A series of Cu/Zn based catalysts with and without Ni, prepared by the co-precipitation method, has been studied for methanol decomposition. CO and H2 are the major products. The Cu/Zn catalysts show a low initial act...A series of Cu/Zn based catalysts with and without Ni, prepared by the co-precipitation method, has been studied for methanol decomposition. CO and H2 are the major products. The Cu/Zn catalysts show a low initial activity and a poor stability. The formation of the CuZn alloys was observed in the deactivated Cu/Zn catalysts which were used for methanol decomposition at 250 . When small amounts of Ni were added in the catalyst, the Cu/Zn/Ni(molar ratio 5/4/ x) catalysts showed a high activity at a low temperature. The activity and the stability of the catalyst depend on the nickel content. The activity of the Cu/Zn/Ni catalysts was maintained at a. relatively stable value of 78% conversion of methanol with 95% selectivity of H2, 93% selectivity of CO, and a more than 70% yield of hydrogen was obtained at 250 C when x >1. The stability of the Cu/Zn/Ni (molar ratio 5/4/x) catalysts showed the maximum (ca 88%) when x=1. The stabilization effect of nickel on the Cu/Zn based catalysts may lead to the increasin展开更多
Catalytic ethane dehydrogenation(EDH) to ethylene over Pt-based catalysts has received increasing interests in recent years as it is a potential alternative route to conventional steam cracking. However, the catalysts...Catalytic ethane dehydrogenation(EDH) to ethylene over Pt-based catalysts has received increasing interests in recent years as it is a potential alternative route to conventional steam cracking. However, the catalysts used in this reaction often suffer from rapid deactivation due to serious coke deposition and metal sintering. Herein, we reported the effects of Zn modification on the stability of Pt/Al2 O3 for EDH.The Zn-modified sample(PtZn2/Al2 O3) exhibits stable ethane conversion(20%) with over 95% ethylene selectivity. More importantly, it exhibits a significantly low deactivation rate of only 0.003 h-1 at 600 °C for70 h, which surpasses most of previously reported catalysts. Detailed characterizations including in situ FT-IR, ethylene adsorption microcalorimetry, and HAADF-STEM etc. reveal that Zn modifier reduces the number of Lewis acid sites on the catalyst surface. Moreover, it could modify Pt sites and preferentially cover the step sites, which decrease surface energy and retard the sintering of Pt particle, then prohibiting the further dehydrogenation of ethylene to ethylidyne. Consequently, the good stability is realized due to anti-sintering and the decrease of coke formation on the Pt Zn2/Al2 O3 catalyst.展开更多
Aqueous Zn-ion battery has emerged as one of the most prospective energy storage devices due to its low cost,high safety,and eco-friendliness.However,Zn-ion batteries are bottlenecked by significant capacity fading du...Aqueous Zn-ion battery has emerged as one of the most prospective energy storage devices due to its low cost,high safety,and eco-friendliness.However,Zn-ion batteries are bottlenecked by significant capacity fading during long-term cycling and poor performance at high current rates.Here,we report an available cooperation of multivariate manganese oxides@carbon hybrids(MnO_(2)/MnO@C and MnO_(2)/Mn_(3)O_(4)@C)via a plasma-assisted design as an attractive Zn-ion cathode.Among them,the MnO_(2)/MnO@C cathode exhibits a reversible specific capacity of 165 m Ah g^(-1)over 200 cycles at a high rate of 0.5 A g^(-1),and possesses great rate performance with high capacities of 110 and 100 m Ah g^(-1)at a high rate of 0.8 and 1 A g^(-1),respectively.The good cathode performance significantly results from the facile charge transfer and ions(Zn^(2+)and H^(+))insertion in the manganese oxides/carbon hybrids featuring phase stability behavior in the available cooperation of multivalence and carbon conductive substrates.This work will promote the Zn-manganese dioxide system for the design of low-cost and high-performance aqueous rechargeable Zn-ion batteries.展开更多
This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- ...This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- crostructures in the laser molten pool were accurately measured. The planar interface structure caused by the high velocity absolute stability was achieved at a growth velocity of 210 mm/s. An implicit expression of the critical solidification velocity for the cellular-planar transition was carried out by nonlinear stability analyses of the planar interface. The results showed a better agreement with the measured critical velocity than that predicted by M-S theory. Cell-free structures were observed throughout the whole molten pool at a scanning velocity of 652 mm/s and the calculated minimum temperature gradient in this molten pool was very close to the critical temperature gradient for high gradient absolute stability （HGAS） of the η phase. This indicates that HGAS was successfully achieved in the present experiments.展开更多
A potentiometric study on the complexes of His,Gly-His,ALa-His,Gly-Gly and Gly—Gly—Gly with Zn(Ⅱ)and Cd(Ⅱ)has been reported.Small-scale potentiometric titrations were car- ried out to determine stabil ity constant...A potentiometric study on the complexes of His,Gly-His,ALa-His,Gly-Gly and Gly—Gly—Gly with Zn(Ⅱ)and Cd(Ⅱ)has been reported.Small-scale potentiometric titrations were car- ried out to determine stabil ity constants of complexes at 25℃ with I=0.10 mol dm^(-3)(KNO_3).The com- puter programs SUPERQUAD were applied for data treatment with satisfactory results.展开更多
When a protein is encapsulated into poly( DL -lactide-co-glycolide)(PLGA) microspheres by means of the double-emulsion method,the harsh microspheres formation process including ultrasonification,exposure to an organic...When a protein is encapsulated into poly( DL -lactide-co-glycolide)(PLGA) microspheres by means of the double-emulsion method,the harsh microspheres formation process including ultrasonification,exposure to an organic solvent and a polymer may cause the denaturation of the protein. In this study,we investigated the enzymatic activity change and the effect of the excipients on the stability of recombinant human Cu,Zn-superoxide dismutase(rhCu,Zn-SOD) during the emulsification. The specific activity recovery was found to be concentration dependent and the excipients involved such as PEG 600 and Tween 20,and trehalose were shown to increase the stability of rhCu,Zn-SOD. The protein structural integrity within the microspheres was analyzed by FTIR. The structure of rhCu,Zn-SOD within PLGA microspheres containing trehalose was found to be similar to that of the native solid state,whereas the protein encapsulated during the preparation in the absence of any excipient changed due to the possible hydrophobic interaction with the polymer. The results suggest that a rational stability strategy for protein to be encapsulated into microspheres should aim at different processes.展开更多
This study investigated the viscoelastic and rheometeric properties of PVC stabilized with tannin-Ca complex as totally bio-based thermal stabilizer. Dynamic mechanical thermal analysis (DMTA) used to characterize the...This study investigated the viscoelastic and rheometeric properties of PVC stabilized with tannin-Ca complex as totally bio-based thermal stabilizer. Dynamic mechanical thermal analysis (DMTA) used to characterize the viscoelastic properties of PVC samples obtained by thermal mixing of PVC with three composition percentages (1.0, 2.0, and 3.0) part per hundred ratios (phr) of tannin-Ca complex with this polymer. The torque rheometery test used to monitor the effect of tannins derivative on the thermal stability and mixing properties of PVC formulations during samples processing. For that purpose, PVC sample with 2 phr commercial thermal stabilizer (Reapak B-NT/ 7060) was used for comparison and considered as reference samples. Before the glass transition temperature of PVC at 30°C - 60°C, the DMTA curves show that the values of storage modulus and tan delta of PVC samples stabilized with tannin derivative were very similar with those of PVC sample stabilized with commercial thermal stabilizer. The glass transition temperature (Tg) of PVC stabilized with commercial thermal stabilizer and with tannin-Ca complex occurred at about 76°C. In a sequence, after the glass transition region of PVC samples, the DMTA scans confirmed that the PVC samples with 2 phr tannin-Ca complex have relatively longer flowing stage which occurs at lower temperatures by 18°C per that of PVC sample stabilized with commercial stabilizer. Global results of the torque rheometery which have suitable plateau stages and the DMTA show that the processing thermal stability and thermal flexibility of PVC are clearly increased with the incorporation of tannin-Ca complex. All the PVC formulations with tannins-Ca complex show excellent viscoelastic properties which were found to be slightly best or much closed to those obtained for PVC stabilized with commercial thermal stabilization.展开更多
基金the financial support for this work from the National Natural Science Foundation of China(Nos.U1764254,51871166)the Tianjin Natural Science Foundation,China(No.20JCYBJC00620)。
文摘A series of Cu/Zn based catalysts with and without Ni, prepared by the co-precipitation method, has been studied for methanol decomposition. CO and H2 are the major products. The Cu/Zn catalysts show a low initial activity and a poor stability. The formation of the CuZn alloys was observed in the deactivated Cu/Zn catalysts which were used for methanol decomposition at 250 . When small amounts of Ni were added in the catalyst, the Cu/Zn/Ni(molar ratio 5/4/ x) catalysts showed a high activity at a low temperature. The activity and the stability of the catalyst depend on the nickel content. The activity of the Cu/Zn/Ni catalysts was maintained at a. relatively stable value of 78% conversion of methanol with 95% selectivity of H2, 93% selectivity of CO, and a more than 70% yield of hydrogen was obtained at 250 C when x >1. The stability of the Cu/Zn/Ni (molar ratio 5/4/x) catalysts showed the maximum (ca 88%) when x=1. The stabilization effect of nickel on the Cu/Zn based catalysts may lead to the increasin
基金supported by the National Natural Science Foundation of China (NNSFC 21573232, 21576251, 21676269, 21878283)the Strategic Priority Research Program of Chinese Academy of Sciences Grant No. XDB17000000+2 种基金National Key Projects for Fundamental Research and Development of China (2016YFA0202801)The Youth Innovation Promotion Association CAS (2017223)Department of Science and Technology of Liaoning province under contract of 2015020086-101。
文摘Catalytic ethane dehydrogenation(EDH) to ethylene over Pt-based catalysts has received increasing interests in recent years as it is a potential alternative route to conventional steam cracking. However, the catalysts used in this reaction often suffer from rapid deactivation due to serious coke deposition and metal sintering. Herein, we reported the effects of Zn modification on the stability of Pt/Al2 O3 for EDH.The Zn-modified sample(PtZn2/Al2 O3) exhibits stable ethane conversion(20%) with over 95% ethylene selectivity. More importantly, it exhibits a significantly low deactivation rate of only 0.003 h-1 at 600 °C for70 h, which surpasses most of previously reported catalysts. Detailed characterizations including in situ FT-IR, ethylene adsorption microcalorimetry, and HAADF-STEM etc. reveal that Zn modifier reduces the number of Lewis acid sites on the catalyst surface. Moreover, it could modify Pt sites and preferentially cover the step sites, which decrease surface energy and retard the sintering of Pt particle, then prohibiting the further dehydrogenation of ethylene to ethylidyne. Consequently, the good stability is realized due to anti-sintering and the decrease of coke formation on the Pt Zn2/Al2 O3 catalyst.
基金supported by the National Natural Science Foundation of China(Nos.51822104,52071144,51831009,and 11575126)the Guangzhou Science and Technology Plan Projects(No.201904020018)the Fundamental Research Funds for the Central Universities,SCUT(No.2019CG24)
文摘Aqueous Zn-ion battery has emerged as one of the most prospective energy storage devices due to its low cost,high safety,and eco-friendliness.However,Zn-ion batteries are bottlenecked by significant capacity fading during long-term cycling and poor performance at high current rates.Here,we report an available cooperation of multivariate manganese oxides@carbon hybrids(MnO_(2)/MnO@C and MnO_(2)/Mn_(3)O_(4)@C)via a plasma-assisted design as an attractive Zn-ion cathode.Among them,the MnO_(2)/MnO@C cathode exhibits a reversible specific capacity of 165 m Ah g^(-1)over 200 cycles at a high rate of 0.5 A g^(-1),and possesses great rate performance with high capacities of 110 and 100 m Ah g^(-1)at a high rate of 0.8 and 1 A g^(-1),respectively.The good cathode performance significantly results from the facile charge transfer and ions(Zn^(2+)and H^(+))insertion in the manganese oxides/carbon hybrids featuring phase stability behavior in the available cooperation of multivalence and carbon conductive substrates.This work will promote the Zn-manganese dioxide system for the design of low-cost and high-performance aqueous rechargeable Zn-ion batteries.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 50201012 and 50471065）.
文摘This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- crostructures in the laser molten pool were accurately measured. The planar interface structure caused by the high velocity absolute stability was achieved at a growth velocity of 210 mm/s. An implicit expression of the critical solidification velocity for the cellular-planar transition was carried out by nonlinear stability analyses of the planar interface. The results showed a better agreement with the measured critical velocity than that predicted by M-S theory. Cell-free structures were observed throughout the whole molten pool at a scanning velocity of 652 mm/s and the calculated minimum temperature gradient in this molten pool was very close to the critical temperature gradient for high gradient absolute stability （HGAS） of the η phase. This indicates that HGAS was successfully achieved in the present experiments.
文摘A potentiometric study on the complexes of His,Gly-His,ALa-His,Gly-Gly and Gly—Gly—Gly with Zn(Ⅱ)and Cd(Ⅱ)has been reported.Small-scale potentiometric titrations were car- ried out to determine stabil ity constants of complexes at 25℃ with I=0.10 mol dm^(-3)(KNO_3).The com- puter programs SUPERQUAD were applied for data treatment with satisfactory results.
文摘When a protein is encapsulated into poly( DL -lactide-co-glycolide)(PLGA) microspheres by means of the double-emulsion method,the harsh microspheres formation process including ultrasonification,exposure to an organic solvent and a polymer may cause the denaturation of the protein. In this study,we investigated the enzymatic activity change and the effect of the excipients on the stability of recombinant human Cu,Zn-superoxide dismutase(rhCu,Zn-SOD) during the emulsification. The specific activity recovery was found to be concentration dependent and the excipients involved such as PEG 600 and Tween 20,and trehalose were shown to increase the stability of rhCu,Zn-SOD. The protein structural integrity within the microspheres was analyzed by FTIR. The structure of rhCu,Zn-SOD within PLGA microspheres containing trehalose was found to be similar to that of the native solid state,whereas the protein encapsulated during the preparation in the absence of any excipient changed due to the possible hydrophobic interaction with the polymer. The results suggest that a rational stability strategy for protein to be encapsulated into microspheres should aim at different processes.
文摘This study investigated the viscoelastic and rheometeric properties of PVC stabilized with tannin-Ca complex as totally bio-based thermal stabilizer. Dynamic mechanical thermal analysis (DMTA) used to characterize the viscoelastic properties of PVC samples obtained by thermal mixing of PVC with three composition percentages (1.0, 2.0, and 3.0) part per hundred ratios (phr) of tannin-Ca complex with this polymer. The torque rheometery test used to monitor the effect of tannins derivative on the thermal stability and mixing properties of PVC formulations during samples processing. For that purpose, PVC sample with 2 phr commercial thermal stabilizer (Reapak B-NT/ 7060) was used for comparison and considered as reference samples. Before the glass transition temperature of PVC at 30°C - 60°C, the DMTA curves show that the values of storage modulus and tan delta of PVC samples stabilized with tannin derivative were very similar with those of PVC sample stabilized with commercial thermal stabilizer. The glass transition temperature (Tg) of PVC stabilized with commercial thermal stabilizer and with tannin-Ca complex occurred at about 76°C. In a sequence, after the glass transition region of PVC samples, the DMTA scans confirmed that the PVC samples with 2 phr tannin-Ca complex have relatively longer flowing stage which occurs at lower temperatures by 18°C per that of PVC sample stabilized with commercial stabilizer. Global results of the torque rheometery which have suitable plateau stages and the DMTA show that the processing thermal stability and thermal flexibility of PVC are clearly increased with the incorporation of tannin-Ca complex. All the PVC formulations with tannins-Ca complex show excellent viscoelastic properties which were found to be slightly best or much closed to those obtained for PVC stabilized with commercial thermal stabilization.
