We report a theoretical study on the electronic structures of O2 chemisorbed on a（8,0） SWNT with different oxygen contents of 6.25,12.5 and 25%,respectively.On the basis of DFT calculations,we find that eight O2 mol...We report a theoretical study on the electronic structures of O2 chemisorbed on a（8,0） SWNT with different oxygen contents of 6.25,12.5 and 25%,respectively.On the basis of DFT calculations,we find that eight O2 molecules chemisorbed on the（8,0） SWNT aligned in the middle row of the circumference of the tube in proportional spacing way,is seen to become metallic,and a significant increase in conductivity is expected.There are different electronic structures of the functionalized systems related to different oxygen contents or O2 molecules＇ chemisorbed positions.展开更多
FePt granular films were prepared by direct current facing-target magnetron sputtering system onto glass substrates and subsequently in-situ annealed in vacuum. Vibrating sample magnetometer, X-ray diffraction and sca...FePt granular films were prepared by direct current facing-target magnetron sputtering system onto glass substrates and subsequently in-situ annealed in vacuum. Vibrating sample magnetometer, X-ray diffraction and scanning probe microscope were applied to study the magnetic properties, microstructures, morphologies and domain structures of the samples. （FePt）27Ti73 bilayer films were fabricated at various conditions to investigate the effect of Ti on FePt grains. The results show that without Ti matrix layer, FePt films deposited onto the glass substrates are fcc disordered; with addition of Ti matrix layer, FePt/Ti films form a ternary （FePt）27Ti73 alloy possessing fcc and L10 （111） mixed texture. FePt/（FePt）27Ti73 films with perfectly ordered L10（111） structure and unique magnetic properties can be obtained at Ti thickness of 35nm and substrate temperature of 250℃. The maximum coercivity is more than 240kA/m and the squareness ratio is more than 0.9. The obtained results suggest that the granular FePt/（FePt）27Ti73 films can be applicable to ultrahigh-density magnetic recording media.展开更多
WnC0＇± （n= 1-6） clusters are investigated by using the density functional theory （DFT） at the B3LYP/LANL2DZ level. We find that the neutral, anionic and cationic ground state structures are similar within th...WnC0＇± （n= 1-6） clusters are investigated by using the density functional theory （DFT） at the B3LYP/LANL2DZ level. We find that the neutral, anionic and cationic ground state structures are similar within the same size, and constituted by substituting a C atom for one W atom in the structures of Wn＋1 clusters. The natural bond orbital （NBO） charge analyses indicate that the direction of electron transfer is from the W atom to the 2p orbital of the C atom. In addition, the calculated infrared spectra of the WnC0＇± （n= 2-6） clusters manifest that the vibrational frequencies of neutral, anionic and cationic clusters are similar in a range of 80 cm-1-864 cm-1. The high frequency, strong peak modes are found to be an almost stretched deformation of the carbide atom. Finally, the polarizabilities of WnC0＇± （n= 1-6） clusters are also discussed.展开更多
To more in depth understand the doping effects of oxygen on SiGe alloys, both the micro-structure and properties of O-doped SiGe （including： bulk, （001） surface, and （110） surface） are calculated by DPT ＋ U me...To more in depth understand the doping effects of oxygen on SiGe alloys, both the micro-structure and properties of O-doped SiGe （including： bulk, （001） surface, and （110） surface） are calculated by DPT ＋ U method in the present work. The calculated results are as follows. （i） The （110） surface is the main exposing surface of SiGe, in which O impurity prefers to occupy the surface vacancy sites. （ii） For O interstitial doping on SiGe （110） surface, the existences of energy states caused by 0 doping in the band gap not only enhance the infrared light absorption, but also improve the behaviors of photo-generated carriers. （iii） The finding about decreased surface work function of O-doped SiGe （110） surface can confirm previous experimental observations. （iv） In all cases, O doing mainly induces the electronic structures near the band gap to vary, but is not directly involved in these variations. Therefore, these findings in the present work not only can provide further explanation and analysis for the corresponding underlying mechanism for some of the experimental findings reported in the literature, but also conduce to the development of μc-SiGe-based solar ceils in the future.展开更多
The reaction of W（CO）6 with pyOSNa （C5H4NOSNa） and Et4NCl in MeCN affords a new tungsten（0）complex [Et4N][W（pyS）（CO）4] 1 （Mr = 536.29）. The crystal and molecular structures have been determined by X-ray si...The reaction of W（CO）6 with pyOSNa （C5H4NOSNa） and Et4NCl in MeCN affords a new tungsten（0）complex [Et4N][W（pyS）（CO）4] 1 （Mr = 536.29）. The crystal and molecular structures have been determined by X-ray single-crystal diffraction. Complex 1 crystallizes in the orthorhombic system, space group P212121 with α= 8.2429（5）, b = 9.1045（4）, c = 26.8851（14） A, β= 90.00°, V=2017.66（18） A3^, Z = 4, Dc = 1.765 g/cm^3, μ= 58.51 cm^-1, F（000） = 1048, the final R = 0.0204 and wR = 0.0400 for 4432 observed reflections with I 〉 2σ（I）. X-ray structure analysis revealed that the molecule is acentric and has large first=order hyperpolarizability （7.2 × 10^-30 esu）, so it could be an IR second=order nonlinear optical candidate material.展开更多
The microhydration structure of nickel sulfate aqueous solution has been determined via density functional theory (DFT) calculation and extended X-ray absorption fine structure (EXAFS) spectroscopy.The geometric optim...The microhydration structure of nickel sulfate aqueous solution has been determined via density functional theory (DFT) calculation and extended X-ray absorption fine structure (EXAFS) spectroscopy.The geometric optimization and energy calculation of nickel sulfate hydrated clusters of the molecular formula [NiSO4(H2O)n ]^0 (n=1-12) were determined via DFT using the B3LYP method.Several possible initial structures were considered for clusters of each size to locate the equilibrium geometry.Based on the DFT calculation,the favorable structure of Ni^2+ includes the six-coordinated form of [NiSO4(H2O)n ]^0 clusters.The results of hydration energy calculation suggest that the six-coordinated contact ion pair (CIP) is the stable configuration for small hydration clusters (n≤5),while the solvent-shared ion pair (SSIP) represents the favorable structure for medium hydration clusters (6≤n≤10).The solvent is separated by x water molecules (xSIP,x≥2 is the number of water molecule between Ni^2+ and SO4^2-) in larger hydration clusters (n≥11).The EXAFS analysis of the NiSO 4 aqueous solutions and NiSO4 ·6H2O solid established that Ni^2+ was surrounded by six water molecules tightly forming an octahedral structure in the first hydration shell,and no CIP was found from 0.70 mol/L to 2.22 mol/L (near saturation).The Ni-O distance and coordinated number were 2.040±0.020 and 6.0±1.0,respectively.These results are consistent with the DFT calculations for [NiSO4(H2O)n ]^0 clusters.DFT and EXAFS are powerful techniques that can be used to enhance the resolution of NiSO 4 solution microstructure.展开更多
The tight reservoirs of the Fengcheng Formation at the southern margin of the Mahu Sag have strong heterogeneity due to the diversity in their pore types, sizes, and structures. The microscopic characteristics of tigh...The tight reservoirs of the Fengcheng Formation at the southern margin of the Mahu Sag have strong heterogeneity due to the diversity in their pore types, sizes, and structures. The microscopic characteristics of tight reservoirs and the mechanisms that generate them are of significance in identifying the distribution of high-quality reservoirs and in improving the prediction accuracy of sweet spots in tight oil reservoirs. In this paper, high-pressure mercury intrusion (HPMI) and nuclear magnetic resonance (NMR) experiments were carried out on samples from the tight reservoirs in the study area. These experimental results were combined with cluster analysis, fractal theory, and microscopic observations to qualitatively and quantitatively evaluate pore types, sizes, and structures. A classification scheme was established that divides the reservoir into four types, based on the microstructure characteristics of samples, and the genetic mechanisms that aided the development of reservoir microstructure were analyzed. The results show that the lower limit for the tight reservoir in the Fengcheng Formation is Φ of 3.5% and K of 0.03 mD. The pore throat size and distribution span gradually decrease from Type I, through Type II and Type III reservoirs to non-reservoirs, and the pore type also evolves from dominantly intergranular pores to intercrystalline pores. The structural trend shows a decrease in the ball-stick pore-throat system and an increase in the branch-like pore-throat system. The dual effects of sedimentation and diagenesis shape the microscopic characteristics of pores and throats. The sorting, roundness, and particle size of the original sediments determine the original physical properties of the reservoir. The diagenetic environment of ‘two alkalinity stages and one acidity stage’ influenced the evolution of pore type and size. Although the cementation of authigenic minerals in the early alkaline environment adversely affected reservoir properties, it also alleviated the damage of the later compaction to some extent. Dissolution in the mid-term acidic environment greatly improved the physical properties of this tight reservoir, making dissolution pores an important reservoir space. The late alkaline environment occurred after large-scale oil and gas accumulation. During this period, the cementation of authigenic minerals had a limited effect on the reservoir space occupied by crude oil. It had a more significant impact on the sand bodies not filled with oil, making them function as barriers.展开更多
Herein,Pd nanoparticles loaded Co_(3)O_(4)catalysts(Pd@Co_(3)O_(4))are constructed from zeolitic imidazolate framework-67(ZIF-67)for the ethanol oxidation reaction(EOR).It is demonstrated for the first time that the e...Herein,Pd nanoparticles loaded Co_(3)O_(4)catalysts(Pd@Co_(3)O_(4))are constructed from zeolitic imidazolate framework-67(ZIF-67)for the ethanol oxidation reaction(EOR).It is demonstrated for the first time that the electrochemical conversion of Co_(3)O_(4)support would result in the charge distribution alignment at the Pd/Co_(3)O_(4)interface and induce the formation of highly reactive Pd-O species(PdO^(*)),which can further catalyze the consequent reactions of the intermediates of the ethanol oxidation.The catalyst,Pd@Co_(3)O_(4)-450,obtained under the optimized conditions exhibits excellent EOR performance with a high mass activity of 590 mA mg-1,prominent operational stability,and extraordinary capability for the electro-oxidation of acetaldehyde intermediates.Importantly,the detailed mechanism investigation reveals that Pd@Co_(3)O_(4)-450 could be benefit to the C-C bond cleavage to promote the desirable C1 pathway for the ethanol oxidation reaction.The present strategy based on the metal-support interaction of the catalyst might provide valuable inspiration for the design of high-performing catalysts for the ethanol oxidation reaction.展开更多
Reaction of Et 4NCl, NaSCH 2COOMe and W(CO) 6 in MeCN affords a new dinuclear tungsten(0) complex Et 4N 2 W 2(CO) 8(SCH 2COOMe) 2 (1). The crystal and molecular structure has been determined by X ray ...Reaction of Et 4NCl, NaSCH 2COOMe and W(CO) 6 in MeCN affords a new dinuclear tungsten(0) complex Et 4N 2 W 2(CO) 8(SCH 2COOMe) 2 (1). The crystal and molecular structure has been determined by X ray single crystal diffraction. 1 Crystallized in the triclinic, space group P 1 with a=11.141(7), b=10.267(4), c=10.798(3) ; α=93.96(3), β=96.88(4), γ=114.97(5)°; V=1003 3, Z=1, D c =1.76 g/cm 3, μ =60.1 cm -1 , R =0.042 and R w =0.050 for 2967 independent reflections with I】3.0 σ(I) . 1 contains a WS 2W planar core with nonbonding W…W distance of 3.9611(5) , and its IR, 13 C NMR, and cyclic voltammetry were measured and discussed.展开更多
Surface engineering and Cu valence regulation are essential factors in improving the C_(2)selectivity during the electrochemical reduction of CO_(2).Herein,we present a sea urchin-like CuO/Cu_(2)O catalyst derived fro...Surface engineering and Cu valence regulation are essential factors in improving the C_(2)selectivity during the electrochemical reduction of CO_(2).Herein,we present a sea urchin-like CuO/Cu_(2)O catalyst derived from rhombic dodecahedra Cu_(2)O through one-step oxidation/etching method where the mixed Cu^(+)/Cu^(0)states are formed via in situ reduction during electrocatalysis.The combined effects of the morphology and the mixed Cu^(+)/Cu^(0)states on C–C coupling are evaluated by the Faradaic efficiency of C_(2)and the C_(2)/C1 ratio obtained in an H-cell.R-Cu^(O)/Cu_(2)O exhibited 49.5%Faradaic efficiency of C_(2)with a C_(2)/C1 ratio of 3.1 at−1.4 V vs.reversible hydrogen electrode,which are 1.5 and 3.2 times higher than those of R-Cu_(2)O,respectively.Using a flow-cell,68.0%Faradaic efficiency of C_(2)is achieved at a current density of 500 mA·cm^(−2).The formation of the mixed Cu^(+)/Cu^(0)states was confirmed by in situ Raman spectra.Additionally,the sea urchin-like structure provides more active sites and enables faster electron transfer.As a result,the excellent C_(2)production on R-CuO/Cu_(2)O is primarily attributed to the synergistic effects of the sea urchin-like structure and the stable mixed Cu^(+)/Cu^(0)states.Therefore,this work presents an integrated strategy for developing Cu-based electrocatalysts for C_(2)production through electrochemical CO_(2)reduction.展开更多
Mg_(3)Bi_(2-x)Sb_(x)(0≤x≤2)have gained significant attention due to their potential in thermoelectric(TE)applications.However,there has been much debating regarding their structural properties and phase diagram as a...Mg_(3)Bi_(2-x)Sb_(x)(0≤x≤2)have gained significant attention due to their potential in thermoelectric(TE)applications.However,there has been much debating regarding their structural properties and phase diagram as a function of pressure,which is crucial for understanding of their TE properties.Here,we investigate a unified phase diagram of Mg_(3)(Bi,Sb)_(2) materials up to 40 GPa at room temperature using high-pressure X-ray diffraction.Two high-pressure phases with the structural transition succession of P3m1→C2/m→P21/n are observed,which is valid for all Mg_(3)Bi_(2-x)Sb_(x)(0≤x≤2)compounds.We further explore the low-pressure phase P3m1 and report that alloying does not change the quasi-isotropic compression of the unit lattice parameters nor has effect on the anisotropic bond compressibility,as recently reported for the end-members.Our study presents a comprehensive picture of Mg_(3)Bi_(2–x)Sb_(x) as a function of pressure and chemical composition providing a solid foundation for the future experimental and theoretical studies searching for the most efficient TE compound in Mg_(3)(Bi,Sb)_(2).展开更多
The source of ore\|forming materials has long been a controversial focus both in metallogenic theory and in ore\|searching practice. This study deals with the helium and argon isotopic characteristics of pyrites from ...The source of ore\|forming materials has long been a controversial focus both in metallogenic theory and in ore\|searching practice. This study deals with the helium and argon isotopic characteristics of pyrites from 11 gold deposits and some country rocks in the gold mineralization\|concentrated areas within the three mantle\|branch structures in the region of North Hebei Province. It is indicated that \{\}\+3He/\+4He ratios in the gold deposits are within the range of \{0.93×10\+\{-6\}\}-\{7.3×10\+\{-6\}\}, with an average of \{3.55\} ×10\+\{-6\}; R/Ra=\{0.66\}-\{4.93\}, averaging \{2.53\}; \{\{\}\+\{40\}Ar/\+\{39\}Ar\} ratios vary between 426 and 2073, with the average value of \{\}\+\{40\}Ar being \{8.32\}; and the average of \{\}\+4He/\{\}\+\{40\}Ar ratios is 2.17. \{\}\+3He/ \{\}\+4He ratios in gneiss and granite in the periphery of the mining district are within the range of \{0.001×10\+\{-6\}\}-\{0.55×10\+\{-6\}\}, reflecting significant differences in their sources. \{\}\+3He and \{\}\+4He fall near the mantle, as is shown in the He concentration diagram. Studies have shown that the ore\|forming materials in this region should come from the deep interior of the Earth. With the multi\|stage evolution of mantle plume, ore\|forming fluids in the deep interior were moving upwards to shallow levels (crust). Under such circumstances, there would be inevitably occur crust/mantle fluid mixing, so their noble gas isotopic characteristics are intermediate between the mantle and the crust.展开更多
A first-principles approach is employed to study the structural, electronic, and magnetic properties of RbCaX2 （X = C, N, and O） full-Heusler compounds. It is observed that RbCaN2 and RbCaO2 are new do half-metals w...A first-principles approach is employed to study the structural, electronic, and magnetic properties of RbCaX2 （X = C, N, and O） full-Heusler compounds. It is observed that RbCaN2 and RbCaO2 are new do half-metals with an integer magnetic moment of 3 μB and 1 μB in their ferrimagnetic ground states, respectively, while RbCaC2 is a common metallic compound. Analysis of the density of states of these compounds indicates that the magnetic moment and furthermore, the half-metallicity primarily originate from the spin-polarization of the p-like states of N and O atoms. The half-metallic （HM） gaps of RbCaN2 and RbCaO2 are notably large; thus, the half-metallicity is robust against lattice distortion. Such materials are suitable to be grown on various semiconductor substrates. In addition, for RbCaN2 and RbCaO2, four possible terminations of the surface are also calculated.展开更多
基金Supported by the National Natural Science Foundation of China (No. 20673019)
文摘We report a theoretical study on the electronic structures of O2 chemisorbed on a（8,0） SWNT with different oxygen contents of 6.25,12.5 and 25%,respectively.On the basis of DFT calculations,we find that eight O2 molecules chemisorbed on the（8,0） SWNT aligned in the middle row of the circumference of the tube in proportional spacing way,is seen to become metallic,and a significant increase in conductivity is expected.There are different electronic structures of the functionalized systems related to different oxygen contents or O2 molecules＇ chemisorbed positions.
基金Project(10274018) supported by the National Natural Science Foundation of China project(Z200102) supported the KeyFoundation of Hebei Normal University project(2002116) supported the Foundation Education Department of of Hebei Provin
文摘FePt granular films were prepared by direct current facing-target magnetron sputtering system onto glass substrates and subsequently in-situ annealed in vacuum. Vibrating sample magnetometer, X-ray diffraction and scanning probe microscope were applied to study the magnetic properties, microstructures, morphologies and domain structures of the samples. （FePt）27Ti73 bilayer films were fabricated at various conditions to investigate the effect of Ti on FePt grains. The results show that without Ti matrix layer, FePt films deposited onto the glass substrates are fcc disordered; with addition of Ti matrix layer, FePt/Ti films form a ternary （FePt）27Ti73 alloy possessing fcc and L10 （111） mixed texture. FePt/（FePt）27Ti73 films with perfectly ordered L10（111） structure and unique magnetic properties can be obtained at Ti thickness of 35nm and substrate temperature of 250℃. The maximum coercivity is more than 240kA/m and the squareness ratio is more than 0.9. The obtained results suggest that the granular FePt/（FePt）27Ti73 films can be applicable to ultrahigh-density magnetic recording media.
基金supported by the National Natural Science Foundation of China (Grant No. 51072072)
文摘WnC0＇± （n= 1-6） clusters are investigated by using the density functional theory （DFT） at the B3LYP/LANL2DZ level. We find that the neutral, anionic and cationic ground state structures are similar within the same size, and constituted by substituting a C atom for one W atom in the structures of Wn＋1 clusters. The natural bond orbital （NBO） charge analyses indicate that the direction of electron transfer is from the W atom to the 2p orbital of the C atom. In addition, the calculated infrared spectra of the WnC0＇± （n= 2-6） clusters manifest that the vibrational frequencies of neutral, anionic and cationic clusters are similar in a range of 80 cm-1-864 cm-1. The high frequency, strong peak modes are found to be an almost stretched deformation of the carbide atom. Finally, the polarizabilities of WnC0＇± （n= 1-6） clusters are also discussed.
基金Project supported by the Natural Science Foundation of Yunnan Province,China(Grant No.2015FB123)the 18th Yunnan Province Young Academic and Technical Leaders Reserve Talent Project,China(Grant No.2015HB015)the National Natural Science Foundation of China(Grant No.U1037604)
文摘To more in depth understand the doping effects of oxygen on SiGe alloys, both the micro-structure and properties of O-doped SiGe （including： bulk, （001） surface, and （110） surface） are calculated by DPT ＋ U method in the present work. The calculated results are as follows. （i） The （110） surface is the main exposing surface of SiGe, in which O impurity prefers to occupy the surface vacancy sites. （ii） For O interstitial doping on SiGe （110） surface, the existences of energy states caused by 0 doping in the band gap not only enhance the infrared light absorption, but also improve the behaviors of photo-generated carriers. （iii） The finding about decreased surface work function of O-doped SiGe （110） surface can confirm previous experimental observations. （iv） In all cases, O doing mainly induces the electronic structures near the band gap to vary, but is not directly involved in these variations. Therefore, these findings in the present work not only can provide further explanation and analysis for the corresponding underlying mechanism for some of the experimental findings reported in the literature, but also conduce to the development of μc-SiGe-based solar ceils in the future.
基金This research was supported by NNSFC (No. 01008) and SKLSC (No. 980148-2)
文摘The reaction of W（CO）6 with pyOSNa （C5H4NOSNa） and Et4NCl in MeCN affords a new tungsten（0）complex [Et4N][W（pyS）（CO）4] 1 （Mr = 536.29）. The crystal and molecular structures have been determined by X-ray single-crystal diffraction. Complex 1 crystallizes in the orthorhombic system, space group P212121 with α= 8.2429（5）, b = 9.1045（4）, c = 26.8851（14） A, β= 90.00°, V=2017.66（18） A3^, Z = 4, Dc = 1.765 g/cm^3, μ= 58.51 cm^-1, F（000） = 1048, the final R = 0.0204 and wR = 0.0400 for 4432 observed reflections with I 〉 2σ（I）. X-ray structure analysis revealed that the molecule is acentric and has large first=order hyperpolarizability （7.2 × 10^-30 esu）, so it could be an IR second=order nonlinear optical candidate material.
基金Nature Science Foundation of Qinghai Province(2018-ZJ-945Q)NSFC(21573268)+1 种基金Joint Foundation of Salt Lake Chemical(U1607106)Instrument function development and technology innovation project of Chinese academy of sciences(2018g108)
文摘The microhydration structure of nickel sulfate aqueous solution has been determined via density functional theory (DFT) calculation and extended X-ray absorption fine structure (EXAFS) spectroscopy.The geometric optimization and energy calculation of nickel sulfate hydrated clusters of the molecular formula [NiSO4(H2O)n ]^0 (n=1-12) were determined via DFT using the B3LYP method.Several possible initial structures were considered for clusters of each size to locate the equilibrium geometry.Based on the DFT calculation,the favorable structure of Ni^2+ includes the six-coordinated form of [NiSO4(H2O)n ]^0 clusters.The results of hydration energy calculation suggest that the six-coordinated contact ion pair (CIP) is the stable configuration for small hydration clusters (n≤5),while the solvent-shared ion pair (SSIP) represents the favorable structure for medium hydration clusters (6≤n≤10).The solvent is separated by x water molecules (xSIP,x≥2 is the number of water molecule between Ni^2+ and SO4^2-) in larger hydration clusters (n≥11).The EXAFS analysis of the NiSO 4 aqueous solutions and NiSO4 ·6H2O solid established that Ni^2+ was surrounded by six water molecules tightly forming an octahedral structure in the first hydration shell,and no CIP was found from 0.70 mol/L to 2.22 mol/L (near saturation).The Ni-O distance and coordinated number were 2.040±0.020 and 6.0±1.0,respectively.These results are consistent with the DFT calculations for [NiSO4(H2O)n ]^0 clusters.DFT and EXAFS are powerful techniques that can be used to enhance the resolution of NiSO 4 solution microstructure.
基金supported by a Major Projects grant of the China National Petroleum Corporation(Project No.2021DJ1003).
文摘The tight reservoirs of the Fengcheng Formation at the southern margin of the Mahu Sag have strong heterogeneity due to the diversity in their pore types, sizes, and structures. The microscopic characteristics of tight reservoirs and the mechanisms that generate them are of significance in identifying the distribution of high-quality reservoirs and in improving the prediction accuracy of sweet spots in tight oil reservoirs. In this paper, high-pressure mercury intrusion (HPMI) and nuclear magnetic resonance (NMR) experiments were carried out on samples from the tight reservoirs in the study area. These experimental results were combined with cluster analysis, fractal theory, and microscopic observations to qualitatively and quantitatively evaluate pore types, sizes, and structures. A classification scheme was established that divides the reservoir into four types, based on the microstructure characteristics of samples, and the genetic mechanisms that aided the development of reservoir microstructure were analyzed. The results show that the lower limit for the tight reservoir in the Fengcheng Formation is Φ of 3.5% and K of 0.03 mD. The pore throat size and distribution span gradually decrease from Type I, through Type II and Type III reservoirs to non-reservoirs, and the pore type also evolves from dominantly intergranular pores to intercrystalline pores. The structural trend shows a decrease in the ball-stick pore-throat system and an increase in the branch-like pore-throat system. The dual effects of sedimentation and diagenesis shape the microscopic characteristics of pores and throats. The sorting, roundness, and particle size of the original sediments determine the original physical properties of the reservoir. The diagenetic environment of ‘two alkalinity stages and one acidity stage’ influenced the evolution of pore type and size. Although the cementation of authigenic minerals in the early alkaline environment adversely affected reservoir properties, it also alleviated the damage of the later compaction to some extent. Dissolution in the mid-term acidic environment greatly improved the physical properties of this tight reservoir, making dissolution pores an important reservoir space. The late alkaline environment occurred after large-scale oil and gas accumulation. During this period, the cementation of authigenic minerals had a limited effect on the reservoir space occupied by crude oil. It had a more significant impact on the sand bodies not filled with oil, making them function as barriers.
基金supported by the National Natural Science Foundation of China(21336005)the Ministry of Science and Technology of China(2014EG111224)+1 种基金the National Key R&D Program of China(2021YFB4001200)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_3185)。
文摘Herein,Pd nanoparticles loaded Co_(3)O_(4)catalysts(Pd@Co_(3)O_(4))are constructed from zeolitic imidazolate framework-67(ZIF-67)for the ethanol oxidation reaction(EOR).It is demonstrated for the first time that the electrochemical conversion of Co_(3)O_(4)support would result in the charge distribution alignment at the Pd/Co_(3)O_(4)interface and induce the formation of highly reactive Pd-O species(PdO^(*)),which can further catalyze the consequent reactions of the intermediates of the ethanol oxidation.The catalyst,Pd@Co_(3)O_(4)-450,obtained under the optimized conditions exhibits excellent EOR performance with a high mass activity of 590 mA mg-1,prominent operational stability,and extraordinary capability for the electro-oxidation of acetaldehyde intermediates.Importantly,the detailed mechanism investigation reveals that Pd@Co_(3)O_(4)-450 could be benefit to the C-C bond cleavage to promote the desirable C1 pathway for the ethanol oxidation reaction.The present strategy based on the metal-support interaction of the catalyst might provide valuable inspiration for the design of high-performing catalysts for the ethanol oxidation reaction.
文摘Reaction of Et 4NCl, NaSCH 2COOMe and W(CO) 6 in MeCN affords a new dinuclear tungsten(0) complex Et 4N 2 W 2(CO) 8(SCH 2COOMe) 2 (1). The crystal and molecular structure has been determined by X ray single crystal diffraction. 1 Crystallized in the triclinic, space group P 1 with a=11.141(7), b=10.267(4), c=10.798(3) ; α=93.96(3), β=96.88(4), γ=114.97(5)°; V=1003 3, Z=1, D c =1.76 g/cm 3, μ =60.1 cm -1 , R =0.042 and R w =0.050 for 2967 independent reflections with I】3.0 σ(I) . 1 contains a WS 2W planar core with nonbonding W…W distance of 3.9611(5) , and its IR, 13 C NMR, and cyclic voltammetry were measured and discussed.
基金supported by the National Natural Science Foundation of China(Grant No.22178266).
文摘Surface engineering and Cu valence regulation are essential factors in improving the C_(2)selectivity during the electrochemical reduction of CO_(2).Herein,we present a sea urchin-like CuO/Cu_(2)O catalyst derived from rhombic dodecahedra Cu_(2)O through one-step oxidation/etching method where the mixed Cu^(+)/Cu^(0)states are formed via in situ reduction during electrocatalysis.The combined effects of the morphology and the mixed Cu^(+)/Cu^(0)states on C–C coupling are evaluated by the Faradaic efficiency of C_(2)and the C_(2)/C1 ratio obtained in an H-cell.R-Cu^(O)/Cu_(2)O exhibited 49.5%Faradaic efficiency of C_(2)with a C_(2)/C1 ratio of 3.1 at−1.4 V vs.reversible hydrogen electrode,which are 1.5 and 3.2 times higher than those of R-Cu_(2)O,respectively.Using a flow-cell,68.0%Faradaic efficiency of C_(2)is achieved at a current density of 500 mA·cm^(−2).The formation of the mixed Cu^(+)/Cu^(0)states was confirmed by in situ Raman spectra.Additionally,the sea urchin-like structure provides more active sites and enables faster electron transfer.As a result,the excellent C_(2)production on R-CuO/Cu_(2)O is primarily attributed to the synergistic effects of the sea urchin-like structure and the stable mixed Cu^(+)/Cu^(0)states.Therefore,this work presents an integrated strategy for developing Cu-based electrocatalysts for C_(2)production through electrochemical CO_(2)reduction.
基金W.Xu acknowledges the National Natural Science Foundation of China(Grants no.12075273)Y.Pan acknowledges the financial support from Alexander von Humboldt Foundation.S.Liu acknowledges National Natural Science Foundation of China under Grant No.51872133Shenzhen Key Program for Long-Term Academic Support Plan 20200925164021002.
文摘Mg_(3)Bi_(2-x)Sb_(x)(0≤x≤2)have gained significant attention due to their potential in thermoelectric(TE)applications.However,there has been much debating regarding their structural properties and phase diagram as a function of pressure,which is crucial for understanding of their TE properties.Here,we investigate a unified phase diagram of Mg_(3)(Bi,Sb)_(2) materials up to 40 GPa at room temperature using high-pressure X-ray diffraction.Two high-pressure phases with the structural transition succession of P3m1→C2/m→P21/n are observed,which is valid for all Mg_(3)Bi_(2-x)Sb_(x)(0≤x≤2)compounds.We further explore the low-pressure phase P3m1 and report that alloying does not change the quasi-isotropic compression of the unit lattice parameters nor has effect on the anisotropic bond compressibility,as recently reported for the end-members.Our study presents a comprehensive picture of Mg_(3)Bi_(2–x)Sb_(x) as a function of pressure and chemical composition providing a solid foundation for the future experimental and theoretical studies searching for the most efficient TE compound in Mg_(3)(Bi,Sb)_(2).
文摘The source of ore\|forming materials has long been a controversial focus both in metallogenic theory and in ore\|searching practice. This study deals with the helium and argon isotopic characteristics of pyrites from 11 gold deposits and some country rocks in the gold mineralization\|concentrated areas within the three mantle\|branch structures in the region of North Hebei Province. It is indicated that \{\}\+3He/\+4He ratios in the gold deposits are within the range of \{0.93×10\+\{-6\}\}-\{7.3×10\+\{-6\}\}, with an average of \{3.55\} ×10\+\{-6\}; R/Ra=\{0.66\}-\{4.93\}, averaging \{2.53\}; \{\{\}\+\{40\}Ar/\+\{39\}Ar\} ratios vary between 426 and 2073, with the average value of \{\}\+\{40\}Ar being \{8.32\}; and the average of \{\}\+4He/\{\}\+\{40\}Ar ratios is 2.17. \{\}\+3He/ \{\}\+4He ratios in gneiss and granite in the periphery of the mining district are within the range of \{0.001×10\+\{-6\}\}-\{0.55×10\+\{-6\}\}, reflecting significant differences in their sources. \{\}\+3He and \{\}\+4He fall near the mantle, as is shown in the He concentration diagram. Studies have shown that the ore\|forming materials in this region should come from the deep interior of the Earth. With the multi\|stage evolution of mantle plume, ore\|forming fluids in the deep interior were moving upwards to shallow levels (crust). Under such circumstances, there would be inevitably occur crust/mantle fluid mixing, so their noble gas isotopic characteristics are intermediate between the mantle and the crust.
基金Project supported by the Science Director Foundation Project of the National Natural Science Foundation of China(Grant No.11347179)
文摘A first-principles approach is employed to study the structural, electronic, and magnetic properties of RbCaX2 （X = C, N, and O） full-Heusler compounds. It is observed that RbCaN2 and RbCaO2 are new do half-metals with an integer magnetic moment of 3 μB and 1 μB in their ferrimagnetic ground states, respectively, while RbCaC2 is a common metallic compound. Analysis of the density of states of these compounds indicates that the magnetic moment and furthermore, the half-metallicity primarily originate from the spin-polarization of the p-like states of N and O atoms. The half-metallic （HM） gaps of RbCaN2 and RbCaO2 are notably large; thus, the half-metallicity is robust against lattice distortion. Such materials are suitable to be grown on various semiconductor substrates. In addition, for RbCaN2 and RbCaO2, four possible terminations of the surface are also calculated.
