Electrocatalytic water splitting is a viable technique for generating hydrogen but is precluded from the sluggish kinetics of oxygen evolution reactions(OER).Small molecule oxidation reactions with lower working poten...Electrocatalytic water splitting is a viable technique for generating hydrogen but is precluded from the sluggish kinetics of oxygen evolution reactions(OER).Small molecule oxidation reactions with lower working potentials,such as methanol oxidation reactions,are good alternatives to OER with faster kinetics.However,the typically employed Ni-based electrocatalysts have poor activity and stability.Herein,a novel three-dimensional(3D)-networking Modoped Ni(OH)_(2) with ultralow Ni-Ni coordination is synthesized,which exhibits a high MOR activity of 100 mA cm^(−2) at 1.39 V,delivering 28 mV dec^(−1) for the Tafel slope.Meanwhile,hydrogen evolution with value-added formate co-generation is boosted with a current density of more than 500 mA cm^(−2) at a cell voltage of 2.00 V for 50 h,showing excellent stability in an industrial alkaline concentration(6 M KOH).Mechanistic studies based on density functional the-ory and X-ray absorption spectroscopy showed that the improved performance is mainly attributed to the ultralow Ni-Ni coordination,3D-networking structures and Mo dopants,which improve the catalytic activity,increase the active site density and strengthen the Ni(OH)_(2)3D-networking structures,respectively.This study paves a new way for designing electrocatalysts with enhanced activity and durability for industrial energy-saving hydrogen production.展开更多
The electrochemistry of (TPP)Co in the presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. With the addition of pyridine to the solution, the reduction peaks of the axial complex co...The electrochemistry of (TPP)Co in the presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. With the addition of pyridine to the solution, the reduction peaks of the axial complex compounds, (TPP)Co(III)(Py) and (TPP)Co(III)(Py)(2) were observed. It was found that the reduction peak of Co(II)/Co(I) shifted to about -1.20V (SCE) with the increase of added pyridine. The new reduction peak may be attributed to the direct reduction of the axially complex (TPP)Co(II)(Py).展开更多
Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the s...Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the structural and electrochemical properties of the Li[Ni1/3Co1/3Mn1/3]O2 materials was studied.It is found that when the molar ratio of ammonia to total transition-metal cations is 2.7:1,uniform particle size distribution of the complex metal hydroxide is observed via scanning electron microscopy.The average particle size of Li[Ni1/3Co1/3Mn1/3]O2 materials was measured to be about 500 nm,and the tap-density was measured to be approximately 2.37 g/cm3,which is comparable with that of commercialized LiCoO2.XRD analysis indicates that the presently synthesized Li[Ni1/3Co1/3Mn1/3]O2 has a hexagonal layered-structure.The initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 positive-electrode material is determined to be 181.5 mA·h/g using a Li/Li[Ni1/3Co1/3Mn1/3]O2 cell operated at 0.1C in the voltage range of 2.8-4.5 V.The discharge capacity at the 50th cycle at 0.5C is 170.6 mA·h/g.展开更多
The effect of pH values on synthesizing single-phase CoTi-substituted barium M-type ferrite ultrafine powders,and BaCoTiFe- 10O- 19, was investigated employing corrosion versus pH plot (E-pH plot) for metal element,...The effect of pH values on synthesizing single-phase CoTi-substituted barium M-type ferrite ultrafine powders,and BaCoTiFe- 10O- 19, was investigated employing corrosion versus pH plot (E-pH plot) for metal element, thermodynamic calculation, and co-dump coprecipitation. The pH values of complete coprecipitation of all Fe 3+, Ti 4+, Co 2+ and Ba 2+ cations are 9-12 and higher than 7.9 on the basis of E-pH plot analysis and thermodynamic calculation, respectively. The minimum pH value necessary to the formation of single-phase BaCoTiFe- 10O- 19 is 8.5 in the light of the co-dump coprecipitation.These results indicate that the coprecipitation process for synthesizing CoTi-substituted barium M-type ferrite ultrafine powders is simultaneously influenced by synergetic coprecipation effect of cations and coordination effect of Cl-anions. The test time of the minimum pH value corresponding to forming a series of single-phase CoTi-substituted barium M-type ferrite ultrafine powders,and BaCo-xTi-xFe- 12-2xO- 19, may be significantly reduced by using the effects of two new factors on the coprecipitation process.展开更多
The delay vehicles experience at signalized intersections is one of the most important indicators for measuring intersection performance. The interpretation of delay variability evolvement at intersections gives a com...The delay vehicles experience at signalized intersections is one of the most important indicators for measuring intersection performance. The interpretation of delay variability evolvement at intersections gives a comprehensive insight into arterial traffic operation. Thus, an analytical model is proposed to investigate delay variability at coordinated intersections. Two different flow rates are assumed for both effective red and green periods in cumulative curves, through which the effect of signal coordination is incorporated in delay estimation. Then, an analogy of Markov chain process is used to explore the mechanism of stochastic overflow queue at signalized intersections. Numerical case studies show that with the decrease of arrival proportions during green, the shape of delay distribution in both undersaturation and oversaturation cases shifts faster towards higher values, implying that the coordination effect between paired intersections has a great effect on the delay distribution. As for delay fluctuation range, favorable coordination is demonstrated to be able to weaken the variability of delay estimates especially for undersaturation conditions.展开更多
Cyclic voltammetry is used to study the electrochemical behavior of CoCl 2, Co(dppe) 2Cl 2 and Co(mbt S,N) 2(dppe) [Hmbt=2 mercaptobenzothiazole; dppe=1,2 (diphenylphosphino)] in DMF or MeCN solution with 0...Cyclic voltammetry is used to study the electrochemical behavior of CoCl 2, Co(dppe) 2Cl 2 and Co(mbt S,N) 2(dppe) [Hmbt=2 mercaptobenzothiazole; dppe=1,2 (diphenylphosphino)] in DMF or MeCN solution with 0.1 mol·L -1 Bu n 4NBF 4 as electrolyte on the Pt electrode. The results indicate that the reduction potential, transfer coefficient and diffusion coefficient of Co(Ⅱ), Co(dppe)(Ⅱ) and Co(mbt S,N) 2(dppe) in DMF and MeCN depend on the solvent coordinated species, the volume and structure of ion. This is the characterization of the synergistic coordination effect.展开更多
Based on the theory of technology spillover in international trade, this paper discusses the technological innovation effect of trade by taking the influence of domestic trade into account. Under the constraint of the...Based on the theory of technology spillover in international trade, this paper discusses the technological innovation effect of trade by taking the influence of domestic trade into account. Under the constraint of the production possibility frontier, there is either complementarity or substitutability between domestic and foreign trade. It must be decided whether resources should be concentrated in one of the sectors (trade specialization) or instead allocated equally (trade equalization) between the two sectors. This paper firstly discusses how domestic trade and foreign trade work together to influence technological innovation, and how trade equalization and specialization affect different types of innovation. Using a provincial-level panel dataset from 2007 to 2015 in China, this paper constructs the indicators of domestic and foreign trade linkage and examines the impact of trade on innovation. The findings show that trade equalization mainly promotes incremental innovation, while trade specialization improves radical innovation. Thus, in the area of incremental innovation, attention should be paid to the equalized development of domestic and foreign trade, while in areas pursuing radical innovation, emphasis should be put on the specialization of the trade sector, avoiding equal allocation of resources to the two sectors.展开更多
Iron-based single-atom catalysts with nitrogen-doped carbon as support(Fe-SA/NPC)are considered effective alternatives to replace Pt-group metals for scalable application in fuel cells.However,synthesizing high-loadin...Iron-based single-atom catalysts with nitrogen-doped carbon as support(Fe-SA/NPC)are considered effective alternatives to replace Pt-group metals for scalable application in fuel cells.However,synthesizing high-loading Fe-SA catalysts by a simple procedure remains challenging.Herein,we report a high-loading(7.5 wt%)Fe-SA/NPC catalyst prepared by carbon-assisted pyrolysis of metal complexes.Both the nitrogen-doped porous carbon(NPC)support with high specific surface area and ο-phenylenediamine(o-PD)play key roles role in the preparation of high-loading Fe-SA/NPC catalysts.The results of X-ray photoelectron spectroscopy,high-angle annular dark-field scanning transmission electron microscopy,and X-ray absorption fine structure spectroscopy experiments show that the Fe atoms are anchored on the carbon carriers in a single-atom site configuration and coordinated with four of the doped nitrogen atoms of the carbon substrates(Fe-N_(4)).The activities of the Fe-SA/NPC catalysts in the oxygen reduction reaction increased with increasing iron loading.The optimized 250Fe-SA/NPC-800 catalyst exhibited an onset potential 0.97 V of and a half-wave potential of 0.85 V.Our study provides a simple approach for the large-scale synthesis of high-loading single-atom catalysts.展开更多
A novel method of patterning high precision copper conductive micropatterns on flexible polymer substrate(polyimide)is developed.We utilized the coordination effect between palladium salts and pyridine structures to f...A novel method of patterning high precision copper conductive micropatterns on flexible polymer substrate(polyimide)is developed.We utilized the coordination effect between palladium salts and pyridine structures to fix the palladium chloride(PdCl_(2))on the surface of polymer film while the 2,6-dimethylpyridine structures formed in the specific areas under ultraviolet light guaranteed the resolution of final patterns.Simultaneous thermal reduction of PdCl_(2) on the surface can be achieved in the process of thermal cyclization of the polymer substrate.As a consequence,the obtained polyimide(PI)film can be patterned with conductive copper micropatterns directly by electroless plating.In particular,we accomplished the deposition of high precision copper pattern with a minimum line width of 50μm and minimum line spacing of 20μm on PI thin films(thickness~10μm)by electroless plating.The prepared conductive copper micropatterns exhibit a low resistivity of 1.78μΩ·cm the same as the pure block copper.And the relationship between the structures of the polymer chains and the physical properties of polymer substrates,such as the dimensional stability,mechanical and dielectric properties were also discussed in detail.This simple and novel method of patterning metal on the polymer surface does not need to achieve the catalytic metal adhesion required for electroless plating at the cost of destroying the substrate surface and avoiding the introduction of unstable interlayers.This patterning method is compatible with the current roll-to-roll production process and can be used to develop high-performance micro-integrated circuits.展开更多
基金We gratefully thank the financial support from the National Natural Science Foundation of China(22272108,21975163 and 22003041)Shenzhen Science and Technology Program(No.KQTD20190929173914967,JCYJ20200109110416441)the Senior Talent Research Start-up Fund of Shenzhen University(000263 and 000265).
文摘Electrocatalytic water splitting is a viable technique for generating hydrogen but is precluded from the sluggish kinetics of oxygen evolution reactions(OER).Small molecule oxidation reactions with lower working potentials,such as methanol oxidation reactions,are good alternatives to OER with faster kinetics.However,the typically employed Ni-based electrocatalysts have poor activity and stability.Herein,a novel three-dimensional(3D)-networking Modoped Ni(OH)_(2) with ultralow Ni-Ni coordination is synthesized,which exhibits a high MOR activity of 100 mA cm^(−2) at 1.39 V,delivering 28 mV dec^(−1) for the Tafel slope.Meanwhile,hydrogen evolution with value-added formate co-generation is boosted with a current density of more than 500 mA cm^(−2) at a cell voltage of 2.00 V for 50 h,showing excellent stability in an industrial alkaline concentration(6 M KOH).Mechanistic studies based on density functional the-ory and X-ray absorption spectroscopy showed that the improved performance is mainly attributed to the ultralow Ni-Ni coordination,3D-networking structures and Mo dopants,which improve the catalytic activity,increase the active site density and strengthen the Ni(OH)_(2)3D-networking structures,respectively.This study paves a new way for designing electrocatalysts with enhanced activity and durability for industrial energy-saving hydrogen production.
文摘The electrochemistry of (TPP)Co in the presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. With the addition of pyridine to the solution, the reduction peaks of the axial complex compounds, (TPP)Co(III)(Py) and (TPP)Co(III)(Py)(2) were observed. It was found that the reduction peak of Co(II)/Co(I) shifted to about -1.20V (SCE) with the increase of added pyridine. The new reduction peak may be attributed to the direct reduction of the axially complex (TPP)Co(II)(Py).
基金Project(50721003)supported by the National Natural Science Foundation of ChinaProject(07JJ6082)supported by the Natural Science Foundation of Hunan Province,ChinaProject supported by the Open Project of State Key Laboratory of Powder Metallurgy in Central South University,China
文摘Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the structural and electrochemical properties of the Li[Ni1/3Co1/3Mn1/3]O2 materials was studied.It is found that when the molar ratio of ammonia to total transition-metal cations is 2.7:1,uniform particle size distribution of the complex metal hydroxide is observed via scanning electron microscopy.The average particle size of Li[Ni1/3Co1/3Mn1/3]O2 materials was measured to be about 500 nm,and the tap-density was measured to be approximately 2.37 g/cm3,which is comparable with that of commercialized LiCoO2.XRD analysis indicates that the presently synthesized Li[Ni1/3Co1/3Mn1/3]O2 has a hexagonal layered-structure.The initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 positive-electrode material is determined to be 181.5 mA·h/g using a Li/Li[Ni1/3Co1/3Mn1/3]O2 cell operated at 0.1C in the voltage range of 2.8-4.5 V.The discharge capacity at the 50th cycle at 0.5C is 170.6 mA·h/g.
文摘The effect of pH values on synthesizing single-phase CoTi-substituted barium M-type ferrite ultrafine powders,and BaCoTiFe- 10O- 19, was investigated employing corrosion versus pH plot (E-pH plot) for metal element, thermodynamic calculation, and co-dump coprecipitation. The pH values of complete coprecipitation of all Fe 3+, Ti 4+, Co 2+ and Ba 2+ cations are 9-12 and higher than 7.9 on the basis of E-pH plot analysis and thermodynamic calculation, respectively. The minimum pH value necessary to the formation of single-phase BaCoTiFe- 10O- 19 is 8.5 in the light of the co-dump coprecipitation.These results indicate that the coprecipitation process for synthesizing CoTi-substituted barium M-type ferrite ultrafine powders is simultaneously influenced by synergetic coprecipation effect of cations and coordination effect of Cl-anions. The test time of the minimum pH value corresponding to forming a series of single-phase CoTi-substituted barium M-type ferrite ultrafine powders,and BaCo-xTi-xFe- 12-2xO- 19, may be significantly reduced by using the effects of two new factors on the coprecipitation process.
基金Project(51278455)supported by the National Natural Science Foundation of ChinaProject(2012M521175)supported by the National Science Foundation for Post-doctoral Scientists of ChinaProject(Bsh1202056)supported by and the Excellent Postdoctoral Science Foundation of Zhejiang Province,China
文摘The delay vehicles experience at signalized intersections is one of the most important indicators for measuring intersection performance. The interpretation of delay variability evolvement at intersections gives a comprehensive insight into arterial traffic operation. Thus, an analytical model is proposed to investigate delay variability at coordinated intersections. Two different flow rates are assumed for both effective red and green periods in cumulative curves, through which the effect of signal coordination is incorporated in delay estimation. Then, an analogy of Markov chain process is used to explore the mechanism of stochastic overflow queue at signalized intersections. Numerical case studies show that with the decrease of arrival proportions during green, the shape of delay distribution in both undersaturation and oversaturation cases shifts faster towards higher values, implying that the coordination effect between paired intersections has a great effect on the delay distribution. As for delay fluctuation range, favorable coordination is demonstrated to be able to weaken the variability of delay estimates especially for undersaturation conditions.
文摘Cyclic voltammetry is used to study the electrochemical behavior of CoCl 2, Co(dppe) 2Cl 2 and Co(mbt S,N) 2(dppe) [Hmbt=2 mercaptobenzothiazole; dppe=1,2 (diphenylphosphino)] in DMF or MeCN solution with 0.1 mol·L -1 Bu n 4NBF 4 as electrolyte on the Pt electrode. The results indicate that the reduction potential, transfer coefficient and diffusion coefficient of Co(Ⅱ), Co(dppe)(Ⅱ) and Co(mbt S,N) 2(dppe) in DMF and MeCN depend on the solvent coordinated species, the volume and structure of ion. This is the characterization of the synergistic coordination effect.
文摘Based on the theory of technology spillover in international trade, this paper discusses the technological innovation effect of trade by taking the influence of domestic trade into account. Under the constraint of the production possibility frontier, there is either complementarity or substitutability between domestic and foreign trade. It must be decided whether resources should be concentrated in one of the sectors (trade specialization) or instead allocated equally (trade equalization) between the two sectors. This paper firstly discusses how domestic trade and foreign trade work together to influence technological innovation, and how trade equalization and specialization affect different types of innovation. Using a provincial-level panel dataset from 2007 to 2015 in China, this paper constructs the indicators of domestic and foreign trade linkage and examines the impact of trade on innovation. The findings show that trade equalization mainly promotes incremental innovation, while trade specialization improves radical innovation. Thus, in the area of incremental innovation, attention should be paid to the equalized development of domestic and foreign trade, while in areas pursuing radical innovation, emphasis should be put on the specialization of the trade sector, avoiding equal allocation of resources to the two sectors.
文摘Iron-based single-atom catalysts with nitrogen-doped carbon as support(Fe-SA/NPC)are considered effective alternatives to replace Pt-group metals for scalable application in fuel cells.However,synthesizing high-loading Fe-SA catalysts by a simple procedure remains challenging.Herein,we report a high-loading(7.5 wt%)Fe-SA/NPC catalyst prepared by carbon-assisted pyrolysis of metal complexes.Both the nitrogen-doped porous carbon(NPC)support with high specific surface area and ο-phenylenediamine(o-PD)play key roles role in the preparation of high-loading Fe-SA/NPC catalysts.The results of X-ray photoelectron spectroscopy,high-angle annular dark-field scanning transmission electron microscopy,and X-ray absorption fine structure spectroscopy experiments show that the Fe atoms are anchored on the carbon carriers in a single-atom site configuration and coordinated with four of the doped nitrogen atoms of the carbon substrates(Fe-N_(4)).The activities of the Fe-SA/NPC catalysts in the oxygen reduction reaction increased with increasing iron loading.The optimized 250Fe-SA/NPC-800 catalyst exhibited an onset potential 0.97 V of and a half-wave potential of 0.85 V.Our study provides a simple approach for the large-scale synthesis of high-loading single-atom catalysts.
基金financially supported by the National Natural Science Foundation of China(No.51833011)the National Key Research and Development Program of China(No.2016YT03C077)。
文摘A novel method of patterning high precision copper conductive micropatterns on flexible polymer substrate(polyimide)is developed.We utilized the coordination effect between palladium salts and pyridine structures to fix the palladium chloride(PdCl_(2))on the surface of polymer film while the 2,6-dimethylpyridine structures formed in the specific areas under ultraviolet light guaranteed the resolution of final patterns.Simultaneous thermal reduction of PdCl_(2) on the surface can be achieved in the process of thermal cyclization of the polymer substrate.As a consequence,the obtained polyimide(PI)film can be patterned with conductive copper micropatterns directly by electroless plating.In particular,we accomplished the deposition of high precision copper pattern with a minimum line width of 50μm and minimum line spacing of 20μm on PI thin films(thickness~10μm)by electroless plating.The prepared conductive copper micropatterns exhibit a low resistivity of 1.78μΩ·cm the same as the pure block copper.And the relationship between the structures of the polymer chains and the physical properties of polymer substrates,such as the dimensional stability,mechanical and dielectric properties were also discussed in detail.This simple and novel method of patterning metal on the polymer surface does not need to achieve the catalytic metal adhesion required for electroless plating at the cost of destroying the substrate surface and avoiding the introduction of unstable interlayers.This patterning method is compatible with the current roll-to-roll production process and can be used to develop high-performance micro-integrated circuits.