Structural model of C100H79O7NS coal organic mass was obtained within density functional theory in the localized orbital basis set using the B3LYP hybrid functional. The model was compared with the known experimental ...Structural model of C100H79O7NS coal organic mass was obtained within density functional theory in the localized orbital basis set using the B3LYP hybrid functional. The model was compared with the known experimental data for coal of different grades and its sorption properties were studied with respect to CH4, CO2 and H2O. It has been shown that macromolecule of coal organic mass has bulk structure with a pore inside it. Interaction between coal and CH4 molecules consists of typical physical adsorption with oligomer formation on the pore border, physical adsorption with elements of chemical adsorption was also observed between coal and H2O molecules. Interaction between coal and H2O molecules included both physical and chemical adsorbion.展开更多
Organic matter(OM)nanopores developed in transitional facies shales,i.e.,the Upper Permian Longtan and Dalong Formations in the Yangtze Platform,China,were investigated to determine the corre-sponding influence of the...Organic matter(OM)nanopores developed in transitional facies shales,i.e.,the Upper Permian Longtan and Dalong Formations in the Yangtze Platform,China,were investigated to determine the corre-sponding influence of thermal maturity and OM types within the geological conditions.A suite of 16 core samples were taken from Type-Ⅲ Longtan shales and Type-Ⅱ Dalong shales from two wells covering a ma-turity(Ro,vitrinite reflectance)ranging from 1.22%to 1.43%and 2.62%to 2.97%,respectively.Integrated analysis of the shale samples was carried out,including field-emission scanning electron microscopy(FESEM),low-pressure N2 and CO2 adsorption,high-pressure CH4 adsorption,and mercury intrusion capillary pressure(MICP)analysis.The fluid inclusions of liquid and gas hydrocarbons trapped in calcite vein samples in Dalong shales of two wells were studied using laser Raman and fluorescence spectroscopy.FE-SEM images indicated that OM pores in different formations varied substantially in terms of shape,size,and distribution density.OM pores in Type-Ⅱ Dalong shales of Well XY1 were mainly micropore,sparsely distributed in the gas-prone kerogen with a spot-like and irregular shape,while bitumen rarely developed observable pores.In contrast,the morphology of OM pores in Type-Ⅲ Longtan shales were significantly different,which was due to differences in the OM type.The primary OM pores in some terrestrial woody debris in Longtan shales had a relatively larger pore diameter,ranging from hundreds of nanometers to a few micrometers and were al-most all rounded in shape,which might be one of the factors contributing to larger pore volume and gas adsorption capacity than Dalong shales of Well XY1.Comparing Dalong shales of Well XY1 with relatively lower thermal maturity,there were abundant spongy-like pores,densely developed in the pyrobitumen in Type-Ⅱ Dalong shales of Well EY1,with an irregular shape and diameter ranging from several to hundreds of nanometers.Many blue fluorescent oil inclusions and a small number of CH4 inclusions mixed with C2H6 could be observed within calcite veins in Dalong shales of Well XY1,whereas only CH4 inclusions could be identified within calcite veins in Dalong shales of Well EJ1.Therefore,thermal maturity not only controlled the type of hydrocarbons generated,but also makes a significant contribution to the formation of OM pores,resulting in larger pore volumes and adsorption capacity of Type-Ⅱ shale samples in the dry gas window.展开更多
Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and str...Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.展开更多
In accordance with the confusion on classification of source rocks, the authors raised a source rock classification for its enriched and dispersed organic matter types based on both Alpern’s idea and maceral genesis/...In accordance with the confusion on classification of source rocks, the authors raised a source rock classification for its enriched and dispersed organic matter types based on both Alpern’s idea and maceral genesis/composition. The determined rock type is roughly similar to palynofacies of Combaz , whereas it is "rock maceral facies (for coal viz. coal facies)" in strictly speaking. Therefore, it is necessary to use the organic ingredients classification proposed by the authors so that it can be used for both maceral analysis and environment research . This source rock classification not only shows sedimentology and diagenetic changes but also acquires organic matter type even if hydrocarbon potential derived from maceral’s geochemical parameters. So, it is considered as genetic classification. The "rock maceral facies" may be transformed to sedimentary organic facies , which is used as quantitative evaluation means if research being perfect.Now, there are many models in terms of structure either for coal or for kerogen. In our opinion, whatever coal or kerogen ought be polymer, then we follow Combaz’s thought and study structure of amorphous kerogens which are accordance with genetic mechanism showing biochemical and geochemical process perfectly. Here, we use the time of flight secondary ion mass spectrometry (TOFSIMS) to expand Combaz’s models from three to five. They are also models for coal.展开更多
The Peierls structural transition in the TTT<sub>2</sub>I<sub>3</sub> (tetrathiotetracene-iodide) crystal, for different values of carrier concentration is studied in 3D approximation. A crysta...The Peierls structural transition in the TTT<sub>2</sub>I<sub>3</sub> (tetrathiotetracene-iodide) crystal, for different values of carrier concentration is studied in 3D approximation. A crystal physical model is applied that considers two of the most important hole-phonon interactions. The first interaction describes the deformation potential and the second one is of polaron type. In the presented physical model, the interaction of carriers with the structural defects is taken into account. This is crucial for the explanation of the transition. The renormalized phonon spectrum is calculated in the random phase approximation for different temperatures applying the method of Green functions. The renormalized phonon frequencies for different temperatures are presented in two cases. In the first case the interaction between TTT chains is neglected. In the second one, this interaction is taken into account. Computer simulations for the 3D physical model of the TTT<sub>2</sub>I<sub>3</sub> crystal are performed for different values of dimensionless Fermi momentum <em>k</em><sub>F</sub>, that is determined by variation of carrier concentration. It is shown that the transition is of Peierls type and strongly depends on iodine concentration. Finally, the Peierls critical temperature was determined.展开更多
Precessing ball solitons (PBS) in a ferromagnet during the first order phase transition is induced by a magnetic field directed along the axis of anisotropy, while the action of the periodic field perpendicular to the...Precessing ball solitons (PBS) in a ferromagnet during the first order phase transition is induced by a magnetic field directed along the axis of anisotropy, while the action of the periodic field perpendicular to the main magnetic field has been analyzed. Under these conditions, the characteristics of arising equilibrium PBS are uniquely determined by the frequency of the periodic field, but the solitons with other frequencies are impossible. For such structure, the entropy increase connected with dissipation is compensated by the decrease of the entropy due to the external periodic field. It is shown that the equilibrium PBS are essentially the “self-organizing systems” that can arise spotaneously in a metastable state of ferromagnet.展开更多
为研究冻融循环作用下硫酸盐渍土热-质迁移规律及结构损伤机理,以河西走廊盐渍土为研究对象,在无压补给条件下进行冻融循环试验,并借助核磁共振和SEM(scanning electron microscope)试验分析冻融循环前、后硫酸盐渍土的孔隙结构损伤机理...为研究冻融循环作用下硫酸盐渍土热-质迁移规律及结构损伤机理,以河西走廊盐渍土为研究对象,在无压补给条件下进行冻融循环试验,并借助核磁共振和SEM(scanning electron microscope)试验分析冻融循环前、后硫酸盐渍土的孔隙结构损伤机理.研究表明:冻融循环作用下硫酸盐渍土内温度传递存在“深度效应”和“时间滞后效应”,时差约为5 h;冻结深度前期不断向下发展,后期逐渐趋于平稳,最大冻深为8.54 cm;溶液补给量随温度降低而增大,升高而减小;冻融循环240 h后水、盐含量在冻结区增大,非冻结区基本不变;盐渍土盐冻胀变形随温度变化呈周期性盐冻胀-融溶沉规律发展,且存在位移滞后温度效应;盐渍土经历一系列反复“冻结—冷凝—结晶—融化—溶解”过程后,中孔隙和大孔隙明显增多,并形成贯通的裂隙,土体结构由冻融前的片层状结构转变为絮状结构.展开更多
文摘Structural model of C100H79O7NS coal organic mass was obtained within density functional theory in the localized orbital basis set using the B3LYP hybrid functional. The model was compared with the known experimental data for coal of different grades and its sorption properties were studied with respect to CH4, CO2 and H2O. It has been shown that macromolecule of coal organic mass has bulk structure with a pore inside it. Interaction between coal and CH4 molecules consists of typical physical adsorption with oligomer formation on the pore border, physical adsorption with elements of chemical adsorption was also observed between coal and H2O molecules. Interaction between coal and H2O molecules included both physical and chemical adsorbion.
基金We would like to thank the National Key R&D program of China(No.2017YFE0103600)the National Natural Science Foundation of China(Nos.41830431,41672139)the China National Science and Technology Major Projects(No.2016ZX05034002-003)for financial assistance to this research.
文摘Organic matter(OM)nanopores developed in transitional facies shales,i.e.,the Upper Permian Longtan and Dalong Formations in the Yangtze Platform,China,were investigated to determine the corre-sponding influence of thermal maturity and OM types within the geological conditions.A suite of 16 core samples were taken from Type-Ⅲ Longtan shales and Type-Ⅱ Dalong shales from two wells covering a ma-turity(Ro,vitrinite reflectance)ranging from 1.22%to 1.43%and 2.62%to 2.97%,respectively.Integrated analysis of the shale samples was carried out,including field-emission scanning electron microscopy(FESEM),low-pressure N2 and CO2 adsorption,high-pressure CH4 adsorption,and mercury intrusion capillary pressure(MICP)analysis.The fluid inclusions of liquid and gas hydrocarbons trapped in calcite vein samples in Dalong shales of two wells were studied using laser Raman and fluorescence spectroscopy.FE-SEM images indicated that OM pores in different formations varied substantially in terms of shape,size,and distribution density.OM pores in Type-Ⅱ Dalong shales of Well XY1 were mainly micropore,sparsely distributed in the gas-prone kerogen with a spot-like and irregular shape,while bitumen rarely developed observable pores.In contrast,the morphology of OM pores in Type-Ⅲ Longtan shales were significantly different,which was due to differences in the OM type.The primary OM pores in some terrestrial woody debris in Longtan shales had a relatively larger pore diameter,ranging from hundreds of nanometers to a few micrometers and were al-most all rounded in shape,which might be one of the factors contributing to larger pore volume and gas adsorption capacity than Dalong shales of Well XY1.Comparing Dalong shales of Well XY1 with relatively lower thermal maturity,there were abundant spongy-like pores,densely developed in the pyrobitumen in Type-Ⅱ Dalong shales of Well EY1,with an irregular shape and diameter ranging from several to hundreds of nanometers.Many blue fluorescent oil inclusions and a small number of CH4 inclusions mixed with C2H6 could be observed within calcite veins in Dalong shales of Well XY1,whereas only CH4 inclusions could be identified within calcite veins in Dalong shales of Well EJ1.Therefore,thermal maturity not only controlled the type of hydrocarbons generated,but also makes a significant contribution to the formation of OM pores,resulting in larger pore volumes and adsorption capacity of Type-Ⅱ shale samples in the dry gas window.
基金supported by the State Key Laboratory of Structural Chemistry, National Natural Science Foundation of China (20873021)the Young Talent Programmed of Fujian Province (No. 2006F3072)
文摘Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.
基金National Natural Science Foundation of China(4 9672 13 1)
文摘In accordance with the confusion on classification of source rocks, the authors raised a source rock classification for its enriched and dispersed organic matter types based on both Alpern’s idea and maceral genesis/composition. The determined rock type is roughly similar to palynofacies of Combaz , whereas it is "rock maceral facies (for coal viz. coal facies)" in strictly speaking. Therefore, it is necessary to use the organic ingredients classification proposed by the authors so that it can be used for both maceral analysis and environment research . This source rock classification not only shows sedimentology and diagenetic changes but also acquires organic matter type even if hydrocarbon potential derived from maceral’s geochemical parameters. So, it is considered as genetic classification. The "rock maceral facies" may be transformed to sedimentary organic facies , which is used as quantitative evaluation means if research being perfect.Now, there are many models in terms of structure either for coal or for kerogen. In our opinion, whatever coal or kerogen ought be polymer, then we follow Combaz’s thought and study structure of amorphous kerogens which are accordance with genetic mechanism showing biochemical and geochemical process perfectly. Here, we use the time of flight secondary ion mass spectrometry (TOFSIMS) to expand Combaz’s models from three to five. They are also models for coal.
文摘The Peierls structural transition in the TTT<sub>2</sub>I<sub>3</sub> (tetrathiotetracene-iodide) crystal, for different values of carrier concentration is studied in 3D approximation. A crystal physical model is applied that considers two of the most important hole-phonon interactions. The first interaction describes the deformation potential and the second one is of polaron type. In the presented physical model, the interaction of carriers with the structural defects is taken into account. This is crucial for the explanation of the transition. The renormalized phonon spectrum is calculated in the random phase approximation for different temperatures applying the method of Green functions. The renormalized phonon frequencies for different temperatures are presented in two cases. In the first case the interaction between TTT chains is neglected. In the second one, this interaction is taken into account. Computer simulations for the 3D physical model of the TTT<sub>2</sub>I<sub>3</sub> crystal are performed for different values of dimensionless Fermi momentum <em>k</em><sub>F</sub>, that is determined by variation of carrier concentration. It is shown that the transition is of Peierls type and strongly depends on iodine concentration. Finally, the Peierls critical temperature was determined.
文摘Precessing ball solitons (PBS) in a ferromagnet during the first order phase transition is induced by a magnetic field directed along the axis of anisotropy, while the action of the periodic field perpendicular to the main magnetic field has been analyzed. Under these conditions, the characteristics of arising equilibrium PBS are uniquely determined by the frequency of the periodic field, but the solitons with other frequencies are impossible. For such structure, the entropy increase connected with dissipation is compensated by the decrease of the entropy due to the external periodic field. It is shown that the equilibrium PBS are essentially the “self-organizing systems” that can arise spotaneously in a metastable state of ferromagnet.
