatalysts in detail,which can guide the preparation and design of photocatalysts with high NRR activity.
