It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(...It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.展开更多
This study is a contribution to improving rice productivity on acidic plateau soils of the tropical rainforest zone. It is based on taking into account the cationic balances of the soil in order to optimize the phosph...This study is a contribution to improving rice productivity on acidic plateau soils of the tropical rainforest zone. It is based on taking into account the cationic balances of the soil in order to optimize the phosphorus (P) nutrition of rice on these acidic soils, where this nutrient constitutes a limiting factor for agricultural production. Three (3) pot trials were conducted in Adiopodoumé in the forested south of Côte d’Ivoire. The interactive effects of calcium carbonate (0, 25, 50 and 75 kg Ca ha<sup>−1</sup>) and magnesium sulfate (0, 25, 50 and 75 kg Mg ha<sup>−1</sup>) were evaluated on the response of NERICA 5 rice at doses 0, 25, 50 and 75 kg P ha<sup>−1</sup> of natural phosphate from Togo, applied only once at the start of the experiment. Additional fertilizers of nitrogen (N) (100 kg N ha<sup>−1</sup>) and potassium (K) (50 kg KCl ha<sup>−1</sup>) were added to each of the tests in a split-plot device. The test results revealed a paddy production potential of approximately 3 to 5 t⋅ha<sup>−1</sup> for NERICA 5 on an acidic soil, under the effect of the interaction of P, Ca and Mg. The quadratic response of rice yield to the doses of these fertilizers would be more dependent on their balance, itself influenced by Ca nutrition. For the sustainability and maintenance of rice production in agro-ecology studied, it was recommended doses of 38 kg Ca ha<sup>−1</sup>, 34 kg Mg ha<sup>−1</sup> in a Ca/Mg ratio (1/1) with intakes of 41 kg P ha<sup>−1</sup>, overall in a ratio 1/1/1 (P/Ca/Mg) more favorable to the availability of free iron considered a guiding element of mineral nutrition. Thus, these promising results should be confirmed in a real environment for better management of the fertilization of rice cultivated on acidic plateau soils in Côte d’Ivoire.展开更多
Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid...Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.展开更多
Planktonic foraminifer Globigerinoides ruber(white)and Trilobatus sacculifer are the most frequently used mixedlayer dwelling species for reconstructing past oceanic environments.Specifically,the Mg/Ca ratios of these...Planktonic foraminifer Globigerinoides ruber(white)and Trilobatus sacculifer are the most frequently used mixedlayer dwelling species for reconstructing past oceanic environments.Specifically,the Mg/Ca ratios of these two foraminiferal species have been used for reconstructing tropical/subtropical changes in sea surface temperature(SST).However,these two species have different morphotypes,of which the spatial and temporal differences in Mg/Ca ratios and their influencing factors are still unclear.Our objective is to investigate the potential differences between the Mg/Ca ratios of these different morphotypes of G.ruber(white)and T.sacculifer in the western Philippine Sea(WPS)and determine their implications for the reconstruction of SST and upper-ocean structure.Mg/Ca measurements are made on two basic morphotypes of G.ruber(white)[sensu stricto(s.s.)and sensu lato(s.l.)]and T.sacculifer[with(w)and without(w/o)a sac-like final chamber]on samples of Site MD06-3047B from the WPS.Our results reveal that Mg/Ca ratios of different G.ruber morphotypes show consistent differences;and those of T.sacculifer morphotypes show staged variations since MIS 3.It is suggested to select a single morphotype for reconstructing SST changes using the Mg/Ca ratios of G.ruber and T.sacculifer in the WPS.Furthermore,the Mg/Ca ratios between G.ruber s.s.and G.ruber s.l.[Δ(Mg/Ca)_(G.ruber s.s.-s.l.)]downcore MD06-3047B covaries with indexes of summer monsoon.Combining with the core-top results,showing regional variation of differences in theΔ(Mg/Ca)_(G.ruber s.s.-s.l.)over the western tropical Pacific,we propose thatΔ(Mg/Ca)_(G.ruber s.s.-s.l.)may tend to reflect summer mixed layer depth.展开更多
Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in ...Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in the Haima cold seeps at a water depth of 1381 m.Based on the scanning electron microscope(SEM)analyses,the prismatic layer and nacreous layer were identified,which are characterized by prismatic structure and stratified structure,respectively.In addition,the profile can be subdivided into two parts:altered and unaltered zones.Laser inductively coupled plasma mass spectrometry(LA-ICP-MS)mapping shows that the element concentrations of the altered zones were influenced by the authigenic carbonate rocks,whereas the element concentrations of unaltered zones remain stable.In-situ X-ray diffraction(XRD)analyses show that the mineral constituent of the prismatic layer is mainly composed of aragonite.Along with the growth profile,Mg/Ca ratios of unaltered zones have minor variations,ranging 0.72-0.97 mmol/mol(mean=0.87 mmol/mol),with estimated temperatures of 3.8-4.1℃,indicating that the temperature of the surrounding seawater remains constant and agree with the measured data of 3.9℃which was conducted by a conductivity-temperature-depth system(CTD).The minor variations of Ba/Ca ratios(0.01-0.06 mmol/mol;mean=0.04 mmol/mol)indicate a relatively stabilized salinity of the surrounding seawater.S/Ca ratios show large variations of 0.04-4.15 mmol/mol(mean=1.37 mmol/mol).S/Ca ratios have regular variations which generally correspond to the variations of the Mg/Ca ratios,highlighting that the S/Ca ratios of bivalve shells show the potential to reflect the growth rate of the Gigantides.However,further studies should be carried out on the understanding of the links between the S/Ca ratios and seepage intensity of cold-seep fluids.展开更多
Sr_(0.5)Ca_(0.5)CuO_2 has been synthesized by the solid state reaction.The compound crystallizes in an orthorhombic unit cell,space group D_(2h)^(17)-Cmcm with a=3.444 ,b=16.11 ,c=3.868 .It decomposes shove 1038℃. ...Sr_(0.5)Ca_(0.5)CuO_2 has been synthesized by the solid state reaction.The compound crystallizes in an orthorhombic unit cell,space group D_(2h)^(17)-Cmcm with a=3.444 ,b=16.11 ,c=3.868 .It decomposes shove 1038℃. Sr_(0.5)Ca_(0.5)CuO_2 is s black p-type semiconductor with resistivity 53Ω.cm at room tempersture.展开更多
Highly textured (Bi,Pb)2Sr2Ca2Cu3Ox superconducting tapes have been fabricated by means of magnetic-field and vibration technique. This method is an effective way of improving the degree of grain alignment and density...Highly textured (Bi,Pb)2Sr2Ca2Cu3Ox superconducting tapes have been fabricated by means of magnetic-field and vibration technique. This method is an effective way of improving the degree of grain alignment and density of oxide core in tapes after heat treatment and pressing cycles.Jc of above 20% was increased than that without treatment.展开更多
The electronic, elastic, vibrational, and thermodynamic properties of Sr_（10）（PO_4）_6F_2（Sr-FAP） and Ca_（10）（PO_4）_6F_2（CaFAP） are systematically investigated by the first-principles calculations. The calc...The electronic, elastic, vibrational, and thermodynamic properties of Sr_（10）（PO_4）_6F_2（Sr-FAP） and Ca_（10）（PO_4）_6F_2（CaFAP） are systematically investigated by the first-principles calculations. The calculated electronic band structure indicates that the Sr-FAP and Ca-FAP are insulator materials with the indirect band gap of 5.273 eV and 5.592 eV, respectively. The elastic constants are obtained by the “stress–strain” method, and elastic modulus are further evaluated and discussed. The vibrational properties, including the phonon dispersion curves, the phonon density of states, the Born effective charge, and associated longitudinal optical and transverse optical（LO–TO） splitting of optical modes, as well as the phonon frequencies at zone-center are obtained within the linear-response approach. Substitution of Ca by Sr causes phonon frequencies to shift to lower values as expected due to the mass effect. Additionally, some phonon-related thermodynamic properties, such as Helmholtz free energy F, internal energy E, entropy S, and specific heat C_V of Sr-FAP and Ca-FAP are predicted with the harmonic approximation. The present calculated results of two apatites are consistent with the reported experimental and theoretical results.展开更多
A simple and selective method for the separation of Be（Ⅱ） was developed using poly[dibenzo-18-crown-6] as a stationary phase in column chromatography. The study was carried out in L-arginine medium. 1.0-8.0 M HCl a...A simple and selective method for the separation of Be（Ⅱ） was developed using poly[dibenzo-18-crown-6] as a stationary phase in column chromatography. The study was carried out in L-arginine medium. 1.0-8.0 M HCl and CH3COOH, 0.5-8.0 M HBr, HClO4 and H2SO4, 0.2-1.0 M EDTA and 0.02-0.12 M ammonium oxalate were found to be an efficient eluents for Be（Ⅱ）. The capacity of polymer was 0.554-0.01 mmol/g of crown polymer. The tolerance limit of various cations and anions were reported. Be（Ⅱ） was quantitatively separated from Mg（Ⅱ）, Ca（Ⅱ）, Sr（Ⅱ） and Ba（Ⅱ）. The selective separation of Be（Ⅱ） was possible from multicomponent mixtures. The method was extended to determine Be（Ⅱ） from geological samples. Method was simple, rapid and selective having good reproducibility （approximately4-2%）.展开更多
基金supported by the National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200)the National Natural Science Foundation of China(Nos.22208373,22376217)+1 种基金the Beijing Nova Program(No.20220484215)the Science Foundation of China University of Petroleum,Beijing(No.2462023YJRC030)。
文摘It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.
文摘This study is a contribution to improving rice productivity on acidic plateau soils of the tropical rainforest zone. It is based on taking into account the cationic balances of the soil in order to optimize the phosphorus (P) nutrition of rice on these acidic soils, where this nutrient constitutes a limiting factor for agricultural production. Three (3) pot trials were conducted in Adiopodoumé in the forested south of Côte d’Ivoire. The interactive effects of calcium carbonate (0, 25, 50 and 75 kg Ca ha<sup>−1</sup>) and magnesium sulfate (0, 25, 50 and 75 kg Mg ha<sup>−1</sup>) were evaluated on the response of NERICA 5 rice at doses 0, 25, 50 and 75 kg P ha<sup>−1</sup> of natural phosphate from Togo, applied only once at the start of the experiment. Additional fertilizers of nitrogen (N) (100 kg N ha<sup>−1</sup>) and potassium (K) (50 kg KCl ha<sup>−1</sup>) were added to each of the tests in a split-plot device. The test results revealed a paddy production potential of approximately 3 to 5 t⋅ha<sup>−1</sup> for NERICA 5 on an acidic soil, under the effect of the interaction of P, Ca and Mg. The quadratic response of rice yield to the doses of these fertilizers would be more dependent on their balance, itself influenced by Ca nutrition. For the sustainability and maintenance of rice production in agro-ecology studied, it was recommended doses of 38 kg Ca ha<sup>−1</sup>, 34 kg Mg ha<sup>−1</sup> in a Ca/Mg ratio (1/1) with intakes of 41 kg P ha<sup>−1</sup>, overall in a ratio 1/1/1 (P/Ca/Mg) more favorable to the availability of free iron considered a guiding element of mineral nutrition. Thus, these promising results should be confirmed in a real environment for better management of the fertilization of rice cultivated on acidic plateau soils in Côte d’Ivoire.
基金supported by the National Natural Science Foundation of China(Grant No.21978066)Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project(Grant No.18964308D)the Key Program of Natural Science Foundation of Hebei Province(Grant No.B2020202048).
文摘Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.
基金The National Natural Science Foundation of China under contract Nos 41830539 and 41906063the Marine S&T Fund of Shandong Province for Pilot National Laboratory for Marine Science and Technology(Qingdao)under contract No.2022QNLM050203the Taishan Scholars Project Funding under contract No.ts20190963。
文摘Planktonic foraminifer Globigerinoides ruber(white)and Trilobatus sacculifer are the most frequently used mixedlayer dwelling species for reconstructing past oceanic environments.Specifically,the Mg/Ca ratios of these two foraminiferal species have been used for reconstructing tropical/subtropical changes in sea surface temperature(SST).However,these two species have different morphotypes,of which the spatial and temporal differences in Mg/Ca ratios and their influencing factors are still unclear.Our objective is to investigate the potential differences between the Mg/Ca ratios of these different morphotypes of G.ruber(white)and T.sacculifer in the western Philippine Sea(WPS)and determine their implications for the reconstruction of SST and upper-ocean structure.Mg/Ca measurements are made on two basic morphotypes of G.ruber(white)[sensu stricto(s.s.)and sensu lato(s.l.)]and T.sacculifer[with(w)and without(w/o)a sac-like final chamber]on samples of Site MD06-3047B from the WPS.Our results reveal that Mg/Ca ratios of different G.ruber morphotypes show consistent differences;and those of T.sacculifer morphotypes show staged variations since MIS 3.It is suggested to select a single morphotype for reconstructing SST changes using the Mg/Ca ratios of G.ruber and T.sacculifer in the WPS.Furthermore,the Mg/Ca ratios between G.ruber s.s.and G.ruber s.l.[Δ(Mg/Ca)_(G.ruber s.s.-s.l.)]downcore MD06-3047B covaries with indexes of summer monsoon.Combining with the core-top results,showing regional variation of differences in theΔ(Mg/Ca)_(G.ruber s.s.-s.l.)over the western tropical Pacific,we propose thatΔ(Mg/Ca)_(G.ruber s.s.-s.l.)may tend to reflect summer mixed layer depth.
基金Supported by the Key Research and Development Project of Guangdong Province(No.2020B1111510001)the National Natural Science Foundation of China(No.U2244224)+1 种基金the PI Project of Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(No.GML2020GD0802)the Guangdong Special Support Team Program(No.2019BT02H594)。
文摘Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in the Haima cold seeps at a water depth of 1381 m.Based on the scanning electron microscope(SEM)analyses,the prismatic layer and nacreous layer were identified,which are characterized by prismatic structure and stratified structure,respectively.In addition,the profile can be subdivided into two parts:altered and unaltered zones.Laser inductively coupled plasma mass spectrometry(LA-ICP-MS)mapping shows that the element concentrations of the altered zones were influenced by the authigenic carbonate rocks,whereas the element concentrations of unaltered zones remain stable.In-situ X-ray diffraction(XRD)analyses show that the mineral constituent of the prismatic layer is mainly composed of aragonite.Along with the growth profile,Mg/Ca ratios of unaltered zones have minor variations,ranging 0.72-0.97 mmol/mol(mean=0.87 mmol/mol),with estimated temperatures of 3.8-4.1℃,indicating that the temperature of the surrounding seawater remains constant and agree with the measured data of 3.9℃which was conducted by a conductivity-temperature-depth system(CTD).The minor variations of Ba/Ca ratios(0.01-0.06 mmol/mol;mean=0.04 mmol/mol)indicate a relatively stabilized salinity of the surrounding seawater.S/Ca ratios show large variations of 0.04-4.15 mmol/mol(mean=1.37 mmol/mol).S/Ca ratios have regular variations which generally correspond to the variations of the Mg/Ca ratios,highlighting that the S/Ca ratios of bivalve shells show the potential to reflect the growth rate of the Gigantides.However,further studies should be carried out on the understanding of the links between the S/Ca ratios and seepage intensity of cold-seep fluids.
文摘Sr_(0.5)Ca_(0.5)CuO_2 has been synthesized by the solid state reaction.The compound crystallizes in an orthorhombic unit cell,space group D_(2h)^(17)-Cmcm with a=3.444 ,b=16.11 ,c=3.868 .It decomposes shove 1038℃. Sr_(0.5)Ca_(0.5)CuO_2 is s black p-type semiconductor with resistivity 53Ω.cm at room tempersture.
文摘Highly textured (Bi,Pb)2Sr2Ca2Cu3Ox superconducting tapes have been fabricated by means of magnetic-field and vibration technique. This method is an effective way of improving the degree of grain alignment and density of oxide core in tapes after heat treatment and pressing cycles.Jc of above 20% was increased than that without treatment.
基金supported by the National High Technology Research and Development Program of China(Grant No.2015AA034202)the National Natural Science Foundation of China(Grant No.11305147)
文摘The electronic, elastic, vibrational, and thermodynamic properties of Sr_（10）（PO_4）_6F_2（Sr-FAP） and Ca_（10）（PO_4）_6F_2（CaFAP） are systematically investigated by the first-principles calculations. The calculated electronic band structure indicates that the Sr-FAP and Ca-FAP are insulator materials with the indirect band gap of 5.273 eV and 5.592 eV, respectively. The elastic constants are obtained by the “stress–strain” method, and elastic modulus are further evaluated and discussed. The vibrational properties, including the phonon dispersion curves, the phonon density of states, the Born effective charge, and associated longitudinal optical and transverse optical（LO–TO） splitting of optical modes, as well as the phonon frequencies at zone-center are obtained within the linear-response approach. Substitution of Ca by Sr causes phonon frequencies to shift to lower values as expected due to the mass effect. Additionally, some phonon-related thermodynamic properties, such as Helmholtz free energy F, internal energy E, entropy S, and specific heat C_V of Sr-FAP and Ca-FAP are predicted with the harmonic approximation. The present calculated results of two apatites are consistent with the reported experimental and theoretical results.
文摘A simple and selective method for the separation of Be（Ⅱ） was developed using poly[dibenzo-18-crown-6] as a stationary phase in column chromatography. The study was carried out in L-arginine medium. 1.0-8.0 M HCl and CH3COOH, 0.5-8.0 M HBr, HClO4 and H2SO4, 0.2-1.0 M EDTA and 0.02-0.12 M ammonium oxalate were found to be an efficient eluents for Be（Ⅱ）. The capacity of polymer was 0.554-0.01 mmol/g of crown polymer. The tolerance limit of various cations and anions were reported. Be（Ⅱ） was quantitatively separated from Mg（Ⅱ）, Ca（Ⅱ）, Sr（Ⅱ） and Ba（Ⅱ）. The selective separation of Be（Ⅱ） was possible from multicomponent mixtures. The method was extended to determine Be（Ⅱ） from geological samples. Method was simple, rapid and selective having good reproducibility （approximately4-2%）.
