Development of efficient and stable metal catalysts for the selective aqueous phase hydrodeoxygenation(HDO)of biomass-derived oxygenates to value-added biofuels is highly desired.An innovative surface microenvironment...Development of efficient and stable metal catalysts for the selective aqueous phase hydrodeoxygenation(HDO)of biomass-derived oxygenates to value-added biofuels is highly desired.An innovative surface microenvironment modulation strategy was used to construct the nitrogen-doped hollow carbon sphere encapsulated with Pd(Pd@NHCS-X,X:600–800)nanoreactors for catalytic HDO of biomass-derived vanillin in water.The specific surface microenvironments of Pd@NHCS catalysts including the electronic property of active Pd centers and the surface wettability and porous structure of NHCS supports could be well-controlled by the calcination temperature of catalysts.Intrinsic kinetic evaluations demonstrated that the Pd@NHCS-600 catalyst presented a high turnover frequency of 337.77 h^(–1)and a low apparent activation energy of 18.63 kJ/mol.The excellent catalytic HDO performance was attributed to the unique surface microenvironment of Pd@NHCS catalyst based on structure-performance relationship analysis and DFT calculations.It revealed that pyridinic N species dominated the electronic property regulation of Pd sites through electronic metal-support interaction(EMSI)and produced numerous electron-rich active Pd centers,which not only intensified the dissociation and activation of H2 molecules,but also substantially improved the activation capability of vanillin via the enhanced adsorption of–C=O group.The fine hydrophilicity and abundant porous structure promoted the uniform dispersion of catalyst and ensured the effective access of reactants to catalytic active centers in water.Additionally,the Pd@NHCS-600 catalyst exhibited excellent catalytic stability and broad substrate applicability for the selective aqueous phase HDO of various biomass-derived carbonyl compounds.The proposed surface microenvironment modulation strategy will provide a new consideration for the rational design of high-performance nitrogen-doped carbon-supported metal catalysts for catalytic biomass transformation.展开更多
Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide(MO_(x))or support has been a common method for improving the catalytic performance of s...Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide(MO_(x))or support has been a common method for improving the catalytic performance of supported metal catalysts.However,few studies have investigated the ternary interactions among the metal,MO_(x),and support.Here,we report for the first time the formation of metal-MO_(x)-support interaction(MMSI)in reducible TiO_(2)-supported PtReO_(x) catalysts,affording 87% yield and 100% ee in the tandem hydrogenation of an aqueous chiral cyclohexane-1,2-dicarboxylic acid into the corresponding diol;the catalytic activity is eight times higher than that obtained with non-reducible support counterparts in the same reaction via traditional batch synthesis with multiple steps and unfriendly reagents.Detailed experimental and computational studies suggest that the TiO_(2) crystalline phase-dependent density of the oxygen vacancies induces different Pt-ReO_(x)-TiO_(2) interactions,which dominate the electron transfer therein and tune the adsorption strength of the carbonyl moiety of the substrate/intermediate,thus promoting the hydrogenation activity and selectivity.In addition,the strong MMSI endows the optimal rutile TiO_(2) supported PtReO_(x) catalyst with an outstanding lifetime of 400 h in a fixed-bed reactor under acidic aqueous conditions and ensures efficient applications in the selective hydrogenation of aliphatic dicarboxylic acids and functional carboxylic acids.This work provides a promising strategy for the development of efficient and stable supported catalysts for the selective hydrogenation of diverse C-O and C=O bonds.展开更多
The rock bridges sandwiched in incipiently jointed rock mass were considered as barriers that block the fluid seepage,and provide certain shear strength reservation.For better revealing the influence of hydraulic pres...The rock bridges sandwiched in incipiently jointed rock mass were considered as barriers that block the fluid seepage,and provide certain shear strength reservation.For better revealing the influence of hydraulic pressure on the failure behaviour of rock bridges,direct shear tests were carried out through a newly proposed method on rock samples that contain two parallel incipient joints.By developing the gypsum-silicone pad coupling samples,a conventional triaxial test system was qualified to implement direct shear tests with satisfied sealing capability.The results showed that the rock bridges could be failed through the tensile failure,shear failure and mixed failure mechanism.The hydraulic pressure would facilitate the tensile failure mechanism and induce rougher fracture surfaces;while the normal stress would facilitate the shear failure mechanism and induce less rough fracture.The hydraulic pressure reduced the global shear strength of the rock block through reducing the efficient normal stress applied on the rock bridge area,which was highly dependent on the joint persistence,k.Moreover,because of the iterating occurrence of the hydraulic pressure lag with the fracture propagation,the rock bridge failure stage in the shear stress-shear displacement curves displayed a fluctuation trend.展开更多
ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles w...ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.展开更多
Enhancing the output capacity of semiconductor bridge(SCB) through the application of composite nano-energetic films is a subject of wide concern. Furthermore, improving the safety, reliability, and production efficie...Enhancing the output capacity of semiconductor bridge(SCB) through the application of composite nano-energetic films is a subject of wide concern. Furthermore, improving the safety, reliability, and production efficiency of energetic semiconductor bridge(ESCB) is the primary focus for large-scale engineering applications in the future. Here, the Al/CuO nano-film ESCB was efficiently fabricated using 3D direct writing. The electrostatic safety of the film is enhanced by precisely adjusting the particle size of Al, while ensuring that the SCB can initiate the film with small energy. The burst characteristics of SCB/ESCB were thoroughly investigated by employing a 100 μF tantalum capacitor to induce SCB and ESCB under an intense voltage gradient. The solid-state heating process of both SCB and ESCB was analyzed with multi physical simulation(MPS). The experimental results demonstrate that the critical burst time of both SCB and ESCB decreases with increasing voltage. Under the same voltage, the critical burst time of ESCB is longer than that of SCB, primarily due to differences in the melting to vaporization stage. The MPS results indicate that the highest temperature is observed at the V-shaped corner of SCB. Due to the thermal contact resistance between SCB and the film, heat conduction becomes more concentrated in the central region of the bridge, resulting in a faster solid-state heating process for ESCB compared to SCB.The results of the gap ignition experiments indicate that at a 19 mm gap, an ESCB with a film mass of 10 mg can ignite nickel hydrazine nitrate(NHN) and cyclotrimethylenetrinitramine(RDX). This suggests that thermite ESCB can serve as a novel, safe, and reliable energy exchange element and initiator in largescale engineering applications.展开更多
The increasingly environmental pollution have drawn global attentions to the development of new techniques that can effectively deal with the pollutants.With the unique set of electronic properties and structural dive...The increasingly environmental pollution have drawn global attentions to the development of new techniques that can effectively deal with the pollutants.With the unique set of electronic properties and structural diversities,N-heterocyclic carbenes(NHCs)and related materials are emerging as potential adsorbing materials for adsorptive decontamination of various pollutant-containing mediums.Recent investigations have revealed the feasibility of molecular and heterogeneous NHCs for adsorptive separation of harmful gases including CO_(2),CO,NO_(x),SO_(2),etc.Rather than simple gas trapping,NHCs functions as effective catalytic centers that activating and transforming the captured gas molecules.Besides,heterogeneous NHCs and their complexes have been applied to adsorptive removal of various organic pollutants and heavy metal ions from water solution with high efficiencies.These advancements have illustrated the significant potential of NHCs and their related materials in environmental decontamination.Instead of the well-known catalytic applications of NHCs in organic transformations,this review aims to offer an overview of the emerging applications of NHCs in the field of environmental decontamination and provide a comprehensive understanding of the mechanisms behind the N-heterocyclic carbene material-mediated environmental decontamination processes.With this in mind,the structure,synthesis,application,and performance of NHCs and related materials in environmental processes including gas separation and wastewater treatment are summarized,and the structure-activity relationship is discussed.Besides,the current challenge and future development of NHC-mediated environmental treatments are proposed.This review is expected to serve as a preliminary database for the environmental applications of NHC and related materials and offer deep insights into the rational design of novel NHC-based environmental materials for greener and efficient environmental processes.展开更多
An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide(CO)as both reductant and carbonyl source,which enables facile access to amide...An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide(CO)as both reductant and carbonyl source,which enables facile access to amides with excellent regioselectivity and broad substrate scope.It is found that the counter anions of the Pd catalyst precursors significantly affect the reaction chemoselectivity and amide regioselectivity.Branched amides were mainly obtained with K2PdCl4 as the metal catalyst,and phosphine ligands had no influence on the regioselectivity but affected the catalytic reactivity.However,phosphine ligands had significant effects on aminocarbonylation regioselectivity when Pd(CH3CN)4(OTf)2 was used;monodentate phosphines tended to form branched amides,and bidentate phosphines mainly formed linear amides.Trapping experiments,primary kinetic studies,and control reactions with all possible N-species reduced from nitroarene indicated that the catalytic synthesis of branched and linear amides produced nitrene(further converted to enamide)and aniline,respectively,different from the previous ligand-controlled regioselective synthesis of amides via the aminocarbonylation of olefins with amines.Furthermore,the proposed synthesis route could be applied in the synthesis of gram-scale propanil under mild conditions.展开更多
The safety and reliability of weapon systems would be significantly affected by changes in the performance of energetic materials due to ambient temperature and humidity.Nanothermites have promising applications due t...The safety and reliability of weapon systems would be significantly affected by changes in the performance of energetic materials due to ambient temperature and humidity.Nanothermites have promising applications due to their excellent reactivity.Therefore it becomes extremely important to understand their aging and failure process in the environment before using them.Here,the aging and failure process of Al/CuO in 71°C/60%RH were investigated,and showed that CuO nanoparticles negatively catalyze Al nanopowders,resulting in rapid hydration.The anti-aging effect of FAS-17-coated Al nanopowder was also examined.The aging process of Al,Al/CuO,and Al@FAS-17/CuO in high humidity and heat environment were revealed by quasi-in situ SEM and TEM methods.Compared with the aging of pure Al,the Al nanopowder in the nanothermites strongly agglomerated with the CuO nanopowder and hydrated earlier.This may be caused by CuO catalyzed hydration of Al nanopowder.The energy release experiments showed that the performance of Al/CuO decreased rapidly and failed to ignite after 4 h of aging.In contrast,the Al@FAS-17/CuO thermite can achieve long-term stability of up to 60 h in the same environment by simple cladding of FAS-17.It is found that FAS-17 coated Al nanopowder can prevent both particle agglomeration and water erosion,which is an effective means to make nanothermites application in high humidity and heat environment.展开更多
The core-shell metastable intermolecular composites(MIC)have attracted much attention in the past few years due to their unique properties.Here,the preparation of Al-Core heterojunction fibers using PVP as a template ...The core-shell metastable intermolecular composites(MIC)have attracted much attention in the past few years due to their unique properties.Here,the preparation of Al-Core heterojunction fibers using PVP as a template is proposed.The nano-Al was directly added to the precursor solution of cupric acetate monohydrate(CAM)/Polyvinylpyrrolidone(PVP),and the initial Al@CAM/PVP fibers were obtained via electrospinning.The core-shell MIC fibers are then obtained by calcining the initial fibers.The morphology,structure,and composition of Al-core MIC fibers were characterized,that the energetic fibers calcined at 300℃,350℃,and 400℃have a core-shell structure with shell compositions CuxO and PVP,CuxO and Cu O,respectively.The energy release characteristics of Al-core MIC were investigated,and preliminary ignition tests were performed using an ignition temperature measuring instrument and a pulsed laser.The energetic fibers calcined at 300℃exhibited unique properties.The decomposition of PVP in the shell layer promoted exotherm,and a low-temperature exothermic peak was shown at 372-458℃.Lower ignition temperatures and higher flame heights were observed in the combustion tests than calcination at 350℃and 400℃.An unexpected result was that PVP can play a positive role in Al/CuO nanothermites.Simultaneously,this preparation method provided an idea for the integrated preparation of core-shell Al-Core MIC fibers and tuning the properties of MIC.展开更多
Catalysis occurs when a catalyst forges a new reaction pathway that is unavailable to an uncatalyzed reaction.Catalysis is involved in almost 80%of chemical processes,and important applications include the synthesis o...Catalysis occurs when a catalyst forges a new reaction pathway that is unavailable to an uncatalyzed reaction.Catalysis is involved in almost 80%of chemical processes,and important applications include the synthesis of pharmaceutically active ingredients,production of petrochemicals and nitrogen fertilizers,the development of renewable energy and the reduction of pollution emission.In particular,green catalysis is at the heart of industrial and environmental challenges on energy,health,and sustainable development.展开更多
Although tandem reactions offer rapid access to structurally complex molecules in one-pot reaction,the selectivity issue needs to be addressed particularly when incompatible step reactions are involved.Herein,we repor...Although tandem reactions offer rapid access to structurally complex molecules in one-pot reaction,the selectivity issue needs to be addressed particularly when incompatible step reactions are involved.Herein,we report the selective synthesis of fused N-heterocycles from nucleophile-tethered alkenylamide and carbon monoxide via palladium(Pd)-catalyzed tandem carbonylative aza-Wacker-type cyclization.The electron-deficient nature of amide N—H and the intramolecular coordination of Pd with alkene accelerate the aminopalladation and effectively prevent the side oxidative carbonylation of diamine moiety to form urea.It is also found that the reported acyl Pd chloride intermediate may not be involved in this tandem cyclization.This work not only provides an efficient synthetic route to fused 1,4-diazepanones and 1,4-diazepanes but also inspires further development of tandem reactions for the diverse synthesis of heterocycles.展开更多
文摘Development of efficient and stable metal catalysts for the selective aqueous phase hydrodeoxygenation(HDO)of biomass-derived oxygenates to value-added biofuels is highly desired.An innovative surface microenvironment modulation strategy was used to construct the nitrogen-doped hollow carbon sphere encapsulated with Pd(Pd@NHCS-X,X:600–800)nanoreactors for catalytic HDO of biomass-derived vanillin in water.The specific surface microenvironments of Pd@NHCS catalysts including the electronic property of active Pd centers and the surface wettability and porous structure of NHCS supports could be well-controlled by the calcination temperature of catalysts.Intrinsic kinetic evaluations demonstrated that the Pd@NHCS-600 catalyst presented a high turnover frequency of 337.77 h^(–1)and a low apparent activation energy of 18.63 kJ/mol.The excellent catalytic HDO performance was attributed to the unique surface microenvironment of Pd@NHCS catalyst based on structure-performance relationship analysis and DFT calculations.It revealed that pyridinic N species dominated the electronic property regulation of Pd sites through electronic metal-support interaction(EMSI)and produced numerous electron-rich active Pd centers,which not only intensified the dissociation and activation of H2 molecules,but also substantially improved the activation capability of vanillin via the enhanced adsorption of–C=O group.The fine hydrophilicity and abundant porous structure promoted the uniform dispersion of catalyst and ensured the effective access of reactants to catalytic active centers in water.Additionally,the Pd@NHCS-600 catalyst exhibited excellent catalytic stability and broad substrate applicability for the selective aqueous phase HDO of various biomass-derived carbonyl compounds.The proposed surface microenvironment modulation strategy will provide a new consideration for the rational design of high-performance nitrogen-doped carbon-supported metal catalysts for catalytic biomass transformation.
文摘Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide(MO_(x))or support has been a common method for improving the catalytic performance of supported metal catalysts.However,few studies have investigated the ternary interactions among the metal,MO_(x),and support.Here,we report for the first time the formation of metal-MO_(x)-support interaction(MMSI)in reducible TiO_(2)-supported PtReO_(x) catalysts,affording 87% yield and 100% ee in the tandem hydrogenation of an aqueous chiral cyclohexane-1,2-dicarboxylic acid into the corresponding diol;the catalytic activity is eight times higher than that obtained with non-reducible support counterparts in the same reaction via traditional batch synthesis with multiple steps and unfriendly reagents.Detailed experimental and computational studies suggest that the TiO_(2) crystalline phase-dependent density of the oxygen vacancies induces different Pt-ReO_(x)-TiO_(2) interactions,which dominate the electron transfer therein and tune the adsorption strength of the carbonyl moiety of the substrate/intermediate,thus promoting the hydrogenation activity and selectivity.In addition,the strong MMSI endows the optimal rutile TiO_(2) supported PtReO_(x) catalyst with an outstanding lifetime of 400 h in a fixed-bed reactor under acidic aqueous conditions and ensures efficient applications in the selective hydrogenation of aliphatic dicarboxylic acids and functional carboxylic acids.This work provides a promising strategy for the development of efficient and stable supported catalysts for the selective hydrogenation of diverse C-O and C=O bonds.
基金the National Natural Science Foundation of China(No.51704183)the Postdoctoral Science Foundation of China(No.2018M640646).
文摘The rock bridges sandwiched in incipiently jointed rock mass were considered as barriers that block the fluid seepage,and provide certain shear strength reservation.For better revealing the influence of hydraulic pressure on the failure behaviour of rock bridges,direct shear tests were carried out through a newly proposed method on rock samples that contain two parallel incipient joints.By developing the gypsum-silicone pad coupling samples,a conventional triaxial test system was qualified to implement direct shear tests with satisfied sealing capability.The results showed that the rock bridges could be failed through the tensile failure,shear failure and mixed failure mechanism.The hydraulic pressure would facilitate the tensile failure mechanism and induce rougher fracture surfaces;while the normal stress would facilitate the shear failure mechanism and induce less rough fracture.The hydraulic pressure reduced the global shear strength of the rock block through reducing the efficient normal stress applied on the rock bridge area,which was highly dependent on the joint persistence,k.Moreover,because of the iterating occurrence of the hydraulic pressure lag with the fracture propagation,the rock bridge failure stage in the shear stress-shear displacement curves displayed a fluctuation trend.
基金supported by the National Natural Science Foundation of China(22078076)Guangxi Natural Science Foundation(2020GXNSFAA159174)the Opening Project of National Enterprise Technology Center of Guangxi Bossco Environmental Protection Technology Co.,Ltd(GXU-BFY-2020-005).
文摘ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.
基金supported by the National Natural Science Foundation of China(Grant Nos.22275092 and 52372084)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(Grant No.KYCX24_0709)+1 种基金the Fundamental Research Funds for the Central Universities(Grant No.30923010920)the State Key Laboratory of Transient Chemical Effects and Control,China,(Grant No.6142602230201).
文摘Enhancing the output capacity of semiconductor bridge(SCB) through the application of composite nano-energetic films is a subject of wide concern. Furthermore, improving the safety, reliability, and production efficiency of energetic semiconductor bridge(ESCB) is the primary focus for large-scale engineering applications in the future. Here, the Al/CuO nano-film ESCB was efficiently fabricated using 3D direct writing. The electrostatic safety of the film is enhanced by precisely adjusting the particle size of Al, while ensuring that the SCB can initiate the film with small energy. The burst characteristics of SCB/ESCB were thoroughly investigated by employing a 100 μF tantalum capacitor to induce SCB and ESCB under an intense voltage gradient. The solid-state heating process of both SCB and ESCB was analyzed with multi physical simulation(MPS). The experimental results demonstrate that the critical burst time of both SCB and ESCB decreases with increasing voltage. Under the same voltage, the critical burst time of ESCB is longer than that of SCB, primarily due to differences in the melting to vaporization stage. The MPS results indicate that the highest temperature is observed at the V-shaped corner of SCB. Due to the thermal contact resistance between SCB and the film, heat conduction becomes more concentrated in the central region of the bridge, resulting in a faster solid-state heating process for ESCB compared to SCB.The results of the gap ignition experiments indicate that at a 19 mm gap, an ESCB with a film mass of 10 mg can ignite nickel hydrazine nitrate(NHN) and cyclotrimethylenetrinitramine(RDX). This suggests that thermite ESCB can serve as a novel, safe, and reliable energy exchange element and initiator in largescale engineering applications.
基金supported by the National Natural Science Foundation of China(grant numbers 22202099 and 22472177)Natural Science Foundation of Hunan Province(grant numbers 2022JJ40366 and 2022JJ40351)the Scientific Research Foundation of Hunan Provincial Education Department(grant numbers 23A0332 and 21B0440).
文摘The increasingly environmental pollution have drawn global attentions to the development of new techniques that can effectively deal with the pollutants.With the unique set of electronic properties and structural diversities,N-heterocyclic carbenes(NHCs)and related materials are emerging as potential adsorbing materials for adsorptive decontamination of various pollutant-containing mediums.Recent investigations have revealed the feasibility of molecular and heterogeneous NHCs for adsorptive separation of harmful gases including CO_(2),CO,NO_(x),SO_(2),etc.Rather than simple gas trapping,NHCs functions as effective catalytic centers that activating and transforming the captured gas molecules.Besides,heterogeneous NHCs and their complexes have been applied to adsorptive removal of various organic pollutants and heavy metal ions from water solution with high efficiencies.These advancements have illustrated the significant potential of NHCs and their related materials in environmental decontamination.Instead of the well-known catalytic applications of NHCs in organic transformations,this review aims to offer an overview of the emerging applications of NHCs in the field of environmental decontamination and provide a comprehensive understanding of the mechanisms behind the N-heterocyclic carbene material-mediated environmental decontamination processes.With this in mind,the structure,synthesis,application,and performance of NHCs and related materials in environmental processes including gas separation and wastewater treatment are summarized,and the structure-activity relationship is discussed.Besides,the current challenge and future development of NHC-mediated environmental treatments are proposed.This review is expected to serve as a preliminary database for the environmental applications of NHC and related materials and offer deep insights into the rational design of novel NHC-based environmental materials for greener and efficient environmental processes.
文摘An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide(CO)as both reductant and carbonyl source,which enables facile access to amides with excellent regioselectivity and broad substrate scope.It is found that the counter anions of the Pd catalyst precursors significantly affect the reaction chemoselectivity and amide regioselectivity.Branched amides were mainly obtained with K2PdCl4 as the metal catalyst,and phosphine ligands had no influence on the regioselectivity but affected the catalytic reactivity.However,phosphine ligands had significant effects on aminocarbonylation regioselectivity when Pd(CH3CN)4(OTf)2 was used;monodentate phosphines tended to form branched amides,and bidentate phosphines mainly formed linear amides.Trapping experiments,primary kinetic studies,and control reactions with all possible N-species reduced from nitroarene indicated that the catalytic synthesis of branched and linear amides produced nitrene(further converted to enamide)and aniline,respectively,different from the previous ligand-controlled regioselective synthesis of amides via the aminocarbonylation of olefins with amines.Furthermore,the proposed synthesis route could be applied in the synthesis of gram-scale propanil under mild conditions.
基金supported by the National Natural Science Foundation of China(Grant No.22275092)。
文摘The safety and reliability of weapon systems would be significantly affected by changes in the performance of energetic materials due to ambient temperature and humidity.Nanothermites have promising applications due to their excellent reactivity.Therefore it becomes extremely important to understand their aging and failure process in the environment before using them.Here,the aging and failure process of Al/CuO in 71°C/60%RH were investigated,and showed that CuO nanoparticles negatively catalyze Al nanopowders,resulting in rapid hydration.The anti-aging effect of FAS-17-coated Al nanopowder was also examined.The aging process of Al,Al/CuO,and Al@FAS-17/CuO in high humidity and heat environment were revealed by quasi-in situ SEM and TEM methods.Compared with the aging of pure Al,the Al nanopowder in the nanothermites strongly agglomerated with the CuO nanopowder and hydrated earlier.This may be caused by CuO catalyzed hydration of Al nanopowder.The energy release experiments showed that the performance of Al/CuO decreased rapidly and failed to ignite after 4 h of aging.In contrast,the Al@FAS-17/CuO thermite can achieve long-term stability of up to 60 h in the same environment by simple cladding of FAS-17.It is found that FAS-17 coated Al nanopowder can prevent both particle agglomeration and water erosion,which is an effective means to make nanothermites application in high humidity and heat environment.
文摘The core-shell metastable intermolecular composites(MIC)have attracted much attention in the past few years due to their unique properties.Here,the preparation of Al-Core heterojunction fibers using PVP as a template is proposed.The nano-Al was directly added to the precursor solution of cupric acetate monohydrate(CAM)/Polyvinylpyrrolidone(PVP),and the initial Al@CAM/PVP fibers were obtained via electrospinning.The core-shell MIC fibers are then obtained by calcining the initial fibers.The morphology,structure,and composition of Al-core MIC fibers were characterized,that the energetic fibers calcined at 300℃,350℃,and 400℃have a core-shell structure with shell compositions CuxO and PVP,CuxO and Cu O,respectively.The energy release characteristics of Al-core MIC were investigated,and preliminary ignition tests were performed using an ignition temperature measuring instrument and a pulsed laser.The energetic fibers calcined at 300℃exhibited unique properties.The decomposition of PVP in the shell layer promoted exotherm,and a low-temperature exothermic peak was shown at 372-458℃.Lower ignition temperatures and higher flame heights were observed in the combustion tests than calcination at 350℃and 400℃.An unexpected result was that PVP can play a positive role in Al/CuO nanothermites.Simultaneously,this preparation method provided an idea for the integrated preparation of core-shell Al-Core MIC fibers and tuning the properties of MIC.
文摘Catalysis occurs when a catalyst forges a new reaction pathway that is unavailable to an uncatalyzed reaction.Catalysis is involved in almost 80%of chemical processes,and important applications include the synthesis of pharmaceutically active ingredients,production of petrochemicals and nitrogen fertilizers,the development of renewable energy and the reduction of pollution emission.In particular,green catalysis is at the heart of industrial and environmental challenges on energy,health,and sustainable development.
基金This work was funded by the National Key R&D Program of China(No.2018YFB1501600)the Natural Science Foundation of China(Nos.21773271 and 21972151)+1 种基金the Light of West China of Chinese Academy of Sciences(CAS)the Key Research Program of Frontier Sciences of CAS(QYZDJSSW-SLH051).
文摘Although tandem reactions offer rapid access to structurally complex molecules in one-pot reaction,the selectivity issue needs to be addressed particularly when incompatible step reactions are involved.Herein,we report the selective synthesis of fused N-heterocycles from nucleophile-tethered alkenylamide and carbon monoxide via palladium(Pd)-catalyzed tandem carbonylative aza-Wacker-type cyclization.The electron-deficient nature of amide N—H and the intramolecular coordination of Pd with alkene accelerate the aminopalladation and effectively prevent the side oxidative carbonylation of diamine moiety to form urea.It is also found that the reported acyl Pd chloride intermediate may not be involved in this tandem cyclization.This work not only provides an efficient synthetic route to fused 1,4-diazepanones and 1,4-diazepanes but also inspires further development of tandem reactions for the diverse synthesis of heterocycles.
