Sodium-ion batteries(SIBs)hold great promise for large-scale energy storage in the post-lithium-ion battery era due to their high rate performance and long lifespan,although their sluggish Na^(+) transformation kineti...Sodium-ion batteries(SIBs)hold great promise for large-scale energy storage in the post-lithium-ion battery era due to their high rate performance and long lifespan,although their sluggish Na^(+) transformation kinetics still require improvement.Encouraged by the excellent electrochemical performance of titanium-based anode materials,here,we present a novel titanium vanadate@carbon(TVO@C)material as anode for SIBs.Our TVO@C material is synthesized via a facile coprecipitation method,with the following annealing process in an acetylene atomosphere.The opened ion channel and the oxygen vacancies within TVO@C facilitate the diffusion of Na^(+) ions,reducing their diffusion barrier.Thus,an ultrahigh rate of 100 A g^(-1)and long life of 10,000 cycles have been achieved.Furthermore,the TVO@C electrode exhibits stable performance,not only at room temperature,but also at temperatures as low as 20 C.The TVO@CjjNa_(3)V_(2)(PO_(4))_(3)@C full cells have also achieved stable discharge/charge for 500 cycles.It is believed that this strategy provides new insight into the development of advanced electrodes and provides a new opportunity for constructing novel high rate electrodes.展开更多
In this work,the influences of surface layer slurry at different temperatures(10℃,14℃,18℃,22℃)on wax patterns deformation,shrinkage,slurry coating characteristics,and the surface quality of the casting were invest...In this work,the influences of surface layer slurry at different temperatures(10℃,14℃,18℃,22℃)on wax patterns deformation,shrinkage,slurry coating characteristics,and the surface quality of the casting were investigated by using a single factor variable method.The surface morphologies of the shell molds produced by different temperatures of the surface(first)layer slurries were observed via electron microscopy.Furthermore,the microscopic composition of these shell molds was obtained by EDS,and the osmotic effect of the slurry on the wax patterns at different temperatures was also assessed by the PZ-200 Contact Angle detector.The forming reasons for the surface cracks and holes of thick and large ZTC4 titanium alloy by investment casting were analyzed.The experimental results show that the surface of the shell molds prepared by the surface layer slurry with a low temperature exhibits noticeable damage,which is mainly due to the poor coating performance and the serious expansion and contraction of wax pattern at low temperatures.The second layer shell material(SiO_(2),Al_(2)O_(3))immerses into the crack area of the surface layer,contacts and reacts with the molten titanium to form surface cracks and holes in the castings.With the increase of the temperature of surface layer slurry,the damage to the shell surface tends to weaken,and the composition of the shell molds'surface becomes more uniform with less impurities.The results show that the surface layer slurry at 22℃is evenly coated on the surface of the wax patterns with appropriate thickness,and there is no surface shell mold rupture caused by sliding slurry after sand leaching.The surface layer slurry temperature is consistent with the wax pattern temperature and the workshop temperature,so there is no damage of the surface layer shell caused by expansion and contraction.Therefore,the shell mold prepared by the surface layer slurry at this temperature has good integrity,isolating the contact between the low inert shell material and the titanium liquid effectively,and the ZTC4 titanium alloy cylinder casting prepared by this shell mold is smooth,without cracks and holes.展开更多
The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentrati...The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentration, anion species and temperature on zinc extraction were examined. The synergistic mechanism was discussed with regard to the structure of extractant and the extracted zinc complexes. It is found that the increase of total ammonia concentration and pH inhibits zinc extraction for all extraction systems due to the formation of zinc ammine complexes in aqueous phase. This effect of HA with CYANEX923 is evidently smaller than that of HA with LIX84I or HA alone system. Effect of anion species on the zinc extraction by HA with CYANEX923 can be neglected, but this effect of HA alone and the mixture of HA with LIX84I decreases in the order of （NH4）2SO4 〉 NH4NO3 〉 NH4Cl.展开更多
Three new rare earth ternary complexes, RE(PB)_3bpy (RE=Sm^(3+) , Eu^(3+) , and Tb^(3+) ), were synthesized by the reaction of 1-(p-phenylethynyl- phenyl)-1,3-butanedione (HPB) and 2,2′-bipyridine (bpy) with rare ear...Three new rare earth ternary complexes, RE(PB)_3bpy (RE=Sm^(3+) , Eu^(3+) , and Tb^(3+) ), were synthesized by the reaction of 1-(p-phenylethynyl- phenyl)-1,3-butanedione (HPB) and 2,2′-bipyridine (bpy) with rare earth chloride RECl_3 , respectively, in alcohol solution. The compositions were characterized by means of infrared (IR) spectra, chemical analysis, elemental analysis, and thermodynamic analysis. Luminescent properties of the three complexes were studied. At room temperature, under UV light excitation, the Sm^(3+) , Eu^(3+) , and Tb^(3+) complexes exhibit characteristic emission of the central ions. The fluorescence spectra show that the fluorescence emission intensity of Eu^(3+) complex is the strongest. The narrow strongest emission band of Eu^(3+) complex is considered to be a valuable material with bright red fluorescence.展开更多
In order to study the luminescent properties of ternary rare earth complexes with fl-diketone ligand, three new β-diketone ligands, 1-phenyl-3-（p-phenylethynylphenyl）-1,3-propanedione（HPPP）, 1-（2-thienyl）-3-（p...In order to study the luminescent properties of ternary rare earth complexes with fl-diketone ligand, three new β-diketone ligands, 1-phenyl-3-（p-phenylethynylphenyl）-1,3-propanedione（HPPP）, 1-（2-thienyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HTPP） and 1-（2-furyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HFPP）, were synthesized by Sonogashira coupling reaction and Claisen condensation. Three new ternary rare earth complexes, TbL3phen （L = PPP, TPP, or FPP）, were synthesized by the reaction of rare earth chloride TbCl3,1,10-phenanthroline （phen） with HPPP, HTPP, or HFPP respectively, in alcohol solution. The compositions were characterized by means of elemental analysis, chemical analysis, and IR spectra. Luminescent properties of the three new complexes have been studied. The results show that the ternary Yb（Ⅲ） complexes only emit the weak fluorescence of the Tb（Ⅲ） ion, which reveals the triplet state energy of the ligands does not match well with the excited state vibrating energy of Tb^3＋ ion.展开更多
A novel carbazole functionalized β-diketone, methyl 6-（9-ethylcarbazole-3-yl）-oxoacetyl-2-pyridinecarboxylate （MEP）, and its corresponding binary Eu（III） complexes Eu（MEP）y2H2O and ternary complex Eu（MEP）aP...A novel carbazole functionalized β-diketone, methyl 6-（9-ethylcarbazole-3-yl）-oxoacetyl-2-pyridinecarboxylate （MEP）, and its corresponding binary Eu（III） complexes Eu（MEP）y2H2O and ternary complex Eu（MEP）aPhen with 1,10-Phenanthroline （Phen） were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ^1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis （TG-DTA）. The investigation of fluorescence properties of the complexes Eu（MEP）3·2H2O and Eu（MEP）3Phen showed that the Eu（III） ion could be sensitized efficiently by the ligand to some extent, in partitular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the n-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.展开更多
Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3- diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The product...Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3- diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The products were formed in high to excellent yields under mild reaction conditions and in short reaction times.展开更多
The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations....The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations.The TIP3P potential is used for water and the EPM2 model is for CO2.The water phase and SC-CO2 phase form a distinct immiscible liquid-liquid interface.The two chelating molecules show interfacial preference.Comparatively,the AA molecules show somewhat more preference for interfacial region,whereas the HFA molecules are preferably near the Sc-CO2 phase.The orientational distribution of the β-diketone molecules and the radial distribution functions between β-diketones and solvents are obtained in order to study the microscopic structural properties of the β-diketones at the water-SC-CO2 interface.It is found that the translational diffusion and rotational diffusion of HFA and AA are obviously anisotropic and decrease as the β-diketone molecules approach the interface.The anisotropic dynamic behavior for the solute molecules is related to the corresponding structural properties.展开更多
Three novel β-diketones （HPPP, HTPP, and HFPP） ligands were synthesized by Sonogashira coupling reaction and Claisen condensation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS...Three novel β-diketones （HPPP, HTPP, and HFPP） ligands were synthesized by Sonogashira coupling reaction and Claisen condensation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu（Ⅲ）, β-diketones, and 1,10-phenanthroline（phen） were synthesized and characterized as TbL3phen （L=PPP, TPP, FPP） with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.展开更多
Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influenci...Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.展开更多
A novel ligand (3), in which the indenyl group is linked to a β-diketone moiety through a three-carbon bridge, andits titanium complex (4) were synthesized. The titanium complex was employed as a metallocene analog w...A novel ligand (3), in which the indenyl group is linked to a β-diketone moiety through a three-carbon bridge, andits titanium complex (4) were synthesized. The titanium complex was employed as a metallocene analog with co-catalystmethylaluminoxane (MAO) in catalytic syndiospecific polymerization of styrene to give highly syndiotactic polystyrene(s-PS, 96%-97%). Polymerization temperature (T_p) strongly influenced the catalytic activity and syndiotacticity of theproduced PS. The activities of catalyst 4 increase from 1.84×10~6 to 3.26×10~6 gPS/molTi·h with the increase of T_p from60℃ to 80℃ and the syndiotacticities of the produced s-PS also increase slightly. Then, both the catalytic activity and thesyndiotacticity of PS decrease at T_p of 90℃.展开更多
Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction ...Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction of a vinyl-terminated β-diketone with the homopolymeric ladderlike polyhydrosilsesquioxane (LPHSQ) and random copolymethylhydrosilsesquioxane (LRPMHSQ) respectively. These new kinds of FBDKLCP with M of 10~4 is thermotroic liquid crystalline polymer and its clearing temperatures T_i's and mesophase range △T's are much higher than those of the corresponding comb-like β-diketone liquid crystalline polysiloxane (DKLCP) by about 200℃. Similar results have been observed with the comparison of the two different structure Cu-coordinating compounds The significant increases in T_((?))'s and △T's of the FBDKLCP and Cu-FBDKLCP are mainly attributed to the great rigidity of the ladderlike polysilsesquioxane backbone.展开更多
Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-gr...Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.展开更多
A new type of palladium chelate of β-diketone-based side chain liquid crystal polysiloxane (Pd-DKLCP) has been synthesized by chelation reaction of palladium dichloride with polymeric ligand, β-diketone polysiloxane...A new type of palladium chelate of β-diketone-based side chain liquid crystal polysiloxane (Pd-DKLCP) has been synthesized by chelation reaction of palladium dichloride with polymeric ligand, β-diketone polysiloxane (DKLCP), using THF as solvent at R.T.. The Pd-chelation results in greatly increasing the phase transition temperature T_K and the enthalpy change △H_K from crystal to liquid crystal state and making the temperature range of LC state △T(△T=T_(Cl)-T_K) widened. All these chelates Pd-DKLCP's do not show T_(Cl) until decomposition at 205℃. It is noteworthy that the Pd-chelation can exert more positive effect on the mesomorphic behaviour of the polymer ligand than the counterpart Cu-DKLCP does. It is probable due to the bigger size of disc-like mesogen formed from β-diketone and Pd^(+2) ion with 4d orbital.展开更多
A new type of metal coordinated liquid crystalline polymers has been synthesized by complexation of metal ions with β-diketone based side chain liquid crystal polysiloxane (DKLCP). The complexation of copper ions wit...A new type of metal coordinated liquid crystalline polymers has been synthesized by complexation of metal ions with β-diketone based side chain liquid crystal polysiloxane (DKLCP). The complexation of copper ions with DKLCP greatly increases the phase transition temperature T_k from crystalline state to liquid crystalline state and T_(cl) from LC to isotropic state and makes the range of phase transition ΔT (ΔT=T_(cl)-T_k) widened. These complexes are soluble in common organic solvents. However, the incorporation of europium ions into DKLCP molecules gives rise to reduction in liquid crystallinity and crosslinking in some cases. The DKLCP coordinated with suitable amount of Eu ions can show good liquid crystallinity and fluorescent property.展开更多
A new type of binuclear europlum β-diketone chelates Eum Y1-m(TTA)3 phen (0≤m≤1) and the influence of the proportion of Y on fluorescence intensity of the Eu-complexes were studied. It was found the proportion of Y...A new type of binuclear europlum β-diketone chelates Eum Y1-m(TTA)3 phen (0≤m≤1) and the influence of the proportion of Y on fluorescence intensity of the Eu-complexes were studied. It was found the proportion of Y3+ could affect the fluorescence properties and the film formation seriously. only m≥0.5.Y3+ could increase the luminescent intensity and improve the film formalion. As a resull. three new binuclear europium β-diketone chelales consisted of Eu, Y1-m (TTA)3phen (m=0.9. 0.7 and 0.5) were designed and synthesized. Their structures were elucidated by IR. UV. DSC and Elementary Analysis. Their PL properties were studied. The results showed that the three binuclear europium β-diketone chelates had better PL properties and film formation than Eu(TYA)3phen. They could emit sharply red light, and fluorescenl wavelength of them was all at 613nm (half bandwidth 10nm). They can be used as red organic electroluminescent materials (OELMs) in organic electrolminescent devices (OELDS).展开更多
Direct reduction based on hydrogen metallurgical gas-based shaft furnace is a promising technology for the efficient and low-carbon smelting of vanadium-titanium magnetite.However,in this process,the sticking of pelle...Direct reduction based on hydrogen metallurgical gas-based shaft furnace is a promising technology for the efficient and low-carbon smelting of vanadium-titanium magnetite.However,in this process,the sticking of pellets occurs due to the aggregation of metal-lic iron between the contact surfaces of adjacent pellets and has a serious negative effect on the continuous operation.This paper presents a detailed experimental study of the effect of TiO2 on the sticking behavior of pellets during direct reduction under different conditions.Results showed that the sticking index(SI)decreased linearly with the increasing TiO2 addition.This phenomenon can be attributed to the increase in unreduced FeTiO3 during reduction,leading to a decrease in the number and strength of metallic iron interconnections at the sticking interface.When the TiO2 addition amount was raised from 0 to 15wt%at 1100°C,the SI also increased from 0.71%to 59.91%.The connection of the slag phase could be attributed to the sticking at a low reduction temperature,corresponding to the low sticking strength.Moreover,the interconnection of metallic iron became the dominant factor,and the SI increased sharply with the increase in re-duction temperature.TiO2 had a greater effect on SI at a high reduction temperature than at a low reduction temperature.展开更多
Titanium(Ti)alloys are widely used in high-tech fields like aerospace and biomedical engineering.Laser additive manufacturing(LAM),as an innovative technology,is the key driver for the development of Ti alloys.Despite...Titanium(Ti)alloys are widely used in high-tech fields like aerospace and biomedical engineering.Laser additive manufacturing(LAM),as an innovative technology,is the key driver for the development of Ti alloys.Despite the significant advancements in LAM of Ti alloys,there remain challenges that need further research and development efforts.To recap the potential of LAM high-performance Ti alloy,this article systematically reviews LAM Ti alloys with up-to-date information on process,materials,and properties.Several feasible solutions to advance LAM Ti alloys are reviewed,including intelligent process parameters optimization,LAM process innovation with auxiliary fields and novel Ti alloys customization for LAM.The auxiliary energy fields(e.g.thermal,acoustic,mechanical deformation and magnetic fields)can affect the melt pool dynamics and solidification behaviour during LAM of Ti alloys,altering microstructures and mechanical performances.Different kinds of novel Ti alloys customized for LAM,like peritecticα-Ti,eutectoid(α+β)-Ti,hybrid(α+β)-Ti,isomorphousβ-Ti and eutecticβ-Ti alloys are reviewed in detail.Furthermore,machine learning in accelerating the LAM process optimization and new materials development is also outlooked.This review summarizes the material properties and performance envelops and benchmarks the research achievements in LAM of Ti alloys.In addition,the perspectives and further trends in LAM of Ti alloys are also highlighted.展开更多
Density Functional Theory method is applied to investigate the enol-keto tautomerism of both acyclic and cyclic α-fluorine-β-diketones. It is shown that, for acyclic cases, α-fluorine could improve the relative sta...Density Functional Theory method is applied to investigate the enol-keto tautomerism of both acyclic and cyclic α-fluorine-β-diketones. It is shown that, for acyclic cases, α-fluorine could improve the relative stability of keto tautomer by lessening intramolecular hydrogen bond of enol form, whereas the relative stability of cyclic enol could be attributed to two factors： destabilization of keto and stabilization of enol. Furthermore, the relative stabilities of all enol tautomers are improved in THF to different extents.展开更多
基金supported by National Nature Science Foundation of China(22105118)Nature Science Foundation of Shandong Provinces(ZR2021QB095)China Postdoctoral Science Foundation(2020TQ0183 and 2021M701979).
文摘Sodium-ion batteries(SIBs)hold great promise for large-scale energy storage in the post-lithium-ion battery era due to their high rate performance and long lifespan,although their sluggish Na^(+) transformation kinetics still require improvement.Encouraged by the excellent electrochemical performance of titanium-based anode materials,here,we present a novel titanium vanadate@carbon(TVO@C)material as anode for SIBs.Our TVO@C material is synthesized via a facile coprecipitation method,with the following annealing process in an acetylene atomosphere.The opened ion channel and the oxygen vacancies within TVO@C facilitate the diffusion of Na^(+) ions,reducing their diffusion barrier.Thus,an ultrahigh rate of 100 A g^(-1)and long life of 10,000 cycles have been achieved.Furthermore,the TVO@C electrode exhibits stable performance,not only at room temperature,but also at temperatures as low as 20 C.The TVO@CjjNa_(3)V_(2)(PO_(4))_(3)@C full cells have also achieved stable discharge/charge for 500 cycles.It is believed that this strategy provides new insight into the development of advanced electrodes and provides a new opportunity for constructing novel high rate electrodes.
文摘In this work,the influences of surface layer slurry at different temperatures(10℃,14℃,18℃,22℃)on wax patterns deformation,shrinkage,slurry coating characteristics,and the surface quality of the casting were investigated by using a single factor variable method.The surface morphologies of the shell molds produced by different temperatures of the surface(first)layer slurries were observed via electron microscopy.Furthermore,the microscopic composition of these shell molds was obtained by EDS,and the osmotic effect of the slurry on the wax patterns at different temperatures was also assessed by the PZ-200 Contact Angle detector.The forming reasons for the surface cracks and holes of thick and large ZTC4 titanium alloy by investment casting were analyzed.The experimental results show that the surface of the shell molds prepared by the surface layer slurry with a low temperature exhibits noticeable damage,which is mainly due to the poor coating performance and the serious expansion and contraction of wax pattern at low temperatures.The second layer shell material(SiO_(2),Al_(2)O_(3))immerses into the crack area of the surface layer,contacts and reacts with the molten titanium to form surface cracks and holes in the castings.With the increase of the temperature of surface layer slurry,the damage to the shell surface tends to weaken,and the composition of the shell molds'surface becomes more uniform with less impurities.The results show that the surface layer slurry at 22℃is evenly coated on the surface of the wax patterns with appropriate thickness,and there is no surface shell mold rupture caused by sliding slurry after sand leaching.The surface layer slurry temperature is consistent with the wax pattern temperature and the workshop temperature,so there is no damage of the surface layer shell caused by expansion and contraction.Therefore,the shell mold prepared by the surface layer slurry at this temperature has good integrity,isolating the contact between the low inert shell material and the titanium liquid effectively,and the ZTC4 titanium alloy cylinder casting prepared by this shell mold is smooth,without cracks and holes.
基金Project (2007CB613601) supported by the National Basic Research Program of ChinaProject (CX2010B112) supported by Hunan Provincial Innovation Foundation for Postgraduate, China
文摘The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentration, anion species and temperature on zinc extraction were examined. The synergistic mechanism was discussed with regard to the structure of extractant and the extracted zinc complexes. It is found that the increase of total ammonia concentration and pH inhibits zinc extraction for all extraction systems due to the formation of zinc ammine complexes in aqueous phase. This effect of HA with CYANEX923 is evidently smaller than that of HA with LIX84I or HA alone system. Effect of anion species on the zinc extraction by HA with CYANEX923 can be neglected, but this effect of HA alone and the mixture of HA with LIX84I decreases in the order of （NH4）2SO4 〉 NH4NO3 〉 NH4Cl.
基金supported by the National Natural Science Foundation of China(No.21141008)the Natural Science Foundation of Inner Mongolia,China(No.2009MS0205)Baotou Science and Technology Bureau,China(No.2010J2004)
文摘Three new rare earth ternary complexes, RE(PB)_3bpy (RE=Sm^(3+) , Eu^(3+) , and Tb^(3+) ), were synthesized by the reaction of 1-(p-phenylethynyl- phenyl)-1,3-butanedione (HPB) and 2,2′-bipyridine (bpy) with rare earth chloride RECl_3 , respectively, in alcohol solution. The compositions were characterized by means of infrared (IR) spectra, chemical analysis, elemental analysis, and thermodynamic analysis. Luminescent properties of the three complexes were studied. At room temperature, under UV light excitation, the Sm^(3+) , Eu^(3+) , and Tb^(3+) complexes exhibit characteristic emission of the central ions. The fluorescence spectra show that the fluorescence emission intensity of Eu^(3+) complex is the strongest. The narrow strongest emission band of Eu^(3+) complex is considered to be a valuable material with bright red fluorescence.
文摘In order to study the luminescent properties of ternary rare earth complexes with fl-diketone ligand, three new β-diketone ligands, 1-phenyl-3-（p-phenylethynylphenyl）-1,3-propanedione（HPPP）, 1-（2-thienyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HTPP） and 1-（2-furyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HFPP）, were synthesized by Sonogashira coupling reaction and Claisen condensation. Three new ternary rare earth complexes, TbL3phen （L = PPP, TPP, or FPP）, were synthesized by the reaction of rare earth chloride TbCl3,1,10-phenanthroline （phen） with HPPP, HTPP, or HFPP respectively, in alcohol solution. The compositions were characterized by means of elemental analysis, chemical analysis, and IR spectra. Luminescent properties of the three new complexes have been studied. The results show that the ternary Yb（Ⅲ） complexes only emit the weak fluorescence of the Tb（Ⅲ） ion, which reveals the triplet state energy of the ligands does not match well with the excited state vibrating energy of Tb^3＋ ion.
基金supported by China Postdoctoral Science Foundation (20080431027)the Postdoctoral Science Foundation of Central South University (50573019)
文摘A novel carbazole functionalized β-diketone, methyl 6-（9-ethylcarbazole-3-yl）-oxoacetyl-2-pyridinecarboxylate （MEP）, and its corresponding binary Eu（III） complexes Eu（MEP）y2H2O and ternary complex Eu（MEP）aPhen with 1,10-Phenanthroline （Phen） were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ^1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis （TG-DTA）. The investigation of fluorescence properties of the complexes Eu（MEP）3·2H2O and Eu（MEP）3Phen showed that the Eu（III） ion could be sensitized efficiently by the ligand to some extent, in partitular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the n-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.
基金support from the Research Council of Mazandaran University
文摘Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3- diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The products were formed in high to excellent yields under mild reaction conditions and in short reaction times.
基金Supported by the National Natural Science Foundation of China （20776066, 20476044） and the Specialized Research Fund for the Doctoral Program of Higher Education of China （20060291002）.
文摘The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations.The TIP3P potential is used for water and the EPM2 model is for CO2.The water phase and SC-CO2 phase form a distinct immiscible liquid-liquid interface.The two chelating molecules show interfacial preference.Comparatively,the AA molecules show somewhat more preference for interfacial region,whereas the HFA molecules are preferably near the Sc-CO2 phase.The orientational distribution of the β-diketone molecules and the radial distribution functions between β-diketones and solvents are obtained in order to study the microscopic structural properties of the β-diketones at the water-SC-CO2 interface.It is found that the translational diffusion and rotational diffusion of HFA and AA are obviously anisotropic and decrease as the β-diketone molecules approach the interface.The anisotropic dynamic behavior for the solute molecules is related to the corresponding structural properties.
基金supported by the Natural Science Foundation of Inner Mongolia (200508010210)the Education Department of Inner Mongolia (NJ06002, NJcxy08124)Science and Technology Bureau of Baotou (2007G1013)
文摘Three novel β-diketones （HPPP, HTPP, and HFPP） ligands were synthesized by Sonogashira coupling reaction and Claisen condensation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu（Ⅲ）, β-diketones, and 1,10-phenanthroline（phen） were synthesized and characterized as TbL3phen （L=PPP, TPP, FPP） with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.
文摘Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.
基金This project was supported by the National Natural Science Foundation of China (No. 29734141).
文摘A novel ligand (3), in which the indenyl group is linked to a β-diketone moiety through a three-carbon bridge, andits titanium complex (4) were synthesized. The titanium complex was employed as a metallocene analog with co-catalystmethylaluminoxane (MAO) in catalytic syndiospecific polymerization of styrene to give highly syndiotactic polystyrene(s-PS, 96%-97%). Polymerization temperature (T_p) strongly influenced the catalytic activity and syndiotacticity of theproduced PS. The activities of catalyst 4 increase from 1.84×10~6 to 3.26×10~6 gPS/molTi·h with the increase of T_p from60℃ to 80℃ and the syndiotacticities of the produced s-PS also increase slightly. Then, both the catalytic activity and thesyndiotacticity of PS decrease at T_p of 90℃.
文摘Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction of a vinyl-terminated β-diketone with the homopolymeric ladderlike polyhydrosilsesquioxane (LPHSQ) and random copolymethylhydrosilsesquioxane (LRPMHSQ) respectively. These new kinds of FBDKLCP with M of 10~4 is thermotroic liquid crystalline polymer and its clearing temperatures T_i's and mesophase range △T's are much higher than those of the corresponding comb-like β-diketone liquid crystalline polysiloxane (DKLCP) by about 200℃. Similar results have been observed with the comparison of the two different structure Cu-coordinating compounds The significant increases in T_((?))'s and △T's of the FBDKLCP and Cu-FBDKLCP are mainly attributed to the great rigidity of the ladderlike polysilsesquioxane backbone.
基金supported by the National Natural Science Foundation of China(Grant Nos.22075159,22002066)Shandong Taishan Scholars Project(Grant Nos.ts20190932,tsqn202103058)+1 种基金Open Fund of Hubei Key Laboratory of Processing and Application of Catalytic Materials(Grant No.202203404)Postdoctoral Applied Research Project in Qingdao,and the Youth Innovation Team Project of Shandong Provincial Education Department(Grant No.2019KJC023).
文摘Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.
文摘A new type of palladium chelate of β-diketone-based side chain liquid crystal polysiloxane (Pd-DKLCP) has been synthesized by chelation reaction of palladium dichloride with polymeric ligand, β-diketone polysiloxane (DKLCP), using THF as solvent at R.T.. The Pd-chelation results in greatly increasing the phase transition temperature T_K and the enthalpy change △H_K from crystal to liquid crystal state and making the temperature range of LC state △T(△T=T_(Cl)-T_K) widened. All these chelates Pd-DKLCP's do not show T_(Cl) until decomposition at 205℃. It is noteworthy that the Pd-chelation can exert more positive effect on the mesomorphic behaviour of the polymer ligand than the counterpart Cu-DKLCP does. It is probable due to the bigger size of disc-like mesogen formed from β-diketone and Pd^(+2) ion with 4d orbital.
文摘A new type of metal coordinated liquid crystalline polymers has been synthesized by complexation of metal ions with β-diketone based side chain liquid crystal polysiloxane (DKLCP). The complexation of copper ions with DKLCP greatly increases the phase transition temperature T_k from crystalline state to liquid crystalline state and T_(cl) from LC to isotropic state and makes the range of phase transition ΔT (ΔT=T_(cl)-T_k) widened. These complexes are soluble in common organic solvents. However, the incorporation of europium ions into DKLCP molecules gives rise to reduction in liquid crystallinity and crosslinking in some cases. The DKLCP coordinated with suitable amount of Eu ions can show good liquid crystallinity and fluorescent property.
文摘A new type of binuclear europlum β-diketone chelates Eum Y1-m(TTA)3 phen (0≤m≤1) and the influence of the proportion of Y on fluorescence intensity of the Eu-complexes were studied. It was found the proportion of Y3+ could affect the fluorescence properties and the film formation seriously. only m≥0.5.Y3+ could increase the luminescent intensity and improve the film formalion. As a resull. three new binuclear europium β-diketone chelales consisted of Eu, Y1-m (TTA)3phen (m=0.9. 0.7 and 0.5) were designed and synthesized. Their structures were elucidated by IR. UV. DSC and Elementary Analysis. Their PL properties were studied. The results showed that the three binuclear europium β-diketone chelates had better PL properties and film formation than Eu(TYA)3phen. They could emit sharply red light, and fluorescenl wavelength of them was all at 613nm (half bandwidth 10nm). They can be used as red organic electroluminescent materials (OELMs) in organic electrolminescent devices (OELDS).
基金the National Natural Science Foundation of China(No.51904063)the Science and Technology Plan Project of Liaoning Province,China(No.2022JH24/10200027)+1 种基金the Key Research and Development Project of Hebei Province,China(No.21314001D)the seventh batch of the Ten Thousand Talents Plan(No.ZX20220553).
文摘Direct reduction based on hydrogen metallurgical gas-based shaft furnace is a promising technology for the efficient and low-carbon smelting of vanadium-titanium magnetite.However,in this process,the sticking of pellets occurs due to the aggregation of metal-lic iron between the contact surfaces of adjacent pellets and has a serious negative effect on the continuous operation.This paper presents a detailed experimental study of the effect of TiO2 on the sticking behavior of pellets during direct reduction under different conditions.Results showed that the sticking index(SI)decreased linearly with the increasing TiO2 addition.This phenomenon can be attributed to the increase in unreduced FeTiO3 during reduction,leading to a decrease in the number and strength of metallic iron interconnections at the sticking interface.When the TiO2 addition amount was raised from 0 to 15wt%at 1100°C,the SI also increased from 0.71%to 59.91%.The connection of the slag phase could be attributed to the sticking at a low reduction temperature,corresponding to the low sticking strength.Moreover,the interconnection of metallic iron became the dominant factor,and the SI increased sharply with the increase in re-duction temperature.TiO2 had a greater effect on SI at a high reduction temperature than at a low reduction temperature.
基金financially supported by the Young Individual Research Grants(Grant No:M22K3c0097)Singapore RIE 2025 plan and Singapore Aerospace Programme Cycle 16(Grant No:M2215a0073)led by C Tan+2 种基金supported by the Singapore A*STAR Career Development Funds(Grant No:C210812047)the National Natural Science Foundation of China(52174361 and 52374385)the support by US NSF DMR-2104933。
文摘Titanium(Ti)alloys are widely used in high-tech fields like aerospace and biomedical engineering.Laser additive manufacturing(LAM),as an innovative technology,is the key driver for the development of Ti alloys.Despite the significant advancements in LAM of Ti alloys,there remain challenges that need further research and development efforts.To recap the potential of LAM high-performance Ti alloy,this article systematically reviews LAM Ti alloys with up-to-date information on process,materials,and properties.Several feasible solutions to advance LAM Ti alloys are reviewed,including intelligent process parameters optimization,LAM process innovation with auxiliary fields and novel Ti alloys customization for LAM.The auxiliary energy fields(e.g.thermal,acoustic,mechanical deformation and magnetic fields)can affect the melt pool dynamics and solidification behaviour during LAM of Ti alloys,altering microstructures and mechanical performances.Different kinds of novel Ti alloys customized for LAM,like peritecticα-Ti,eutectoid(α+β)-Ti,hybrid(α+β)-Ti,isomorphousβ-Ti and eutecticβ-Ti alloys are reviewed in detail.Furthermore,machine learning in accelerating the LAM process optimization and new materials development is also outlooked.This review summarizes the material properties and performance envelops and benchmarks the research achievements in LAM of Ti alloys.In addition,the perspectives and further trends in LAM of Ti alloys are also highlighted.
基金This project was supported by the Natural Science Foundation of China (No. 20502022) and the Ph.D. Fund of Ningbo (No. 2004A610010)
文摘Density Functional Theory method is applied to investigate the enol-keto tautomerism of both acyclic and cyclic α-fluorine-β-diketones. It is shown that, for acyclic cases, α-fluorine could improve the relative stability of keto tautomer by lessening intramolecular hydrogen bond of enol form, whereas the relative stability of cyclic enol could be attributed to two factors： destabilization of keto and stabilization of enol. Furthermore, the relative stabilities of all enol tautomers are improved in THF to different extents.
