Direct photocatalytic coupling of methanol to ethylene glycol(EG)is highly attractive.The reported photocatalysts for this reaction are all metal sulfide semiconductors,which may suffer from photocorrosion and have lo...Direct photocatalytic coupling of methanol to ethylene glycol(EG)is highly attractive.The reported photocatalysts for this reaction are all metal sulfide semiconductors,which may suffer from photocorrosion and have low stability.Thus,the development of non‐sulfide photocatalysts for efficient photocatalytic coupling of methanol to EG and H2 with high stability is urgent but extremely challenging.Herein,the first metal oxide photocatalyst,tantalum‐based semiconductor,is reported for preferential activation of C−H bond within methanol to form hydroxymethyl radical(•CH_(2)OH)and subsequent C−C coupling to EG.Compared with other metal oxide photocatalysts,such as TiO2,ZnO,WO_(3),Nb_(2)O_(5),tantalum oxide(Ta_(2)O_(5))is unique in that it can realize the selective photocatalytic coupling of methanol to EG.The co‐catalyst free nitrogen doped tantalum oxide(2%N‐Ta_(2)O_(5))shows an EG formation rate as high as 4.0 mmol gcat−1 h−1,about 9 times higher than that of Ta_(2)O_(5),with a selectivity higher than 70%.The high charge separation ability of nitrogen doped tantalum oxide plays a key role in its high activity for EG production.This catalyst also shows excellent stability longer than 160 h,which has not been achieved over the reported metal sulfide photocatalysts.Tantalum‐based photocatalyst is an environmentally friendly and highly stable candidate for photocatalytic coupling of methanol to EG.展开更多
Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O_(2) activation, copper-dependent metalloenzymes such as particulate methane monooxygenases(pM MOs), lytic polysaccharide mo...Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O_(2) activation, copper-dependent metalloenzymes such as particulate methane monooxygenases(pM MOs), lytic polysaccharide monooxygenases(LPMOs) and binuclear copper enzymes PHM and DβM, are able to perform various challenging C–H bond activations. Meanwhile, various copper-oxygen core containing complexes have been synthetized to mimic the active species of metalloenzymes. Dioxygen activation by mononuclear copper active site may generate various copper-oxygen intermediates, including Cu(Ⅱ)-superoxo, Cu(Ⅱ)-hydroperoxo, Cu(Ⅱ)-oxyl as well as the Cu(Ⅲ)-hydroxide species. Intriguingly, all these species have been invoked as the potential active intermediates for C–H/O–H activations in either biological or synthetic systems. Due to the poor understanding on reactivities of copper-oxygen complex, the nature of active species in both biological and synthetic systems are highly controversial. In this account, we will compare the reactivities of various mononuclear copper-oxygen species between biological systems and the synthetic systems. The present study is expected to provide the consistent understanding on reactivities of various copper-oxygen active species in both biological and synthetic systems.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
Seven types of activated carbon were used to investigate the effect of their structure on separation of CO2 from（H2 ＋ CO2） gas mixture by the adsorption method at ambient temperature and higher pressures. The resul...Seven types of activated carbon were used to investigate the effect of their structure on separation of CO2 from（H2 ＋ CO2） gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO2 from 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture and from 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture were different at 20 °C and about 2 MPa. The best separation result could be achieved when the pore diameter of the activated carbon ranged from 0.77 to 1.20 nm, and the median particle size was about2.07 lm for 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture and 1.41 lm for 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture. The effect of specific area and pore diameter of activated carbon on separation CO2 from 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture was more significant than that from 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture. CO2 in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.展开更多
Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions,therefore,new methods to achieve them are anticipated.In this study,a formal[3+2]method,through the reactions of an o...Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions,therefore,new methods to achieve them are anticipated.In this study,a formal[3+2]method,through the reactions of an osmapentalyne with benzyl carbanions,was developed.The reactions underwent a nucleophilic attack of carbanions to the Os≡C bond,followed by C—H activation to form the five-membered osmacyclopentadiene ring.Most of the reactions were carried out at room temperature,the substituents on the aromatic rings of benzyl carbanions are diverse,and the resulting products contain an Os—H bond,representing a novel type of 10C-carbolong complexes.This work provides a new convenient route to construct metallacyclopentadienes,which is expected to further promote the development of such a type of substances.展开更多
3d-Metal-catalyzed tertiary C(sp^(3))–H bond activation has been a formidable challenge.Herein,a tertiary C(sp^(3))–H bond is smoothly activated by Ni–Al bimetallic catalysts for dual C–H annulation of formamides ...3d-Metal-catalyzed tertiary C(sp^(3))–H bond activation has been a formidable challenge.Herein,a tertiary C(sp^(3))–H bond is smoothly activated by Ni–Al bimetallic catalysts for dual C–H annulation of formamides with alkynes,delivering a series of δ-lactams with a quaternary carbon up to 98%yield.Various tertiary C(sp^(3))–H bonds such as noncyclic,monocyclic and bridged-ring tertiary C(sp^(3))–H bonds are all compatible with the reaction.展开更多
The construction of N-fused polycyclic compounds at room temperature via the combination of transition-metal catalyst and photocatalyst has been reported.This novel work has successfully realized LED irradiated C—H a...The construction of N-fused polycyclic compounds at room temperature via the combination of transition-metal catalyst and photocatalyst has been reported.This novel work has successfully realized LED irradiated C—H activation of iodonium ylides.The strategy shows wide substrate scope and ideal functional group tolerance.Our work would be useful for the construction of various heterocyclic compounds.展开更多
文摘Direct photocatalytic coupling of methanol to ethylene glycol(EG)is highly attractive.The reported photocatalysts for this reaction are all metal sulfide semiconductors,which may suffer from photocorrosion and have low stability.Thus,the development of non‐sulfide photocatalysts for efficient photocatalytic coupling of methanol to EG and H2 with high stability is urgent but extremely challenging.Herein,the first metal oxide photocatalyst,tantalum‐based semiconductor,is reported for preferential activation of C−H bond within methanol to form hydroxymethyl radical(•CH_(2)OH)and subsequent C−C coupling to EG.Compared with other metal oxide photocatalysts,such as TiO2,ZnO,WO_(3),Nb_(2)O_(5),tantalum oxide(Ta_(2)O_(5))is unique in that it can realize the selective photocatalytic coupling of methanol to EG.The co‐catalyst free nitrogen doped tantalum oxide(2%N‐Ta_(2)O_(5))shows an EG formation rate as high as 4.0 mmol gcat−1 h−1,about 9 times higher than that of Ta_(2)O_(5),with a selectivity higher than 70%.The high charge separation ability of nitrogen doped tantalum oxide plays a key role in its high activity for EG production.This catalyst also shows excellent stability longer than 160 h,which has not been achieved over the reported metal sulfide photocatalysts.Tantalum‐based photocatalyst is an environmentally friendly and highly stable candidate for photocatalytic coupling of methanol to EG.
文摘Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O_(2) activation, copper-dependent metalloenzymes such as particulate methane monooxygenases(pM MOs), lytic polysaccharide monooxygenases(LPMOs) and binuclear copper enzymes PHM and DβM, are able to perform various challenging C–H bond activations. Meanwhile, various copper-oxygen core containing complexes have been synthetized to mimic the active species of metalloenzymes. Dioxygen activation by mononuclear copper active site may generate various copper-oxygen intermediates, including Cu(Ⅱ)-superoxo, Cu(Ⅱ)-hydroperoxo, Cu(Ⅱ)-oxyl as well as the Cu(Ⅲ)-hydroxide species. Intriguingly, all these species have been invoked as the potential active intermediates for C–H/O–H activations in either biological or synthetic systems. Due to the poor understanding on reactivities of copper-oxygen complex, the nature of active species in both biological and synthetic systems are highly controversial. In this account, we will compare the reactivities of various mononuclear copper-oxygen species between biological systems and the synthetic systems. The present study is expected to provide the consistent understanding on reactivities of various copper-oxygen active species in both biological and synthetic systems.
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the Talent Scientific Research Fund of LSHU (No. 2016XJJ-015)the fund of the Liaoning Provincial Department of Education (No. L2017LQN005)the National Natural Science Foundation of China (No. 21606120)
文摘Seven types of activated carbon were used to investigate the effect of their structure on separation of CO2 from（H2 ＋ CO2） gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO2 from 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture and from 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture were different at 20 °C and about 2 MPa. The best separation result could be achieved when the pore diameter of the activated carbon ranged from 0.77 to 1.20 nm, and the median particle size was about2.07 lm for 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture and 1.41 lm for 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture. The effect of specific area and pore diameter of activated carbon on separation CO2 from 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture was more significant than that from 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture. CO2 in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.
基金the NSFC(Nos.22071098,21931002 and 22101123)the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)+2 种基金the Shenzhen Science and Technology Innovation Committee(No.JCYJ20200109140812302)Introduction of Major Talent Projects in Guangdong Province(No.2019CX01C079)Outstanding Talents Training Fund in Shenzhen,for their financial support.
文摘Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions,therefore,new methods to achieve them are anticipated.In this study,a formal[3+2]method,through the reactions of an osmapentalyne with benzyl carbanions,was developed.The reactions underwent a nucleophilic attack of carbanions to the Os≡C bond,followed by C—H activation to form the five-membered osmacyclopentadiene ring.Most of the reactions were carried out at room temperature,the substituents on the aromatic rings of benzyl carbanions are diverse,and the resulting products contain an Os—H bond,representing a novel type of 10C-carbolong complexes.This work provides a new convenient route to construct metallacyclopentadienes,which is expected to further promote the development of such a type of substances.
基金the National Key R&D Program of China(grant no.2022YFA1504300)the National Natural Science Foundation of China(grant nos.22188101 and 22325103)+1 种基金the Haihe Laboratory of Sustainable Chemical Transformations and“Frontiers Science Center for New Organic Matter,”Nankai University(grant no.63181206)the Fundamental Research Funds for the Central Universities for financial support.
文摘3d-Metal-catalyzed tertiary C(sp^(3))–H bond activation has been a formidable challenge.Herein,a tertiary C(sp^(3))–H bond is smoothly activated by Ni–Al bimetallic catalysts for dual C–H annulation of formamides with alkynes,delivering a series of δ-lactams with a quaternary carbon up to 98%yield.Various tertiary C(sp^(3))–H bonds such as noncyclic,monocyclic and bridged-ring tertiary C(sp^(3))–H bonds are all compatible with the reaction.
基金the support from Sichuan Science and Technology Program(No.2020YJ0221).
文摘The construction of N-fused polycyclic compounds at room temperature via the combination of transition-metal catalyst and photocatalyst has been reported.This novel work has successfully realized LED irradiated C—H activation of iodonium ylides.The strategy shows wide substrate scope and ideal functional group tolerance.Our work would be useful for the construction of various heterocyclic compounds.
