A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DE...A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DESs) were used as electron-donors for aerobic oxidative desulfurization(AODS) of diesel fuel. Different compositions of DESs were used and the polyethylene glycol 2000(PEG2000)/2.5 BSA system showed the highest desulfurization activity, with the removal of dibenzothiophene(DBT) at 60 ℃ reaching 95% in 60 min. The excellent desulfurization activity of the system is due to the in situ formation of peroxysulfonate via a biomimetic process. By constructing a coupled redox system, Fe-Anderson type POMs as ETMs reduce the activation energy of oxygen-activated sulfonate. The physical characteristics of four different DESs were tested. The results show that the conductivity of DESs is correlated with the composition of BSA-based DESs. However, there is no similar trend in viscosity testing at the same temperature, and the maximum viscosity value is obtained for the PEG2000/2.5 BSA system at 60 ℃, which may be associated with the stronger hydrogen bonds. It is worth noting that the PEG2000/2.5 BSA system also possesses the best desulfurization activity, which suggests that the activity of the desulfurization system is related to the strength of the hydrogen bond in DESs. Finally, the biomimetic desulfurization system exhibits excellent performance and good stability under mild reaction conditions(60 ℃, atmospheric pressure, oxygen as the oxidant).展开更多
With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are ...With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are excellent substitutes for ionic liquids because of their good biocompatibility,low cost,and easy preparation,except for good conductivity.In this work,we synthesized a reactive quaternary ammonium monomer(3-acrylamidopropyl)octadecyldimethyl ammonium bromide with a hydrophobic chain of 18 carbons via the quaternization of 1-bromooctadecane and N-dimethylaminopropyl acrylamide at first,then we mixed quaternary ammonium with choline chloride,acrylic acid and glycerol to obtain a hydrophobic deep eutectic solvent,and initialized polymerization in UV light of 365 nm to obtain the ionic conductive eutectogel based on polyacrylamide copolymer with long hydrophobic chain.The obtained eutectogel exibits good stretchability(1200%),Young's modulus(0.185 MPa),toughness(4.2 MJ/m^(3)),conductivity(0.315 S/m).The eutectogel also shows desireable moisture resistance with the maximum water absorption of 11.7 wt%after one week at 25℃and 60%humidity,while the water absorption of eutectogel without hydrophobic long chains is 24.0 wt%.The introduction of long-chain hydrophobic groups not only improves the mechanical strength of the gels,but also significantly improves moisture resistance of the eutectogel.This work provides a simpler and more effective method for the preparation of ionic conductive eutectogels,which can further provide a reference for the applications of ionic conductive eutectogels in the field of flexible electronic devices.展开更多
Conventional 3D metal printings are generally time-consuming as well as lacking of high performance printable inks.From an alternative way,here we proposed the method of liquid phase 3D printing for quickly making con...Conventional 3D metal printings are generally time-consuming as well as lacking of high performance printable inks.From an alternative way,here we proposed the method of liquid phase 3D printing for quickly making conductive metal objects.Through introducing metal alloys whose melting point is slightly above room temperature as printing inks,several representative structures spanning from one,two and three dimension to more complex patterns were demonstrated to be quickly fabricated.Compared with the air-cooling in a conventional 3D printing,the liquid-phase-manufacturing offers a much higher cooling rate and thus significantly improves the speed in fabricating the target metal objects.This unique strategy also efficiently prevents the liquid metal inks from air oxidation,which is hard to avoid otherwise in an ordinary 3D printing.The key physical factors(such as properties of the cooling fluid,air pressure within the syringe barrel and needle diameter,types and properties of the printing ink)and several interesting intermediate fluids interaction phenomena between liquid metal and conventional cooling fluids such as water or ethanol,which evidently affecting the printing quality,were disclosed.In addition,a basic route to make future liquid phase 3D printer incorporated with both syringe pump and needle arrays was also suggested.The liquid phase 3D printing,which owns potential values not available in a conventional method,opens an efficient way for quickly making conductive metal objects in the coming time.展开更多
Investigations were made both in laboratorial and industrial scales on formation of non-metallic inclusions with relatively lower melting temperatures to improve the fatigue property of the special steels which contai...Investigations were made both in laboratorial and industrial scales on formation of non-metallic inclusions with relatively lower melting temperatures to improve the fatigue property of the special steels which contained extra low oxygen.It was found in laboratory studies that steel/slag reaction time largely affected non-metallic inclusions in steel.With the slag/steel reaction time increasing from 30 to 90 min,inclusions of MgO-Al2O3 spinel were gradually changed into CaO-MgO-Al2O3 system inclusions which were surrounded by lower melting temperature softer CaO-Al2O3 surface layers.By using high basicity and as much as 41 mass% Al2O3 refining slag,the ratio of the lower melting temperature CaO-MgO-Al2O3 system inclusions was remarkably increased to above 80%.In the industrial experiments,it was found that the inclusions changed in the order of "Al2O3 →MgO-Al2O3 system→CaO-MgO-Al2O3 system" in the secondary refining,and the change from MgO-Al2O3 system to CaO-MgO-Al2O3 system took place from the outside to the inside.The diffusion of CaO and MgO inside the layer of CaO-MgO-Al2O3 was considered as the controlling step of the inclusion transfer.Through LF and RH refining,most inclusions could be transferred to lower melting temperature CaO-Al2O3 and CaO-MgO-Al2O3 system inclusions.展开更多
文摘A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DESs) were used as electron-donors for aerobic oxidative desulfurization(AODS) of diesel fuel. Different compositions of DESs were used and the polyethylene glycol 2000(PEG2000)/2.5 BSA system showed the highest desulfurization activity, with the removal of dibenzothiophene(DBT) at 60 ℃ reaching 95% in 60 min. The excellent desulfurization activity of the system is due to the in situ formation of peroxysulfonate via a biomimetic process. By constructing a coupled redox system, Fe-Anderson type POMs as ETMs reduce the activation energy of oxygen-activated sulfonate. The physical characteristics of four different DESs were tested. The results show that the conductivity of DESs is correlated with the composition of BSA-based DESs. However, there is no similar trend in viscosity testing at the same temperature, and the maximum viscosity value is obtained for the PEG2000/2.5 BSA system at 60 ℃, which may be associated with the stronger hydrogen bonds. It is worth noting that the PEG2000/2.5 BSA system also possesses the best desulfurization activity, which suggests that the activity of the desulfurization system is related to the strength of the hydrogen bond in DESs. Finally, the biomimetic desulfurization system exhibits excellent performance and good stability under mild reaction conditions(60 ℃, atmospheric pressure, oxygen as the oxidant).
基金This work was supported by the National Science and Technology Major Project of the Ministry of Science and Technology of China(No.2016ZX05016 and No.2016ZX05046).
文摘With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are excellent substitutes for ionic liquids because of their good biocompatibility,low cost,and easy preparation,except for good conductivity.In this work,we synthesized a reactive quaternary ammonium monomer(3-acrylamidopropyl)octadecyldimethyl ammonium bromide with a hydrophobic chain of 18 carbons via the quaternization of 1-bromooctadecane and N-dimethylaminopropyl acrylamide at first,then we mixed quaternary ammonium with choline chloride,acrylic acid and glycerol to obtain a hydrophobic deep eutectic solvent,and initialized polymerization in UV light of 365 nm to obtain the ionic conductive eutectogel based on polyacrylamide copolymer with long hydrophobic chain.The obtained eutectogel exibits good stretchability(1200%),Young's modulus(0.185 MPa),toughness(4.2 MJ/m^(3)),conductivity(0.315 S/m).The eutectogel also shows desireable moisture resistance with the maximum water absorption of 11.7 wt%after one week at 25℃and 60%humidity,while the water absorption of eutectogel without hydrophobic long chains is 24.0 wt%.The introduction of long-chain hydrophobic groups not only improves the mechanical strength of the gels,but also significantly improves moisture resistance of the eutectogel.This work provides a simpler and more effective method for the preparation of ionic conductive eutectogels,which can further provide a reference for the applications of ionic conductive eutectogels in the field of flexible electronic devices.
基金supported by the Key Research Program of the Chinese Academy of Sciences(Grant No.KGZD-EW-T04)
文摘Conventional 3D metal printings are generally time-consuming as well as lacking of high performance printable inks.From an alternative way,here we proposed the method of liquid phase 3D printing for quickly making conductive metal objects.Through introducing metal alloys whose melting point is slightly above room temperature as printing inks,several representative structures spanning from one,two and three dimension to more complex patterns were demonstrated to be quickly fabricated.Compared with the air-cooling in a conventional 3D printing,the liquid-phase-manufacturing offers a much higher cooling rate and thus significantly improves the speed in fabricating the target metal objects.This unique strategy also efficiently prevents the liquid metal inks from air oxidation,which is hard to avoid otherwise in an ordinary 3D printing.The key physical factors(such as properties of the cooling fluid,air pressure within the syringe barrel and needle diameter,types and properties of the printing ink)and several interesting intermediate fluids interaction phenomena between liquid metal and conventional cooling fluids such as water or ethanol,which evidently affecting the printing quality,were disclosed.In addition,a basic route to make future liquid phase 3D printer incorporated with both syringe pump and needle arrays was also suggested.The liquid phase 3D printing,which owns potential values not available in a conventional method,opens an efficient way for quickly making conductive metal objects in the coming time.
基金supported by the National Basic Research Program of China (Grant No. 2010CB630806)
文摘Investigations were made both in laboratorial and industrial scales on formation of non-metallic inclusions with relatively lower melting temperatures to improve the fatigue property of the special steels which contained extra low oxygen.It was found in laboratory studies that steel/slag reaction time largely affected non-metallic inclusions in steel.With the slag/steel reaction time increasing from 30 to 90 min,inclusions of MgO-Al2O3 spinel were gradually changed into CaO-MgO-Al2O3 system inclusions which were surrounded by lower melting temperature softer CaO-Al2O3 surface layers.By using high basicity and as much as 41 mass% Al2O3 refining slag,the ratio of the lower melting temperature CaO-MgO-Al2O3 system inclusions was remarkably increased to above 80%.In the industrial experiments,it was found that the inclusions changed in the order of "Al2O3 →MgO-Al2O3 system→CaO-MgO-Al2O3 system" in the secondary refining,and the change from MgO-Al2O3 system to CaO-MgO-Al2O3 system took place from the outside to the inside.The diffusion of CaO and MgO inside the layer of CaO-MgO-Al2O3 was considered as the controlling step of the inclusion transfer.Through LF and RH refining,most inclusions could be transferred to lower melting temperature CaO-Al2O3 and CaO-MgO-Al2O3 system inclusions.
