Aim To synthesize trans and cis-3, 4′, 5-trihydroxystilbene by a new convenient route. Methods The reaction of 3, 5-dimethoxybenzaldehyde （3） and 4-methoxy phenylacetonitrile （4） formed the stilbene skeleton. Aft...Aim To synthesize trans and cis-3, 4′, 5-trihydroxystilbene by a new convenient route. Methods The reaction of 3, 5-dimethoxybenzaldehyde （3） and 4-methoxy phenylacetonitrile （4） formed the stilbene skeleton. After hydrolyzation, decarboxylation, and demethylation, we obtained trans-3, 4′, 5-trihydroxystilbene （resveratrol）, which can be converted to its cis-isomer by photochemical isomerization. Results Starting from 3 and 4, trans and cis-3, 4′, 5-trihydroxystilbene were synthesized, respectively. Conclusion A facile method for the synthesis of trans and cis-hydroxystilbenes from readily available materials was established.展开更多
Urea-isobutyraldehyde-formaldehyde (UIF) resin was synthesized from urea, isobutyraldehyde, and formaldehyde using sulfuric acid as a catalyst by one pot method. The effects of molar ratios of isobutyraldehyde to form...Urea-isobutyraldehyde-formaldehyde (UIF) resin was synthesized from urea, isobutyraldehyde, and formaldehyde using sulfuric acid as a catalyst by one pot method. The effects of molar ratios of isobutyraldehyde to formaldehyde (n(I)/n(F)) and aldehyde to urea (n(A)/n(U)) on the yield, hydroxyl value (vs KOH) and softening point of the resin were investigated. The structure of the resin was characterized by FT-IR, 1H-NMR and 13C-NMR. The results show that when the molar ratio of urea to isobutyraldehyde to formaldehyde (n(U)/n(I)/n(F)) is 1.0/3.0/3.0, the yield UIF resin is 67.1%, and the softening point and hydroxyl value are 88 ℃ and 37 mg/g, respectively. The FT-IR, 1H-NMR and 13C-NMR results show that the lactam is formed by aminomethylation from urea, isobutyraldehyde, and formaldehyde.展开更多
Results of researches on study of the kinetics and isomerization mechanism of the alkyladamantanes in the presence of the heterogeneous catalysts of the acid type are considered as detection and experimental proof of ...Results of researches on study of the kinetics and isomerization mechanism of the alkyladamantanes in the presence of the heterogeneous catalysts of the acid type are considered as detection and experimental proof of a new intramolecular rearrangement of the carbcations bridged alicyclic hydrocarbons--2,4-moving of the methyl groups （β-methyl shift）. The proof of realization of such rearrangement is direct and primary formation 1,4-dimethyladamantane from 1,2-dimethyladamatane, passing a formation stage of the thermodynamic much stable 1,3-dimethyladamantane; direct formation 1,3,6-trimethyladamantane from 1,3,4-trimethyladamantane, excepting a formation stage 1,3.5-trimethyladamantane, and also other isomers which formation is impossible to explain by means of known 1,2-methyl shift （a-methyl shift）.展开更多
The structures and isomerization of magnesium fluorosilylenoid H2SiFMgF were investigated by ab initio molecular orbital theory. Four equilibrium structures and three isomeric transition states were located and fully ...The structures and isomerization of magnesium fluorosilylenoid H2SiFMgF were investigated by ab initio molecular orbital theory. Four equilibrium structures and three isomeric transition states were located and fully optimized at the B3LYP/6-31G（d,p） and G3MP2B3 levels, respectively. Based on the B3LYP/6- 31G（d,p） optimized geometries, harmonic frequencies of various structures were obtained and 29Si chemical shifts were calculated. The solvent effects were investigated by means of the polarizable continuum model using THF as a solvent at B3LYP/6-31G（d,p） level. Isomerization paths for isomers were confirmed by intrinsic reaction coordinate calculations. The calculated results show that tetrahedral structure has the lowest energy and is the most stable; tetrahedral, three-membered ring, and p-complex structures are suggested to be the experimentally detectable ones; and a-complex structure has the highest energy and will not exist.展开更多
Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory （B3LYP） and two post- Hartree-Fock approaches （MP2, CCSD...Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory （B3LYP） and two post- Hartree-Fock approaches （MP2, CCSD（T））, several stable isomers for new three pnictogen dianionic Sb4^2-, Bi4^2-, and （SbBi）2^2- species were determined. For two homoatomic Sb4^2- and Bi4^2- species, there are three stable isomers： square （D4h）, roof-shaped （C2v-1）, and C2v-2 structure with the square isomer being the ground state. For the heteroatomic dian- ionic （SbBi）2^2- species, there are also three stable isomers： rhombus （D2h）, roof-shaped （C1）, and C2v structures with the rhombic isomer being the ground state. The calculated NICS values show that nucleus-independent chemical shifts （NICS） values of roof-shaped isomers for Sb4^2-, Bi4^2-, and （SbBi）2^2- species are all negative, consequently indicating that these roof-shaped isomers possess aromaticities. NICS values for the planar ring isomers are all positive, suggesting that these three planar ring isomers have antiaromatic characters. The aromaticity for the two stable roof-shaped and square isomers are preliminarily explained and discussed with MO analysis.展开更多
1. Introduction Zeolites are widely used in acid heterogeneous catalysis [1, 2]. Due to the unique physical and chemical properties ofzeolites, they are widely used in commercial catalytic processes, such as fluidized...1. Introduction Zeolites are widely used in acid heterogeneous catalysis [1, 2]. Due to the unique physical and chemical properties ofzeolites, they are widely used in commercial catalytic processes, such as fluidized catalytic cracking, hydrocracking, methanol conversion to gasoline or olefins, ethylbenzene production, xylene isomerization, aromatics hydrogenation [3-9]. Acidity, high thermal stability, and shape selectivity determine the use of zeolites as catalysts in reaction processes through acid mechanisms [ 10].展开更多
The development of cost-effective and highperformance electrocatalysts has been increasingly studied to mitigate upcoming energy and environmental challenges.Amorphization and heterointerface engineering have played s...The development of cost-effective and highperformance electrocatalysts has been increasingly studied to mitigate upcoming energy and environmental challenges.Amorphization and heterointerface engineering have played significant roles in the rational design of electrocatalysts and modulation of their electrocatalytic activities.However,the synergistic effect between amorphization and heterointerfaces has been scarcely reported.As a proof-of-concept attempt,we develop amorphous FeMo(a-FeMo)electrocatalysts with an abundance of heterointerfaces that are composed of amorphous components and evaluate their electrocatalytic performances toward the nitrogen reduction reaction and oxygen evolution reaction(OER).Benefitting from the synergistic effect between the amorphous nature of the a-FeMo electrocatalysts,which offer a high density of active sites,and significant electron redistribution at the heterointerfaces,the electrocatalysts exhibit a high Faradaic efficiency of 29.15%,an elevated yield rate of 71.78μg_(NH_(3)) mg_(cat.)^(-1) h^(-1) with long-term stability at a potential of-0.1V vs.reversible hydrogen electrode and excellent electrocatalytic activity toward the OER.This study provides a promising and effective method for the rational design of low-cost heterogeneous catalysts with desirable efficiency,selectivity,and stability.展开更多
The ever-growing market demands for lithium ion batteries have stimulated numerous research efforts aiming at the exploration of novel electrode materials with higher capacity and long-term cycling stability.Two-dimen...The ever-growing market demands for lithium ion batteries have stimulated numerous research efforts aiming at the exploration of novel electrode materials with higher capacity and long-term cycling stability.Two-dimensional (2D)nanomaterials and their heterostructures are an intense area of study and promise great potential in electrochemical lithium storage owing to their unique properties that result from structural planar confinement.Here we report a microwave chemistry strategy to integrate ultrathin SnO2 nanosheets into graphene layer to construct surface-to-surface 2D heterostructured architectures,which can provide unique structural planar confinement for highly reversible electrochemical lithium storage.The as-synthesized 2D SnO2/graphene heterostructures can exhibit high reversible capacity of 688.5mAh g^-1 over 500cycles with excellent long-term cycling stability and good rate capability when used as anode materials for lithium ion batteries.The present work definitely reveals the advantages of 2D heterostructures featured with a surface-to-surface stack between two different nanosheets in energy storage and conversion devices.展开更多
文摘Aim To synthesize trans and cis-3, 4′, 5-trihydroxystilbene by a new convenient route. Methods The reaction of 3, 5-dimethoxybenzaldehyde （3） and 4-methoxy phenylacetonitrile （4） formed the stilbene skeleton. After hydrolyzation, decarboxylation, and demethylation, we obtained trans-3, 4′, 5-trihydroxystilbene （resveratrol）, which can be converted to its cis-isomer by photochemical isomerization. Results Starting from 3 and 4, trans and cis-3, 4′, 5-trihydroxystilbene were synthesized, respectively. Conclusion A facile method for the synthesis of trans and cis-hydroxystilbenes from readily available materials was established.
基金Project(2006A10902001) supported by the Science and Technology Plan of Guangdong Province, ChinaProject(2007Z3-D0351) supported by the Science and Technology Plan of Guangzhou City, China
文摘Urea-isobutyraldehyde-formaldehyde (UIF) resin was synthesized from urea, isobutyraldehyde, and formaldehyde using sulfuric acid as a catalyst by one pot method. The effects of molar ratios of isobutyraldehyde to formaldehyde (n(I)/n(F)) and aldehyde to urea (n(A)/n(U)) on the yield, hydroxyl value (vs KOH) and softening point of the resin were investigated. The structure of the resin was characterized by FT-IR, 1H-NMR and 13C-NMR. The results show that when the molar ratio of urea to isobutyraldehyde to formaldehyde (n(U)/n(I)/n(F)) is 1.0/3.0/3.0, the yield UIF resin is 67.1%, and the softening point and hydroxyl value are 88 ℃ and 37 mg/g, respectively. The FT-IR, 1H-NMR and 13C-NMR results show that the lactam is formed by aminomethylation from urea, isobutyraldehyde, and formaldehyde.
文摘Results of researches on study of the kinetics and isomerization mechanism of the alkyladamantanes in the presence of the heterogeneous catalysts of the acid type are considered as detection and experimental proof of a new intramolecular rearrangement of the carbcations bridged alicyclic hydrocarbons--2,4-moving of the methyl groups （β-methyl shift）. The proof of realization of such rearrangement is direct and primary formation 1,4-dimethyladamantane from 1,2-dimethyladamatane, passing a formation stage of the thermodynamic much stable 1,3-dimethyladamantane; direct formation 1,3,6-trimethyladamantane from 1,3,4-trimethyladamantane, excepting a formation stage 1,3.5-trimethyladamantane, and also other isomers which formation is impossible to explain by means of known 1,2-methyl shift （a-methyl shift）.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20574043） and the Natural Science Foundation of Shandong Province （No.Z2007B02）.
文摘The structures and isomerization of magnesium fluorosilylenoid H2SiFMgF were investigated by ab initio molecular orbital theory. Four equilibrium structures and three isomeric transition states were located and fully optimized at the B3LYP/6-31G（d,p） and G3MP2B3 levels, respectively. Based on the B3LYP/6- 31G（d,p） optimized geometries, harmonic frequencies of various structures were obtained and 29Si chemical shifts were calculated. The solvent effects were investigated by means of the polarizable continuum model using THF as a solvent at B3LYP/6-31G（d,p） level. Isomerization paths for isomers were confirmed by intrinsic reaction coordinate calculations. The calculated results show that tetrahedral structure has the lowest energy and is the most stable; tetrahedral, three-membered ring, and p-complex structures are suggested to be the experimentally detectable ones; and a-complex structure has the highest energy and will not exist.
文摘Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory （B3LYP） and two post- Hartree-Fock approaches （MP2, CCSD（T））, several stable isomers for new three pnictogen dianionic Sb4^2-, Bi4^2-, and （SbBi）2^2- species were determined. For two homoatomic Sb4^2- and Bi4^2- species, there are three stable isomers： square （D4h）, roof-shaped （C2v-1）, and C2v-2 structure with the square isomer being the ground state. For the heteroatomic dian- ionic （SbBi）2^2- species, there are also three stable isomers： rhombus （D2h）, roof-shaped （C1）, and C2v structures with the rhombic isomer being the ground state. The calculated NICS values show that nucleus-independent chemical shifts （NICS） values of roof-shaped isomers for Sb4^2-, Bi4^2-, and （SbBi）2^2- species are all negative, consequently indicating that these roof-shaped isomers possess aromaticities. NICS values for the planar ring isomers are all positive, suggesting that these three planar ring isomers have antiaromatic characters. The aromaticity for the two stable roof-shaped and square isomers are preliminarily explained and discussed with MO analysis.
文摘1. Introduction Zeolites are widely used in acid heterogeneous catalysis [1, 2]. Due to the unique physical and chemical properties ofzeolites, they are widely used in commercial catalytic processes, such as fluidized catalytic cracking, hydrocracking, methanol conversion to gasoline or olefins, ethylbenzene production, xylene isomerization, aromatics hydrogenation [3-9]. Acidity, high thermal stability, and shape selectivity determine the use of zeolites as catalysts in reaction processes through acid mechanisms [ 10].
基金supported by the National Natural Science Foundation of China(U2032149)Shenzhen Science and Technology Project(JCYJ20180507182246321)+3 种基金Hunan Provincial Natural Science Foundation of China(2020JJ2001)Hefei National Laboratory for Physical Sciences at the Microscale(KF2020108)the Fundamental Research Funds for the Central UniversitiesChina Postdoctoral Science Foundation(2019M663058 and 2019M652749).
文摘The development of cost-effective and highperformance electrocatalysts has been increasingly studied to mitigate upcoming energy and environmental challenges.Amorphization and heterointerface engineering have played significant roles in the rational design of electrocatalysts and modulation of their electrocatalytic activities.However,the synergistic effect between amorphization and heterointerfaces has been scarcely reported.As a proof-of-concept attempt,we develop amorphous FeMo(a-FeMo)electrocatalysts with an abundance of heterointerfaces that are composed of amorphous components and evaluate their electrocatalytic performances toward the nitrogen reduction reaction and oxygen evolution reaction(OER).Benefitting from the synergistic effect between the amorphous nature of the a-FeMo electrocatalysts,which offer a high density of active sites,and significant electron redistribution at the heterointerfaces,the electrocatalysts exhibit a high Faradaic efficiency of 29.15%,an elevated yield rate of 71.78μg_(NH_(3)) mg_(cat.)^(-1) h^(-1) with long-term stability at a potential of-0.1V vs.reversible hydrogen electrode and excellent electrocatalytic activity toward the OER.This study provides a promising and effective method for the rational design of low-cost heterogeneous catalysts with desirable efficiency,selectivity,and stability.
基金supported by China Ministry of Science and Technology under Contract of 2016YFA(0202801)the National Natural Science Foundation of China(21521091,21390393,U1463202,21471089,21671117,21703219 and 21371023)China Postdoctoral Science Foundation(2017M620738)
文摘The ever-growing market demands for lithium ion batteries have stimulated numerous research efforts aiming at the exploration of novel electrode materials with higher capacity and long-term cycling stability.Two-dimensional (2D)nanomaterials and their heterostructures are an intense area of study and promise great potential in electrochemical lithium storage owing to their unique properties that result from structural planar confinement.Here we report a microwave chemistry strategy to integrate ultrathin SnO2 nanosheets into graphene layer to construct surface-to-surface 2D heterostructured architectures,which can provide unique structural planar confinement for highly reversible electrochemical lithium storage.The as-synthesized 2D SnO2/graphene heterostructures can exhibit high reversible capacity of 688.5mAh g^-1 over 500cycles with excellent long-term cycling stability and good rate capability when used as anode materials for lithium ion batteries.The present work definitely reveals the advantages of 2D heterostructures featured with a surface-to-surface stack between two different nanosheets in energy storage and conversion devices.
