A novel triple-site diphosphinoamine (PNP) ligand was synthesized and characterized. In combination with Cr(III) and methylaluminoxane (MAO), it generated active catalytic systems for ethylene tetramerization toward 1...A novel triple-site diphosphinoamine (PNP) ligand was synthesized and characterized. In combination with Cr(III) and methylaluminoxane (MAO), it generated active catalytic systems for ethylene tetramerization toward 1-octene with high catalytic activity and long lifetime. The effects of reaction temperature, molar ratio of Al/Cr and molar ratio of ligand/Cr on catalytic activity and selectivity to 1-octene were studied with reaction kinetics of the catalytic system for ethylene tetramerization described. At the Al/Cr molar ratio of 100, the catalytic activity is up to 2.29×106 g·mol-1 (Cr)·h-1 and the selectivity to 1-octene is 49.65 wt%.展开更多
文章立足于电池储能应急支撑与规模化应用背景,指出电池储能电站(Battery Energy Storage Power Station,BESPS)即插即用(Plug and Play,PNP)的现实需求。通过分析2018年7月投运的江苏镇江MW级BESPS典型架构,首次提出实现BESPS PNP运行...文章立足于电池储能应急支撑与规模化应用背景,指出电池储能电站(Battery Energy Storage Power Station,BESPS)即插即用(Plug and Play,PNP)的现实需求。通过分析2018年7月投运的江苏镇江MW级BESPS典型架构,首次提出实现BESPS PNP运行的关键技术应从信息流和能量流两个维度进行考虑。针对信息流层面分层通信要求,提出了BESPS并网自描述模型建立方法与信息交互机制,并阐述了分层通信的具体实现方法。针对能量流层面的物理接口集成驱动技术要求,研究并综述BESPS多状态平滑切换、主动电压与频率支撑、削峰填谷以及黑启动等高级应用。最后,采用多状态平滑切换的控制算法,通过仿真对BESPS能量流层面的柔性接入与退出响应过程进行验证。文章的研究工作对开发具有增强的可扩展性PNP功能BESPS设备,解决BESPS规模化灵活并网等实现问题有十分积极的指导意义与参考价值。展开更多
A silylated PNP ligand with asymmetric structure was synthesized using(γ-aminopropyl)triethoxysilane and chlorodiphenyl phosphine as raw materials.The optimal synthetic conditions of the PNP ligand were obtained by c...A silylated PNP ligand with asymmetric structure was synthesized using(γ-aminopropyl)triethoxysilane and chlorodiphenyl phosphine as raw materials.The optimal synthetic conditions of the PNP ligand were obtained by conditional experiments and were as follows:dichloromethane was solvent,triethylamine was acid acceptor,the mole ratio of chlorodiphenylphosphine and(γ-aminopropyl)triethoxysilane was 2.1∶1,the dropping temperature of chlorodiphenylphosphine was-5℃,the dropping time was 30 min,the reaction temperature was 25℃and the reaction time was 12 h.Under the conditions,the yield of the silylated PNP ligand was 91.20%.Based on grey correlation analysis,the dropping temperature was the main factor for the yield of the silylated PNP ligand.The single-active central chromium catalyst based on the silylated PNP ligand was synthesized by complexation reaction with the silylated PNP ligand and chromium chloride tetrahydrofuran complex as materials,and the yield was 95.25%.The chemical structures of the silylated PNP ligand and the corresponding chromium catalyst were confirmed by elemental analysis,FT-IR,^(1)H NMR,MS and ICP.The single-active central chromium catalyst based on the silylated PNP ligand had good catalytic activity for ethylene oligomerization,and the content of C_(8)olefin was 72.40%,which was superior to Si-Schiff-Cr based on intermolecular coordination.展开更多
Asymmetric hydrogenation of dialkyl imines to chiral amines is difficult because the two alkyls of imines are so similar in spatial and electronic structure that chiral catalysts are difficult to distinguish between t...Asymmetric hydrogenation of dialkyl imines to chiral amines is difficult because the two alkyls of imines are so similar in spatial and electronic structure that chiral catalysts are difficult to distinguish between them.In this study,we described an asymmetric hydrogenation of dialkyl imines by a chiral iridium catalyst containing spiro phosphine-amine-phosphine ligand.By precisely adjusting the chiral pocket of catalyst,a highly efficient catalyst was developed.Using this catalyst,a variety of dialkyl imines were hydrogenated to chiral amines with high yield and enantioselectivity.展开更多
基金the Program for New Century Excellent Talents in University (NCET)the Program for New Century Excellent Talents in Heilongjiang Provincial Universities (Grant No. NCET-06-010)
文摘A novel triple-site diphosphinoamine (PNP) ligand was synthesized and characterized. In combination with Cr(III) and methylaluminoxane (MAO), it generated active catalytic systems for ethylene tetramerization toward 1-octene with high catalytic activity and long lifetime. The effects of reaction temperature, molar ratio of Al/Cr and molar ratio of ligand/Cr on catalytic activity and selectivity to 1-octene were studied with reaction kinetics of the catalytic system for ethylene tetramerization described. At the Al/Cr molar ratio of 100, the catalytic activity is up to 2.29×106 g·mol-1 (Cr)·h-1 and the selectivity to 1-octene is 49.65 wt%.
文摘文章立足于电池储能应急支撑与规模化应用背景,指出电池储能电站(Battery Energy Storage Power Station,BESPS)即插即用(Plug and Play,PNP)的现实需求。通过分析2018年7月投运的江苏镇江MW级BESPS典型架构,首次提出实现BESPS PNP运行的关键技术应从信息流和能量流两个维度进行考虑。针对信息流层面分层通信要求,提出了BESPS并网自描述模型建立方法与信息交互机制,并阐述了分层通信的具体实现方法。针对能量流层面的物理接口集成驱动技术要求,研究并综述BESPS多状态平滑切换、主动电压与频率支撑、削峰填谷以及黑启动等高级应用。最后,采用多状态平滑切换的控制算法,通过仿真对BESPS能量流层面的柔性接入与退出响应过程进行验证。文章的研究工作对开发具有增强的可扩展性PNP功能BESPS设备,解决BESPS规模化灵活并网等实现问题有十分积极的指导意义与参考价值。
基金supported by Key Research and Development Project of Heilongjiang Province(JD22A026)
文摘A silylated PNP ligand with asymmetric structure was synthesized using(γ-aminopropyl)triethoxysilane and chlorodiphenyl phosphine as raw materials.The optimal synthetic conditions of the PNP ligand were obtained by conditional experiments and were as follows:dichloromethane was solvent,triethylamine was acid acceptor,the mole ratio of chlorodiphenylphosphine and(γ-aminopropyl)triethoxysilane was 2.1∶1,the dropping temperature of chlorodiphenylphosphine was-5℃,the dropping time was 30 min,the reaction temperature was 25℃and the reaction time was 12 h.Under the conditions,the yield of the silylated PNP ligand was 91.20%.Based on grey correlation analysis,the dropping temperature was the main factor for the yield of the silylated PNP ligand.The single-active central chromium catalyst based on the silylated PNP ligand was synthesized by complexation reaction with the silylated PNP ligand and chromium chloride tetrahydrofuran complex as materials,and the yield was 95.25%.The chemical structures of the silylated PNP ligand and the corresponding chromium catalyst were confirmed by elemental analysis,FT-IR,^(1)H NMR,MS and ICP.The single-active central chromium catalyst based on the silylated PNP ligand had good catalytic activity for ethylene oligomerization,and the content of C_(8)olefin was 72.40%,which was superior to Si-Schiff-Cr based on intermolecular coordination.
基金supported by the National Key R&D Program of China(grant no.2022YFA1504302)the National Natural Science Foundation of China(grant nos.22188101,91956000,and 92256301)the Fundamental Research Funds for the Central Universities,and the Haihe Laboratory of Sustainable Chemical Transformations.
文摘Asymmetric hydrogenation of dialkyl imines to chiral amines is difficult because the two alkyls of imines are so similar in spatial and electronic structure that chiral catalysts are difficult to distinguish between them.In this study,we described an asymmetric hydrogenation of dialkyl imines by a chiral iridium catalyst containing spiro phosphine-amine-phosphine ligand.By precisely adjusting the chiral pocket of catalyst,a highly efficient catalyst was developed.Using this catalyst,a variety of dialkyl imines were hydrogenated to chiral amines with high yield and enantioselectivity.
