Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention...Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention.CLHP demands redox catalysts with high oxygen capacity,regulatable reactivity,and structural integrity even under harsh operational conditions.Currently,sintering,agglomeration,and inactivation of redox catalysts during cyclic lattice oxygen release and restoration are challenging,hindering the wide industrialization of the chemical looping(CL)process.Moreover,the precise control of activity and reaction rate of the redox catalysts to flexibly accommodate the demands of various reaction substrates remains unclear.This paper introduces the design of a nano-scaled redox catalyst featuring a unique core-shell structure.By precisely controlling the shell thickness,a series of hierarchical Fe_(2)O_(3)@SiO_(2)redox catalysts were successfully synthesized.Building on this achievement,an in-depth investigation was conducted into the impact of the thickness and spatial structure of the inert support on the stability and mass transfer rate of the redox catalyst,aiming to achieve a perfect balance between these two factors during the CLHP process.A thin shell(70 nm)exhibits excellent cyclic stability,maintaining consistent performance in 30 consecutive redox cycles,while a thicker shell(200 nm)undergoes rapid deactivation due to the formation of a substantial amount of iron silicate.In-situ transmission electron microscopy(TEM)reveals that the SiO_(2)shell effectively restricts the agglomeration of Fe_(2)O_(3).The unique core-shell structure and controllable shell thickness offer novel insights into the flexible design of efficient and durable hierarchical redox catalysts with spatial structure.展开更多
Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the...Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.展开更多
By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2...By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2) into CO.Generally,NiFe_(2_)O_(4) oxygen carriers have demonstrated remarkable efficiency in chemical looping CO_(2) conversion.Nevertheless,the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear.Consequently,the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers.Thus,in this study,we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe_(2_)O_(4) oxygen carriers during H_(2) reduction and CO_(2)/lab air oxidation cycles.We discovered that during the H_(2) reduction step,lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species,while Ni leaches from the material and migrates to the surface.During the CO_(2) splitting step,Ni migrates toward the core of the bimetallic oxygen carrier,forming Fe–Ni alloys.During the air oxidation step,Fe–Ni migrates outward,creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen.The metal atom migration paths depend on the oxygen transfer rates.These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers.This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.展开更多
Two total synthetic routes for the preparation of myricetin were designed and explored.It was validated that route B presented an efficient approach to synthesizing myricetin,starting from commercially available and i...Two total synthetic routes for the preparation of myricetin were designed and explored.It was validated that route B presented an efficient approach to synthesizing myricetin,starting from commercially available and inexpensive phloroglucinol.Myricetin was synthesized with an overall yield of 60%across three steps without the need of column chromatography separation.The successful preparation of myricetin on a 25-g scale underscored the potential of this approach.展开更多
身份认证是车联网安全防护的关键,然而,现有的很多认证方案效率低且不兼容国产密码算法。为进一步提升认证效率,丰富国产密码算法在车联网领域的应用,提出了一种基于国密SM2的匿名切换认证协议。该协议结合伪身份认证机制,强化了车辆隐...身份认证是车联网安全防护的关键,然而,现有的很多认证方案效率低且不兼容国产密码算法。为进一步提升认证效率,丰富国产密码算法在车联网领域的应用,提出了一种基于国密SM2的匿名切换认证协议。该协议结合伪身份认证机制,强化了车辆隐私信息保护,有效隐藏车辆的真实身份和行驶数据。该协议不仅融合了国产密码算法,在认证效率上也表现良好,特别在密集车辆环境下,该协议设计了一种巧妙的批量认证算法。为了验证协议性能,基于Fedora系统的QT平台,对协议的批量认证算法进行测试,测试认证车辆数为10,20,40,…,320的批量认证效率。随着认证车辆数的增加,批量认证算法展示出的效率优势越发明显,当认证车辆数达到320辆时,路侧单元(road side unit,RSU)认证效率提升了约65%,极大地减轻了RSU并发认证压力。理论和AVISPA工具实验分析证明,所设计的协议在车联网安全的自主可控性方面更有优势,不仅能够有效抵抗重放攻击和中间人攻击等攻击行为,并且在认证效率上也有显著提升,为车联网系统的身份认证提供了更为安全有效的解决方案。展开更多
We explore the incorporation of an oscillating water column(OWC)device into a monopile foundation designed for offshore wind power generation.The hydrodynamic characteristics of the structure are investigated,includin...We explore the incorporation of an oscillating water column(OWC)device into a monopile foundation designed for offshore wind power generation.The hydrodynamic characteristics of the structure are investigated,including the free water surface and air pressure response inside the OwC chamber,the wave energy capture performance,and the wave load response under various power take-off(PTO)damping and wave conditions.An orifice is employed to represent the quadratic PTO damping effect.Results indicate that increasing the PTO opening ratio increases the peak frequency of the water surface oscillation coefficient inside the OWC chamber,as well as the OWC pneumatic power.The load-reduction effect of the OWC device in the positive direction is likely related to the water surface oscillation inside the chamber and the wave energy extraction efficiency.At high wave frequencies,the water surface oscillation coefficient is relatively small,while the pneumatic power remains at a large value,and the OwC device can effectively reduce wave loads in the direction of incoming waves.The optimal opening ratio of 1.51%may balance wave energy utilization efficiency with structural protection for the device.展开更多
AIM： To establish a rapid and convenient animal model with hepatitis B virus （HBV） replication.METHODS： A naked DNA solution of HBV-replicationcompetent plasmid was transferred to BALB/C mice via the tail vein, us...AIM： To establish a rapid and convenient animal model with hepatitis B virus （HBV） replication.METHODS： A naked DNA solution of HBV-replicationcompetent plasmid was transferred to BALB/C mice via the tail vein, using a hydrodynamic in vivo transfection procedure. After injection, these mice were sacrificed on d 1, 3, 4, 5, 7 and 10. HBV DNA replication intermediates in the liver were analyzed by Southern blot hybridization. The expression of hepatitis B core antigen （HBcAg） and hepatitis B surface antigen （HBsAg） in the liver was checked by immunohistochemistry. Serum HBsAg and hepatitis B e antigen （HBeAg） was detected by enzyme- linked immunosorbent assay （ELISA）. Inhibition of HBV replication was compared in HBV replication model mice treated intraperitoneally with polyinosinic-polytidylin acid （polyIC） or phosphate-buffered saline （PBS）.RESULTS： After hydrodynamic in vivo transfection, HBV DNA replication intermediates in the mouse liver were detectable on d 1 and abundant on d 3 and 4, the levels were slightly decreased and remained relatively stable between d 5 and 7, and were almost undetectable on d 10. The expression patterns of HBcAg and HBsAg were similar to that of HBV replication intermediate DNA, except that they reached a peak on d 1 after injection. No obvious differences in HBV DNA replication intermediates were observed in the left, right and middle lobes of the liver. After treatment with polyIC, the level of HBV intermediate DNA in the liver was lower than that in the control mice injected with PBS.CONCLUSION： A rapid and convenient mouse model with a high level of HBV replication was developed and used to investigate the inhibitory effect of polyIC on HBV replication, which provides a useful tool for future functional studies of the HBV genome.展开更多
Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a m...Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process： in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction （XRD） analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis （TGA） reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy （SEM） test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.展开更多
基金financial support from the National Natural Science Foundation of China(52076209,22179027,22469006)the Foundation and Applied Foundation Research of Guangdong Province(2022B1515020045)the Heilongjiang Key Research and Development Project of China(JD22A026)。
文摘Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention.CLHP demands redox catalysts with high oxygen capacity,regulatable reactivity,and structural integrity even under harsh operational conditions.Currently,sintering,agglomeration,and inactivation of redox catalysts during cyclic lattice oxygen release and restoration are challenging,hindering the wide industrialization of the chemical looping(CL)process.Moreover,the precise control of activity and reaction rate of the redox catalysts to flexibly accommodate the demands of various reaction substrates remains unclear.This paper introduces the design of a nano-scaled redox catalyst featuring a unique core-shell structure.By precisely controlling the shell thickness,a series of hierarchical Fe_(2)O_(3)@SiO_(2)redox catalysts were successfully synthesized.Building on this achievement,an in-depth investigation was conducted into the impact of the thickness and spatial structure of the inert support on the stability and mass transfer rate of the redox catalyst,aiming to achieve a perfect balance between these two factors during the CLHP process.A thin shell(70 nm)exhibits excellent cyclic stability,maintaining consistent performance in 30 consecutive redox cycles,while a thicker shell(200 nm)undergoes rapid deactivation due to the formation of a substantial amount of iron silicate.In-situ transmission electron microscopy(TEM)reveals that the SiO_(2)shell effectively restricts the agglomeration of Fe_(2)O_(3).The unique core-shell structure and controllable shell thickness offer novel insights into the flexible design of efficient and durable hierarchical redox catalysts with spatial structure.
基金support of National Natural Science Foundation of China(22179027)gratefully acknowledged.This work was also supported by the Natural Science Foundation of Guangxi Province(2021GXNSFAA075063,2018GXNSFDA281005)+1 种基金the National Key Research and Development Program of China(2017YFE0105500)Science&Technology Research Project of Guangdong Province(2017A020216009).
文摘Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.
基金National Natural Science Foundation of China,Grant/Award Numbers:52076209,52006224,52106285,22179027Foundation and Applied Foundation Research of Guangdong Province,Grant/Award Number:2022B1515020045+1 种基金Natural Science Foundation of Guangxi Province,Grant/Award Number:2021GXNSFAA075036Young Talent Support Project of Guangzhou Association for Science and Technology,Grant/Award Number:QT‐2023‐042。
文摘By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2) into CO.Generally,NiFe_(2_)O_(4) oxygen carriers have demonstrated remarkable efficiency in chemical looping CO_(2) conversion.Nevertheless,the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear.Consequently,the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers.Thus,in this study,we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe_(2_)O_(4) oxygen carriers during H_(2) reduction and CO_(2)/lab air oxidation cycles.We discovered that during the H_(2) reduction step,lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species,while Ni leaches from the material and migrates to the surface.During the CO_(2) splitting step,Ni migrates toward the core of the bimetallic oxygen carrier,forming Fe–Ni alloys.During the air oxidation step,Fe–Ni migrates outward,creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen.The metal atom migration paths depend on the oxygen transfer rates.These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers.This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.
基金The Clinical Medicine Special Project of Nantong University for financial support(Grant No.2022JQ011)。
文摘Two total synthetic routes for the preparation of myricetin were designed and explored.It was validated that route B presented an efficient approach to synthesizing myricetin,starting from commercially available and inexpensive phloroglucinol.Myricetin was synthesized with an overall yield of 60%across three steps without the need of column chromatography separation.The successful preparation of myricetin on a 25-g scale underscored the potential of this approach.
文摘身份认证是车联网安全防护的关键,然而,现有的很多认证方案效率低且不兼容国产密码算法。为进一步提升认证效率,丰富国产密码算法在车联网领域的应用,提出了一种基于国密SM2的匿名切换认证协议。该协议结合伪身份认证机制,强化了车辆隐私信息保护,有效隐藏车辆的真实身份和行驶数据。该协议不仅融合了国产密码算法,在认证效率上也表现良好,特别在密集车辆环境下,该协议设计了一种巧妙的批量认证算法。为了验证协议性能,基于Fedora系统的QT平台,对协议的批量认证算法进行测试,测试认证车辆数为10,20,40,…,320的批量认证效率。随着认证车辆数的增加,批量认证算法展示出的效率优势越发明显,当认证车辆数达到320辆时,路侧单元(road side unit,RSU)认证效率提升了约65%,极大地减轻了RSU并发认证压力。理论和AVISPA工具实验分析证明,所设计的协议在车联网安全的自主可控性方面更有优势,不仅能够有效抵抗重放攻击和中间人攻击等攻击行为,并且在认证效率上也有显著提升,为车联网系统的身份认证提供了更为安全有效的解决方案。
基金supported by the“Pioneer”R&D Program of Zhejiang(No.2022C03009)the National Natural Science Foundation of China(Nos.52022092,51979247,and 52211530092),the Talent Program of Zhejiang Province(No.2021R52050)the Natural Science Foundation of Zhejiang Province(No.LZ23E090001),China.
文摘We explore the incorporation of an oscillating water column(OWC)device into a monopile foundation designed for offshore wind power generation.The hydrodynamic characteristics of the structure are investigated,including the free water surface and air pressure response inside the OwC chamber,the wave energy capture performance,and the wave load response under various power take-off(PTO)damping and wave conditions.An orifice is employed to represent the quadratic PTO damping effect.Results indicate that increasing the PTO opening ratio increases the peak frequency of the water surface oscillation coefficient inside the OWC chamber,as well as the OWC pneumatic power.The load-reduction effect of the OWC device in the positive direction is likely related to the water surface oscillation inside the chamber and the wave energy extraction efficiency.At high wave frequencies,the water surface oscillation coefficient is relatively small,while the pneumatic power remains at a large value,and the OwC device can effectively reduce wave loads in the direction of incoming waves.The optimal opening ratio of 1.51%may balance wave energy utilization efficiency with structural protection for the device.
基金Supported by the National Science Fund for Distinguished Young Scholars from the National Natural Science Foundation of China,No.30325036a grant from the National Natural Science Foundation of China,No.30571640
文摘AIM： To establish a rapid and convenient animal model with hepatitis B virus （HBV） replication.METHODS： A naked DNA solution of HBV-replicationcompetent plasmid was transferred to BALB/C mice via the tail vein, using a hydrodynamic in vivo transfection procedure. After injection, these mice were sacrificed on d 1, 3, 4, 5, 7 and 10. HBV DNA replication intermediates in the liver were analyzed by Southern blot hybridization. The expression of hepatitis B core antigen （HBcAg） and hepatitis B surface antigen （HBsAg） in the liver was checked by immunohistochemistry. Serum HBsAg and hepatitis B e antigen （HBeAg） was detected by enzyme- linked immunosorbent assay （ELISA）. Inhibition of HBV replication was compared in HBV replication model mice treated intraperitoneally with polyinosinic-polytidylin acid （polyIC） or phosphate-buffered saline （PBS）.RESULTS： After hydrodynamic in vivo transfection, HBV DNA replication intermediates in the mouse liver were detectable on d 1 and abundant on d 3 and 4, the levels were slightly decreased and remained relatively stable between d 5 and 7, and were almost undetectable on d 10. The expression patterns of HBcAg and HBsAg were similar to that of HBV replication intermediate DNA, except that they reached a peak on d 1 after injection. No obvious differences in HBV DNA replication intermediates were observed in the left, right and middle lobes of the liver. After treatment with polyIC, the level of HBV intermediate DNA in the liver was lower than that in the control mice injected with PBS.CONCLUSION： A rapid and convenient mouse model with a high level of HBV replication was developed and used to investigate the inhibitory effect of polyIC on HBV replication, which provides a useful tool for future functional studies of the HBV genome.
基金Supported by the National Natural Science Foundation of China (No.50574046 and 50164002, )Natural Science Foun-dation of Yunnan Province (No. 2004E0012Q).
文摘Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process： in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction （XRD） analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis （TGA） reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy （SEM） test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.
