A new type of dinuclear titanocene was prepared by the reaction of bis(N,N-diethoxyl-aniline)-methane with pentamethylpentadienyl titanium trichloride in the presence of excessive triethylamine.The dinuclear titanocen...A new type of dinuclear titanocene was prepared by the reaction of bis(N,N-diethoxyl-aniline)-methane with pentamethylpentadienyl titanium trichloride in the presence of excessive triethylamine.The dinuclear titanocene displays catalytic activities towards the syndiospecific polymerization of styrene in the presence of modified methylaluminoxane(MMAO) as a cocatalyst,and produces higher molecular weight and syndiotacticity polystyrenes having bimodal molecular weight distribution than their mother complex Cp*TiCl3.Also,the study of polymerization behavior of dinuclear titanocene was carried out under the different polymerization temperature and Al/Ti molar ratio.展开更多
Developing sustainable and clean electrochemical energy conversion technologies is a crucial step in addressing the challenges of energy shortage and environmental pollution. Exploring and developing new electrocataly...Developing sustainable and clean electrochemical energy conversion technologies is a crucial step in addressing the challenges of energy shortage and environmental pollution. Exploring and developing new electrocatalysts with excellent performance and low cost will facilitate the commercial use of these energy conversion technologies. Recently, dual-atom catalysts(DACs) have attracted considerable research interest since they exhibit higher metal atom loading and more flexible active sites compared to single-atom catalysts(SACs). In this paper, the latest preparation methods and characterization techniques of DACs are systematically reviewed. The advantages of homonuclear and heteronuclear DACs and the catalytic mechanism and identification technologies between the two DACs are highlighted. The current applications of DACs in the field of electrocatalysis are summarized. The development opportunities and challenges of DACs in the future are prospected. The ultimate goal is to provide new ideas for the preparation of new catalysts with excellent properties by customizing diatomic catalysts for electrochemical applications.展开更多
Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the cataly...Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the catalytic properties of ruthenium dimers have not yet been explored for visible light‐driven water oxidation.Herein,the photocatalytic performance of a dipyridyl propane‐bridged ruthenium dimer2was investigated in comparison with its monomeric precursor,[Ru(bda)(pic)2](1),in CH3CN/phosphate buffer mixed solvent in a three‐component system including a photosensitizer and a sacrificial electron acceptor.Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH3CN in the phosphate buffer,which not only affected the driving force for water oxidation,but also altered the kinetics of the reaction,probably through different mechanisms associated with the O–O bond formation.As a result,dimer2showedsignificantly higher activity than monomer1in the solvent containing a low content of CH3CN,and comparable activities were attained with a high content of CH3CN in the solvent.Under the optimal conditions,complex2achieved a turnover number of638for photocatalytic O2evolution.展开更多
The complex [Rh（CO）（Pz）（TPPMS）]2, （TPPMS = m-sulfonatophenyl-diphenylphosphine, Pz = Pirazolate） was evaluated as a catalyst precursor in the hydroformylation of allylbenzenes （eugenol and estragol） and terp...The complex [Rh（CO）（Pz）（TPPMS）]2, （TPPMS = m-sulfonatophenyl-diphenylphosphine, Pz = Pirazolate） was evaluated as a catalyst precursor in the hydroformylation of allylbenzenes （eugenol and estragol） and terpenes （limonene and myrcene） and in the hydrogenation of α,β-unsaturated aldehydes （crotonaldehyde, cinnamaldehyde and citral） in a biphasic medium toluene/ionic liquid. Under the reaction conditions studied （P = 600 psi, T= 95 ℃, S/C = 300：1）, the rhodium system showed a high activity and selectivity towards the desired aldehydes. The catalytic phase could be recycled up to five times without any evident loss of activity or selectivity.展开更多
Binuclear iron phthalocyanine/reduced graphene oxide(bi-Fe Pc/RGO) nanocomposite with good electrocatalytic activity for ORR in alkaline medium was prepared in one step. High angle annular dark field image scanning tr...Binuclear iron phthalocyanine/reduced graphene oxide(bi-Fe Pc/RGO) nanocomposite with good electrocatalytic activity for ORR in alkaline medium was prepared in one step. High angle annular dark field image scanning transmission electron microscopy(HAADF-STEM) and energy dispersive X-ray spectroscopy element mapping results show bi-Fe Pc was uniformly distributed on RGO. An obvious cathodic peak located at about-0.23 V(vs. SCE) in CV and an onset potential of-0.004 V(vs. SCE) in LSV indicate the as-prepared bi-Fe Pc/RGO nanocomposite possesses high activity which is closed to Pt/C for ORR. The ORR on bi-Fe Pc/RGO nanocomposite follows four-electron transfer pathway in alkaline medium. Compared with Pt/C, there is only a slight decrease(about 0.02 V vs. SCE) for bi-Fe Pc/RGO nanocomposite when the methanol exists. The excellent activity and methanol tolerance in alkaline solutions proves that bi-Fe Pc/RGO nanocomposite could be considered as a promising cathode catalyst for alkaline fuel cells.展开更多
文摘A new type of dinuclear titanocene was prepared by the reaction of bis(N,N-diethoxyl-aniline)-methane with pentamethylpentadienyl titanium trichloride in the presence of excessive triethylamine.The dinuclear titanocene displays catalytic activities towards the syndiospecific polymerization of styrene in the presence of modified methylaluminoxane(MMAO) as a cocatalyst,and produces higher molecular weight and syndiotacticity polystyrenes having bimodal molecular weight distribution than their mother complex Cp*TiCl3.Also,the study of polymerization behavior of dinuclear titanocene was carried out under the different polymerization temperature and Al/Ti molar ratio.
文摘Developing sustainable and clean electrochemical energy conversion technologies is a crucial step in addressing the challenges of energy shortage and environmental pollution. Exploring and developing new electrocatalysts with excellent performance and low cost will facilitate the commercial use of these energy conversion technologies. Recently, dual-atom catalysts(DACs) have attracted considerable research interest since they exhibit higher metal atom loading and more flexible active sites compared to single-atom catalysts(SACs). In this paper, the latest preparation methods and characterization techniques of DACs are systematically reviewed. The advantages of homonuclear and heteronuclear DACs and the catalytic mechanism and identification technologies between the two DACs are highlighted. The current applications of DACs in the field of electrocatalysis are summarized. The development opportunities and challenges of DACs in the future are prospected. The ultimate goal is to provide new ideas for the preparation of new catalysts with excellent properties by customizing diatomic catalysts for electrochemical applications.
基金supported by the National Basic Research Program of China (973 Program, 2014CB239402)the National Natural Science Foundation of China (21476043)+1 种基金the Fundamental Research Funds for the Central Universities (DUT17ZD204)the Swedish Energy Agency and K&A Wallenberg Foundation~~
文摘Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the catalytic properties of ruthenium dimers have not yet been explored for visible light‐driven water oxidation.Herein,the photocatalytic performance of a dipyridyl propane‐bridged ruthenium dimer2was investigated in comparison with its monomeric precursor,[Ru(bda)(pic)2](1),in CH3CN/phosphate buffer mixed solvent in a three‐component system including a photosensitizer and a sacrificial electron acceptor.Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH3CN in the phosphate buffer,which not only affected the driving force for water oxidation,but also altered the kinetics of the reaction,probably through different mechanisms associated with the O–O bond formation.As a result,dimer2showedsignificantly higher activity than monomer1in the solvent containing a low content of CH3CN,and comparable activities were attained with a high content of CH3CN in the solvent.Under the optimal conditions,complex2achieved a turnover number of638for photocatalytic O2evolution.
文摘The complex [Rh（CO）（Pz）（TPPMS）]2, （TPPMS = m-sulfonatophenyl-diphenylphosphine, Pz = Pirazolate） was evaluated as a catalyst precursor in the hydroformylation of allylbenzenes （eugenol and estragol） and terpenes （limonene and myrcene） and in the hydrogenation of α,β-unsaturated aldehydes （crotonaldehyde, cinnamaldehyde and citral） in a biphasic medium toluene/ionic liquid. Under the reaction conditions studied （P = 600 psi, T= 95 ℃, S/C = 300：1）, the rhodium system showed a high activity and selectivity towards the desired aldehydes. The catalytic phase could be recycled up to five times without any evident loss of activity or selectivity.
基金supported by the National Natural Science Foundation of China (21275014, 21375005)the Excellent Young Scientists Fund of NSFC (21322501)+2 种基金the Importation and Development of High-Caliber Talents Project of Beijing Municipal Institutions (CIT& TCD20140309)the Program for New Century Excellent Talents in University (NCET-12-0603)the Beijing Natural Science Foundation Program and Scientific Research Key Program of the Beijing Municipal Commission of Education (KZ201310005001)
文摘Binuclear iron phthalocyanine/reduced graphene oxide(bi-Fe Pc/RGO) nanocomposite with good electrocatalytic activity for ORR in alkaline medium was prepared in one step. High angle annular dark field image scanning transmission electron microscopy(HAADF-STEM) and energy dispersive X-ray spectroscopy element mapping results show bi-Fe Pc was uniformly distributed on RGO. An obvious cathodic peak located at about-0.23 V(vs. SCE) in CV and an onset potential of-0.004 V(vs. SCE) in LSV indicate the as-prepared bi-Fe Pc/RGO nanocomposite possesses high activity which is closed to Pt/C for ORR. The ORR on bi-Fe Pc/RGO nanocomposite follows four-electron transfer pathway in alkaline medium. Compared with Pt/C, there is only a slight decrease(about 0.02 V vs. SCE) for bi-Fe Pc/RGO nanocomposite when the methanol exists. The excellent activity and methanol tolerance in alkaline solutions proves that bi-Fe Pc/RGO nanocomposite could be considered as a promising cathode catalyst for alkaline fuel cells.
