Based on the measurement of the released hydrogen gas pressure （PH2）, the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of...Based on the measurement of the released hydrogen gas pressure （PH2）, the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH2 powder and aluminum melt was studied. The results show that the-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism： （a） 700-750°C, （b） 750-800°C, and （c） 800-1000°C. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800°C, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range （800-1000°C）, the dominant controlling mechanism is diffusion.展开更多
Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of hig...Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of high-quality TiC powders with low cost and high efficiency is crucial for industrial applications;however major challenges face its realization.Herein,the methods for synthesizing TiC powders based on a reaction system are reviewed.This analysis is focused on the underlying mechanisms by which synthesis methods affect the quality of powders.Notably,strategies for improving the synthesis of highquality powders are analyzed from the perspective of enhancing heat and mass transfer processes.Furthermore,the critical issues,challenges,and development trends of the synthesis technology and application of high-quality TiC powder are discussed.展开更多
he axial coordination reactions of tetraphenylporphinatocobalt (Ⅲ) chloride(Co TPPC1) with various imidazoles RIm ( HIm . imidazole; Melm , 2-methylimida-zole) were investigated in acetone and dichloromethand so...he axial coordination reactions of tetraphenylporphinatocobalt (Ⅲ) chloride(Co TPPC1) with various imidazoles RIm ( HIm . imidazole; Melm , 2-methylimida-zole) were investigated in acetone and dichloromethand solvents at different temper-atures. The reaction mechanisms were proposed and the differences between experi-mental results in the two solvents h ave been interpreted using the proposed mecha-nisms and rate equations for the first time , and the reaction scheme for the axial re-action of the metalloporphyrin has been developed. Hydrogen bonding plays an im-portant role in the reactions. The effects of various imidazoles for these reactionsand the solvents are reported. The comparison between iron and cobalt porphyrinsin the kinetics are discussed.展开更多
The kinetics of forward extraction of Ti（IV） from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti（IV）,the rate of forward extraction at ...The kinetics of forward extraction of Ti（IV） from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti（IV）,the rate of forward extraction at 298 K can be represented by F（kmol·m-2·s-1）=10-5.07 [TiO 2 ＋ ][H＋]-1 [NaHA 2 ]（o）·Analysis of the rate expression reveals that the rate determining step is（TiO）（i）2＋ ＋（HA 2）（i）-[TiO（HA2）]（i）＋.The values of Ea,H±,S±,and G±298 are calculated to be 22 kJ·mol-1,25 kJ·mol-1,-218 J·mol-1·K-1,and 25 kJ·mol-1,respectively.The experimental negative S± values indicate that the reaction step occurs via SN2 mechanism.展开更多
A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylben...A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene(3 F) or styrene(St) blocking units on the surface of glassy carbon(GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3 F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via(1) the radical coupling interaction between the two metallo-oxyl radicals(I2 M) in the homo-coupling polymer(poly-1), and(2) the water nucleophilic attack(WNA) pathway in poly-1+P3 F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.展开更多
The fluorescence kinetic characteristics of binary complex Ti-3,5-dibromosalicylfluorone (Ti-3,5-DBSAF) was studied by stopped-flow fluorescence kinetic method, the results showthat its rate equation is R=k.[Ti4+].[H4...The fluorescence kinetic characteristics of binary complex Ti-3,5-dibromosalicylfluorone (Ti-3,5-DBSAF) was studied by stopped-flow fluorescence kinetic method, the results showthat its rate equation is R=k.[Ti4+].[H4R] [H3+ O]-1, refering to Eigen-Tamm mechanism, the reasonable mechanism is derivated. The possibile geometric structure of the binary complex was alsodiscussed.展开更多
文摘Based on the measurement of the released hydrogen gas pressure （PH2）, the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH2 powder and aluminum melt was studied. The results show that the-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism： （a） 700-750°C, （b） 750-800°C, and （c） 800-1000°C. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800°C, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range （800-1000°C）, the dominant controlling mechanism is diffusion.
基金supported by Basic Frontier Scientific Research of the Chinese Academy of Sciences(ZDBS-LY-JSC041)the National Natural Science Foundation of China(22178348)+1 种基金the open research fund of the State Key Laboratory of Mesoscience and Engineering(MESO-23-D06)the Youth Innovation Promotion Association CAS(292021000085)。
文摘Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of high-quality TiC powders with low cost and high efficiency is crucial for industrial applications;however major challenges face its realization.Herein,the methods for synthesizing TiC powders based on a reaction system are reviewed.This analysis is focused on the underlying mechanisms by which synthesis methods affect the quality of powders.Notably,strategies for improving the synthesis of highquality powders are analyzed from the perspective of enhancing heat and mass transfer processes.Furthermore,the critical issues,challenges,and development trends of the synthesis technology and application of high-quality TiC powder are discussed.
文摘he axial coordination reactions of tetraphenylporphinatocobalt (Ⅲ) chloride(Co TPPC1) with various imidazoles RIm ( HIm . imidazole; Melm , 2-methylimida-zole) were investigated in acetone and dichloromethand solvents at different temper-atures. The reaction mechanisms were proposed and the differences between experi-mental results in the two solvents h ave been interpreted using the proposed mecha-nisms and rate equations for the first time , and the reaction scheme for the axial re-action of the metalloporphyrin has been developed. Hydrogen bonding plays an im-portant role in the reactions. The effects of various imidazoles for these reactionsand the solvents are reported. The comparison between iron and cobalt porphyrinsin the kinetics are discussed.
基金supported by the Key Subject of Shanghai Municipality (S30109)the Opening Project of Key Laboratory of Solid Waste Treatment and Resource Recycle (SWUST),the Ministry of Education (09zxgk02)Research Program of Science and Technology Commission of Shanghai Municipality (09dz1204403)
文摘The kinetics of forward extraction of Ti（IV） from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti（IV）,the rate of forward extraction at 298 K can be represented by F（kmol·m-2·s-1）=10-5.07 [TiO 2 ＋ ][H＋]-1 [NaHA 2 ]（o）·Analysis of the rate expression reveals that the rate determining step is（TiO）（i）2＋ ＋（HA 2）（i）-[TiO（HA2）]（i）＋.The values of Ea,H±,S±,and G±298 are calculated to be 22 kJ·mol-1,25 kJ·mol-1,-218 J·mol-1·K-1,and 25 kJ·mol-1,respectively.The experimental negative S± values indicate that the reaction step occurs via SN2 mechanism.
文摘A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene(3 F) or styrene(St) blocking units on the surface of glassy carbon(GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3 F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via(1) the radical coupling interaction between the two metallo-oxyl radicals(I2 M) in the homo-coupling polymer(poly-1), and(2) the water nucleophilic attack(WNA) pathway in poly-1+P3 F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.
文摘The fluorescence kinetic characteristics of binary complex Ti-3,5-dibromosalicylfluorone (Ti-3,5-DBSAF) was studied by stopped-flow fluorescence kinetic method, the results showthat its rate equation is R=k.[Ti4+].[H4R] [H3+ O]-1, refering to Eigen-Tamm mechanism, the reasonable mechanism is derivated. The possibile geometric structure of the binary complex was alsodiscussed.
