Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robus...Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.展开更多
The relationship between the electronic structures of manganese nitrido complexes and the substituted ligands is investigated by using density functional theory.By designing a series of manganese nitrido complexes [Mn...The relationship between the electronic structures of manganese nitrido complexes and the substituted ligands is investigated by using density functional theory.By designing a series of manganese nitrido complexes [Mn（SalenR）N]＋ with different para ring substituents（R = H,CH_3,NH_2,OCH_3,NMeF,etc） of the ancillary ligand,the properties of manganese-nitrogen bonds were compared for two kinds of electronic structures,of which the radical resides on metal center or the coordinated ring ligand.Our calculation shows that for R = H,CH_3 and NH_2,the [Mn（SalenR）N]＋ complexes have a high-valent Mn（VI） center,and for R = OCH_3 and NMeF,the complexes represent a configuration where the radical delocalizes on the ligand.It is found that the relative energies of these two species depend on electronic properties of the substituent,originating from the intrinsic property of HOMO-LUMO gaps.展开更多
Nitrogen doping is a promising way to modulate the electrical properties of graphene to realize graphene-based electronics and promise fascinating properties and applications.Herein,we report a method to noncovalently...Nitrogen doping is a promising way to modulate the electrical properties of graphene to realize graphene-based electronics and promise fascinating properties and applications.Herein,we report a method to noncovalently assembly titanium(Ⅳ) bis(ammoniumlactato) dihydroxide(Ti complex) on nitrogen-doped graphene to create a reliable hybrids which can be used as a reversible chemical induced switching.As the adsorption and desorption of Ti complex in sequential treatments,the conductance of the nitrogen-doped graphene transistors was finely modulated.Control experiments with pristine graphene clearly demonstrated the important effort of the nitrogen in this chemical sensor.Under optimized conditions,nitrogen-doped graphene transistors open up new ways to develop multifunctional devices with high sensitivity.展开更多
Iron tetranitrosyl complex bearing the thiosulfate ligand (TNIC) is an efficient nitrogen monoxide donor (NO). He shows antitumor properties and may be used as an original drug for the therapy of acute coronary syndro...Iron tetranitrosyl complex bearing the thiosulfate ligand (TNIC) is an efficient nitrogen monoxide donor (NO). He shows antitumor properties and may be used as an original drug for the therapy of acute coronary syndrome. In this work, the reaction of the TNIC with adenosine triphosphoric acid (ATP) was studied. Formation of the products for the reaction of ATP with TNIC was shown by electronic microscopy. The kinetics of the reaction was controlled by spectrofluorometric method, and the complexation constant was measured. The mechanism of interaction of ATP with TNIC was proposed, and the relevant kinetic model satisfactorily described the experimental data, which permitted to calculate the rate constants for these process stages. NMR, IR, and M?ssbauer studies were used for determination of the reaction product structure. NMR study showed TNIC interaction only with adenine part of ATP. The method of IR spectroscopy identified both the absence NO in the reaction products and the occurrence of new Fe-S and Fe-N bonds. M?ssbauer study showed that iron in the reaction products was presented by two forms: Fe(II) and Fe(III). Thus, the structures for the [ATP-Fe2+S] and [ATP-Fe3+S] complexes were proposed.展开更多
The catalytic property of propylene dimerization by several nickel (Ⅱ), cobalt (Ⅱ) complexes containing N-P bidentate ligands was studied in combination with organoaluminum co-catalysts. The effects of the type of a...The catalytic property of propylene dimerization by several nickel (Ⅱ), cobalt (Ⅱ) complexes containing N-P bidentate ligands was studied in combination with organoaluminum co-catalysts. The effects of the type of aluminum co-catalysts and its relative amount, the nature of precursors in terms of ligand backbone and metal center were investigated. The results indicated that precursor I (N,N-dimethyl-2-(diphenylphosphino)aniline nickel (Ⅱ) dichloride) exhibited high activity in propylene dimerization in the presence of the strong Lewis acid Et3Al2Cl3, whereas low productivity by its cobalt analogues was observed under identical reaction conditions.展开更多
基金supported by the National Key R&D Program of China(2017YFA0700102)the National Natural Science Foundation of China(21573222 and 91545202)+1 种基金the Outstanding Youth Talent Project of Dalian(2017RJ03)the DMTO Project of Dalian Institute of Chemical Physics,CAS(DICP DMTO201702),the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020200),the Youth Innovation Promotion Association,CAS(2015145)~~
文摘Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.
基金supported by the Project of National Natural Science Foundation of China(No.21573237,21603227,21403242,21703246)Natural Science Foundation of Fujian Province(2017J05032)
文摘The relationship between the electronic structures of manganese nitrido complexes and the substituted ligands is investigated by using density functional theory.By designing a series of manganese nitrido complexes [Mn（SalenR）N]＋ with different para ring substituents（R = H,CH_3,NH_2,OCH_3,NMeF,etc） of the ancillary ligand,the properties of manganese-nitrogen bonds were compared for two kinds of electronic structures,of which the radical resides on metal center or the coordinated ring ligand.Our calculation shows that for R = H,CH_3 and NH_2,the [Mn（SalenR）N]＋ complexes have a high-valent Mn（VI） center,and for R = OCH_3 and NMeF,the complexes represent a configuration where the radical delocalizes on the ligand.It is found that the relative energies of these two species depend on electronic properties of the substituent,originating from the intrinsic property of HOMO-LUMO gaps.
文摘Nitrogen doping is a promising way to modulate the electrical properties of graphene to realize graphene-based electronics and promise fascinating properties and applications.Herein,we report a method to noncovalently assembly titanium(Ⅳ) bis(ammoniumlactato) dihydroxide(Ti complex) on nitrogen-doped graphene to create a reliable hybrids which can be used as a reversible chemical induced switching.As the adsorption and desorption of Ti complex in sequential treatments,the conductance of the nitrogen-doped graphene transistors was finely modulated.Control experiments with pristine graphene clearly demonstrated the important effort of the nitrogen in this chemical sensor.Under optimized conditions,nitrogen-doped graphene transistors open up new ways to develop multifunctional devices with high sensitivity.
文摘Iron tetranitrosyl complex bearing the thiosulfate ligand (TNIC) is an efficient nitrogen monoxide donor (NO). He shows antitumor properties and may be used as an original drug for the therapy of acute coronary syndrome. In this work, the reaction of the TNIC with adenosine triphosphoric acid (ATP) was studied. Formation of the products for the reaction of ATP with TNIC was shown by electronic microscopy. The kinetics of the reaction was controlled by spectrofluorometric method, and the complexation constant was measured. The mechanism of interaction of ATP with TNIC was proposed, and the relevant kinetic model satisfactorily described the experimental data, which permitted to calculate the rate constants for these process stages. NMR, IR, and M?ssbauer studies were used for determination of the reaction product structure. NMR study showed TNIC interaction only with adenine part of ATP. The method of IR spectroscopy identified both the absence NO in the reaction products and the occurrence of new Fe-S and Fe-N bonds. M?ssbauer study showed that iron in the reaction products was presented by two forms: Fe(II) and Fe(III). Thus, the structures for the [ATP-Fe2+S] and [ATP-Fe3+S] complexes were proposed.
文摘The catalytic property of propylene dimerization by several nickel (Ⅱ), cobalt (Ⅱ) complexes containing N-P bidentate ligands was studied in combination with organoaluminum co-catalysts. The effects of the type of aluminum co-catalysts and its relative amount, the nature of precursors in terms of ligand backbone and metal center were investigated. The results indicated that precursor I (N,N-dimethyl-2-(diphenylphosphino)aniline nickel (Ⅱ) dichloride) exhibited high activity in propylene dimerization in the presence of the strong Lewis acid Et3Al2Cl3, whereas low productivity by its cobalt analogues was observed under identical reaction conditions.
