A novel reduction system is reported here in which the compounds with terminal C-C triple bond and disubstituted C-C triple bond react with NaBH4/Pd(PPh3)(4) in a base condition and only terminal C-C triple bond is re...A novel reduction system is reported here in which the compounds with terminal C-C triple bond and disubstituted C-C triple bond react with NaBH4/Pd(PPh3)(4) in a base condition and only terminal C-C triple bond is reduced.展开更多
The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-...The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.展开更多
Methyl, ethyl, n-propyl, and benzyl p-hydroxyphenyl ketones and 6-hydroxy-1-tetralone are shown under the condition of ethylene ketal formation to undergo alkyl-carbonyl C-C bondscission, but not with p-hydroxybenzoph...Methyl, ethyl, n-propyl, and benzyl p-hydroxyphenyl ketones and 6-hydroxy-1-tetralone are shown under the condition of ethylene ketal formation to undergo alkyl-carbonyl C-C bondscission, but not with p-hydroxybenzophenone, p-hydroxyisobutyrophenone, and 5-hydroxy-1-indanone. It is suggested that the scissiou is preceded by an aldol condensation.展开更多
A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition m...A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .展开更多
3-Methoxy-, 3, 5-dimethoxy-, and 3-phenyl-4-hydroxyacetophenones suffered alkyl carbonyl C-C bond scission to yield 4-hydroxybenzoate esters and 4-isopropenylphenols under standard conditions of ethylene ketal formati...3-Methoxy-, 3, 5-dimethoxy-, and 3-phenyl-4-hydroxyacetophenones suffered alkyl carbonyl C-C bond scission to yield 4-hydroxybenzoate esters and 4-isopropenylphenols under standard conditions of ethylene ketal formation; the latter underwent in situ dimerization, cyclization, and rearrangement to give substituted indanols. The isopropenylphenol derived from 3,5-ditertbutyl-4-hydroxyacetophenone did not dimerize but condensed with its precursor to yield a substituted diphenylpropanone. 3-nitro-, 3,5-dinitro-, and 3,5-dibromo-4-hydroxyacetophenones on the other hand reacted normally to give ethylene ketals in good yields.展开更多
Over the past 20 years, small molecule solid phase synthesis has become a powerful tool in the discovery of novel molecular materials. In the development of organic chemistry, the carbon-carbon bond formation has alwa...Over the past 20 years, small molecule solid phase synthesis has become a powerful tool in the discovery of novel molecular materials. In the development of organic chemistry, the carbon-carbon bond formation has always been one of the most useful and fundamental reaction. The current review summarizes recent developments in metal-catalyzed coupling reactions. The following method is discussed in detail—the cross-coupling of aryl halides with aryl boronic acids (the Suzuki coupling), and the others C-C bond formation reactions as the palladium-catalyzed reaction between an aryl and (or) alkyl halide and a vinyl functionality (the Heck reaction);and the palladium-catalyzed cross-coupling reaction of organostannyl reagents with a variety of organic electrophiles (the Stille reaction)—are mentioned.展开更多
The application of Sb_(2)S_(3)with marvelous theoretical capacity for alkali metal-ion batteries is seriously limited by its poor electrical conductivity and low initial coulombic efficiency(ICE).In this work,natural ...The application of Sb_(2)S_(3)with marvelous theoretical capacity for alkali metal-ion batteries is seriously limited by its poor electrical conductivity and low initial coulombic efficiency(ICE).In this work,natural stibnite modified by carbon dots(Sb_(2)S_(3)@xCDs)is elaborately designed with high ICE.Greatly,chemical processes of local oxidation–partial reduction–deep coupling for stibnite reduction of CDs are clearly demonstrated,confirmed with in situ high-temperature X-ray diffraction.More impressively,the ICE for lithium-ion batteries(LIBs)is enhanced to 85%,through the effect of oxygen-rich carbon matrix on C–S bonds which inhibit the conversion of sulfur to sulfite,well supported by X-ray photoelectron spectroscopy characterization of solid electrolyte interphase layers helped with density functional theory calculations.Not than less,it is found that Sb–O–C bonds existed in the interface effectively promote the electronic conductivity and expedite ion transmission by reducing the bandgap and restraining the slip of the dislocation.As a result,the optimal sample delivers a tremendous reversible capacity of 660 mAh g^(−1)in LIBs at a high current rate of 5 A g^(−1).This work provides a new methodology for enhancing the electrochemical energy storage performance of metal sulfides,especially for improving the ICE.展开更多
An important part of the "Belt and Road " Initiative is to achieve people-to-people bonds. People-to-people bonds are certainly based on cultural self-confidence and cultural self-awareness. Cultural self-co...An important part of the "Belt and Road " Initiative is to achieve people-to-people bonds. People-to-people bonds are certainly based on cultural self-confidence and cultural self-awareness. Cultural self-confidence is an important cultural strategy put forward by the party and the country in the vision of contemporary society,and an important deployment to realize the great rejuvenation of the Chinese nation. This paper first gives a brief overview of the advantages of cultural self-confidence in external communication,and then analyzes the opportunities and challenges that cultural self-confidence faces in external communication in the newera. Finally,it focuses on exploration on the external communication ways of cultural self-confidence in the "Belt and Road"Initiative. O nly based on the deep understanding of local culture can we can shape the soul of culture in the process of further opening-up and external communication to the outside world,and enhance the cultural self-aw areness of the people; build a solid foundation of culture and promote cultural exchanges with other countries.展开更多
A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, t...A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.展开更多
Transverse crack often occurs in the trailing edge region of the bladewhen subjected to the excessive edgewise fatigue load.In this paper a refined model was established through local mesh refinement methods in order ...Transverse crack often occurs in the trailing edge region of the bladewhen subjected to the excessive edgewise fatigue load.In this paper a refined model was established through local mesh refinement methods in order to investigate the initiation mechanism of crack and its extension in blade trailing edge.The material stress around the crack in trailing edge region under different thicknesses is calculated based on the fracture mechanics theory.The factors affecting the fatigue robustness of blade trailing edge are concluded by investigating the results of finite element analysis and coupons test.Compared with the laminate,the lower fatigue strength of the adhesive is the cause of the transverse crack of the adhesive joint at the trailing edge.The increase of the adhesive thickness at the adhesive joint will significantly increase the stress concentration factor at the crack region and accelerate the crack extension of the laminate.In final,a practical design scheme to prevent crack initiation is given for the manufacture of the wind turbine blade.展开更多
The catalytic transformation of cellulose, the major component of abundant and renewable lignocellulosic biomass, into building-block chemicals is a key to establishing sustainable chemical processes. Cellulose is a p...The catalytic transformation of cellulose, the major component of abundant and renewable lignocellulosic biomass, into building-block chemicals is a key to establishing sustainable chemical processes. Cellulose is a polymer of glucose and a lot research effort has been devoted to the conversion of cellulose to six-carbon platform compounds such as glucose and glucose derivatives through C-O bond activation. There also ex- ist considerable studies on the catalytic cleavage of C-C bonds in biomass for the production of high-value chemicals, in particular polyols and organic acids such as ethylene glycol and lactic acid. This review article highlights recent advances in the development of new catalytic systems and new strategies for the selective cleavage of C-C bonds in cellulose and its derived carbohydrates under inert, reductive and oxidative atmospheres to produce Q -Cs polyols and organic acids. The key factors that influence the catalytic performance will be clarified to provide insights for the design of more efficient catalysts for the transformation of cellulose with precise cleavage of C-C bonds to high-value chemicals. The reaction mechanisms will also be discussed to understand deeply how the selective cleavage of C-C bonds can be achieved in biomass.展开更多
A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contra...A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contrast, the deconstruction and functionalization of bicyclic skeletons has been less developed and has mainly focused on the ring expansion process. Inspired by the aromatization-driven C-C bond cleavage, here we demonstrate a ring-opening/aminocarbonylation cascade under copper catalysis, in which the formation of a stable γ-lactam or succinimide skeleton reverses the selectivity of C-C cleavage. Remarkably, the photo and thermal assistance is not required when the succinimide skeleton is formed during the ring opening process. DFT calculations revealed that this unexpected ring-opening process is thermodynamically and kinetically favourable.展开更多
Lignin is a rich renewable aromatic resource that can produce high-value-added chemicals. Lignin is regarded as one of the three major components of lignocellulosic biomass, which is composed of phenylpropane units co...Lignin is a rich renewable aromatic resource that can produce high-value-added chemicals. Lignin is regarded as one of the three major components of lignocellulosic biomass, which is composed of phenylpropane units connected by C-O bond and C-C bond. The cleavage of two chemical bonds is the main catalytic pathway in the production of chemicals and fuels from lignin. Although the cleavage of C-O converts lignin into valuable aromatic compounds and renewable carbon sources, selective depolymerization for C-C bonds is an important method to increase the yield of aromatic monomers. Therefore, in this review, we summarized the latest research trends on C-C bond selective cleavage in lignin and lignin model compounds, focusing on various catalytic systems, including hydrogenolysis, oxidate, photocatalysis, and electrocatalysis. By analyzing the current status of C-C bond breakage, the core issues and challenges related to this process and the expectations for future research were emphasized.展开更多
基金the National Natural Science Foundation of China (No. 29772012)
文摘A novel reduction system is reported here in which the compounds with terminal C-C triple bond and disubstituted C-C triple bond react with NaBH4/Pd(PPh3)(4) in a base condition and only terminal C-C triple bond is reduced.
基金financially supported by the National Natural Science Foundation of China(21972099)the Application Foundation Program of Sichuan Province(2021YJ0305)+1 种基金the 111 project(B17030).Shanghai Synchrotron Radiation Facility(SSRF)for XAS experiments and the support by the project from NPL of CAEP(2019BB08)。
文摘The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.
文摘Methyl, ethyl, n-propyl, and benzyl p-hydroxyphenyl ketones and 6-hydroxy-1-tetralone are shown under the condition of ethylene ketal formation to undergo alkyl-carbonyl C-C bondscission, but not with p-hydroxybenzophenone, p-hydroxyisobutyrophenone, and 5-hydroxy-1-indanone. It is suggested that the scissiou is preceded by an aldol condensation.
文摘A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .
文摘3-Methoxy-, 3, 5-dimethoxy-, and 3-phenyl-4-hydroxyacetophenones suffered alkyl carbonyl C-C bond scission to yield 4-hydroxybenzoate esters and 4-isopropenylphenols under standard conditions of ethylene ketal formation; the latter underwent in situ dimerization, cyclization, and rearrangement to give substituted indanols. The isopropenylphenol derived from 3,5-ditertbutyl-4-hydroxyacetophenone did not dimerize but condensed with its precursor to yield a substituted diphenylpropanone. 3-nitro-, 3,5-dinitro-, and 3,5-dibromo-4-hydroxyacetophenones on the other hand reacted normally to give ethylene ketals in good yields.
基金gratefully acknowledged for the financial support of the Polish National Centre of Progress of Explorations Grant no.NR05-0017-10/2010 and Wroclaw University of Technology.
文摘Over the past 20 years, small molecule solid phase synthesis has become a powerful tool in the discovery of novel molecular materials. In the development of organic chemistry, the carbon-carbon bond formation has always been one of the most useful and fundamental reaction. The current review summarizes recent developments in metal-catalyzed coupling reactions. The following method is discussed in detail—the cross-coupling of aryl halides with aryl boronic acids (the Suzuki coupling), and the others C-C bond formation reactions as the palladium-catalyzed reaction between an aryl and (or) alkyl halide and a vinyl functionality (the Heck reaction);and the palladium-catalyzed cross-coupling reaction of organostannyl reagents with a variety of organic electrophiles (the Stille reaction)—are mentioned.
基金financially supported by the National Natural Science Foundation of China (51904342, 52074359, U21A20284)Hunan Provincial Science and Technology Plan (2020JJ3048)the Science and Technology Innovation Program of Hunan Province (2021RC3014, 2020RC4005, 2019RS1004)
文摘The application of Sb_(2)S_(3)with marvelous theoretical capacity for alkali metal-ion batteries is seriously limited by its poor electrical conductivity and low initial coulombic efficiency(ICE).In this work,natural stibnite modified by carbon dots(Sb_(2)S_(3)@xCDs)is elaborately designed with high ICE.Greatly,chemical processes of local oxidation–partial reduction–deep coupling for stibnite reduction of CDs are clearly demonstrated,confirmed with in situ high-temperature X-ray diffraction.More impressively,the ICE for lithium-ion batteries(LIBs)is enhanced to 85%,through the effect of oxygen-rich carbon matrix on C–S bonds which inhibit the conversion of sulfur to sulfite,well supported by X-ray photoelectron spectroscopy characterization of solid electrolyte interphase layers helped with density functional theory calculations.Not than less,it is found that Sb–O–C bonds existed in the interface effectively promote the electronic conductivity and expedite ion transmission by reducing the bandgap and restraining the slip of the dislocation.As a result,the optimal sample delivers a tremendous reversible capacity of 660 mAh g^(−1)in LIBs at a high current rate of 5 A g^(−1).This work provides a new methodology for enhancing the electrochemical energy storage performance of metal sulfides,especially for improving the ICE.
基金one of the research findings of Open Fund of“Research Center for Sustainable Development of Three Gorges Reservoir Area”in2016(No:16sxxyjd04).
文摘An important part of the "Belt and Road " Initiative is to achieve people-to-people bonds. People-to-people bonds are certainly based on cultural self-confidence and cultural self-awareness. Cultural self-confidence is an important cultural strategy put forward by the party and the country in the vision of contemporary society,and an important deployment to realize the great rejuvenation of the Chinese nation. This paper first gives a brief overview of the advantages of cultural self-confidence in external communication,and then analyzes the opportunities and challenges that cultural self-confidence faces in external communication in the newera. Finally,it focuses on exploration on the external communication ways of cultural self-confidence in the "Belt and Road"Initiative. O nly based on the deep understanding of local culture can we can shape the soul of culture in the process of further opening-up and external communication to the outside world,and enhance the cultural self-aw areness of the people; build a solid foundation of culture and promote cultural exchanges with other countries.
基金Supported by the National Natural Science Foundation of China(No.20773014 and 20933001)the Research Foundation of Education Bureau of Hebei Province(No.Z2011115)+3 种基金the 111 Project of China(No.B07012)the Natural Science Foundation of Hebei Province(No.B2012105002)the Research Foundation of Tangshan Administration of Science&Technology(121302011a)the Research Foundation of Tangshan normal college(2013A04)for their support of this work
文摘A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.
基金This research was funded by Natural Science Foundation of Shandong Province(Grant No.ZR2019MEE076)National Natural Science Foundation of China(Grant No.52075305).
文摘Transverse crack often occurs in the trailing edge region of the bladewhen subjected to the excessive edgewise fatigue load.In this paper a refined model was established through local mesh refinement methods in order to investigate the initiation mechanism of crack and its extension in blade trailing edge.The material stress around the crack in trailing edge region under different thicknesses is calculated based on the fracture mechanics theory.The factors affecting the fatigue robustness of blade trailing edge are concluded by investigating the results of finite element analysis and coupons test.Compared with the laminate,the lower fatigue strength of the adhesive is the cause of the transverse crack of the adhesive joint at the trailing edge.The increase of the adhesive thickness at the adhesive joint will significantly increase the stress concentration factor at the crack region and accelerate the crack extension of the laminate.In final,a practical design scheme to prevent crack initiation is given for the manufacture of the wind turbine blade.
基金supported by the National Natural Science Foundation of China (21173172 and 21473141)the Research Fund for the Doctorial Program of Higher Education (No. 20130121130001)the Program for Innovative Research Team in University (No. IRT_14R31)
文摘The catalytic transformation of cellulose, the major component of abundant and renewable lignocellulosic biomass, into building-block chemicals is a key to establishing sustainable chemical processes. Cellulose is a polymer of glucose and a lot research effort has been devoted to the conversion of cellulose to six-carbon platform compounds such as glucose and glucose derivatives through C-O bond activation. There also ex- ist considerable studies on the catalytic cleavage of C-C bonds in biomass for the production of high-value chemicals, in particular polyols and organic acids such as ethylene glycol and lactic acid. This review article highlights recent advances in the development of new catalytic systems and new strategies for the selective cleavage of C-C bonds in cellulose and its derived carbohydrates under inert, reductive and oxidative atmospheres to produce Q -Cs polyols and organic acids. The key factors that influence the catalytic performance will be clarified to provide insights for the design of more efficient catalysts for the transformation of cellulose with precise cleavage of C-C bonds to high-value chemicals. The reaction mechanisms will also be discussed to understand deeply how the selective cleavage of C-C bonds can be achieved in biomass.
基金supported by the National Natural Science Foundation of China (Nos. 22171220)the Fundamental Research Funds of the Central Universities (No. xtr072022003)。
文摘A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contrast, the deconstruction and functionalization of bicyclic skeletons has been less developed and has mainly focused on the ring expansion process. Inspired by the aromatization-driven C-C bond cleavage, here we demonstrate a ring-opening/aminocarbonylation cascade under copper catalysis, in which the formation of a stable γ-lactam or succinimide skeleton reverses the selectivity of C-C cleavage. Remarkably, the photo and thermal assistance is not required when the succinimide skeleton is formed during the ring opening process. DFT calculations revealed that this unexpected ring-opening process is thermodynamically and kinetically favourable.
基金the financial support from the Foundation(No.JSBEM-S-202314)of Key Laboratory of Biomass Energy and Material of Jiangsu Provincethe National Natural Science Foundation of China(No.32171713,No.31870714).
文摘Lignin is a rich renewable aromatic resource that can produce high-value-added chemicals. Lignin is regarded as one of the three major components of lignocellulosic biomass, which is composed of phenylpropane units connected by C-O bond and C-C bond. The cleavage of two chemical bonds is the main catalytic pathway in the production of chemicals and fuels from lignin. Although the cleavage of C-O converts lignin into valuable aromatic compounds and renewable carbon sources, selective depolymerization for C-C bonds is an important method to increase the yield of aromatic monomers. Therefore, in this review, we summarized the latest research trends on C-C bond selective cleavage in lignin and lignin model compounds, focusing on various catalytic systems, including hydrogenolysis, oxidate, photocatalysis, and electrocatalysis. By analyzing the current status of C-C bond breakage, the core issues and challenges related to this process and the expectations for future research were emphasized.
