Aqueous rechargeable Zn/MnO2 zinc-ion batteries(ZIBs)are reviving recently due to their low cost,non-toxicity,and natural abundance.However,their energy storage mechanism remains controversial due to their complicated...Aqueous rechargeable Zn/MnO2 zinc-ion batteries(ZIBs)are reviving recently due to their low cost,non-toxicity,and natural abundance.However,their energy storage mechanism remains controversial due to their complicated electrochemical reactions.Meanwhile,to achieve satisfactory cyclic stability and rate performance of the Zn/MnO2 ZIBs,Mn2+ is introduced in the electrolyte(e.g.,ZnSO4 solution),which leads to more complicated reactions inside the ZIBs systems.Herein,based on comprehensive analysis methods including electrochemical analysis and Pourbaix diagram,we provide novel insights into the energy storage mechanism of Zn/MnO2 batteries in the presence of Mn2+.A complex series of electrochemical reactions with the coparticipation of Zn2+,H+,Mn2+,SO42-,and OH-were revealed.During the first discharge process,co-insertion of Zn2+ and H+ promotes the transformation of MnO2 into ZnxMnO4,MnOOH,and Mn2O3,accompanying with increased electrolyte pH and the formation of ZnSO4·3 Zn(OH)2-5 H2O.During the subsequent charge process,ZnxMnO4,MnOOH,and Mn2O3 revert to a-MnO2 with the extraction of Zn2+ and H+,while ZnSO4·3Zn(OH)2·5H2O reacts with Mn2+ to form ZnMn3O7·3 H2O.In the following charge/discharge processes,besides aforementioned electrochemical reactions,Zn2+ reversibly insert into/extract from α-MnO2,ZnxMnO4,and ZnMn3O7·3H2O hosts;ZnSO4·3Zn(OH)2·5 H2O,Zn2Mn3O8,and ZnMn2O4 convert mutually with the participation of Mn2+.This work is believed to provide theoretical guidance for further research on high-performance ZIBs.展开更多
Herein,a bottom-down design is presented to successfully fabricate ZIF-derived Co3O4,grown in situ on a one-dimensional(1D)α-MnO2 material,denoted as α-MnO2@Co3O4.The synergistic effect derived from the coupled inte...Herein,a bottom-down design is presented to successfully fabricate ZIF-derived Co3O4,grown in situ on a one-dimensional(1D)α-MnO2 material,denoted as α-MnO2@Co3O4.The synergistic effect derived from the coupled interface constructed betweenα-MnO2 and Co3O4 is responsible for the enhanced catalytic activity.The resultantα-MnO2@Co3O4 catalyst exhibits excellent catalytic activity at a T90%(temperature required to achieve a toluene conversion of 90%)of approximately 229℃,which is 47 and 28℃ lower than those of the pureα-MnO2 nanowire and Co3O4-b obtained via pyrolysis of ZIF-67,respectively.This activity is attributed to the increase in the number of surface-adsorbed oxygen species,which accelerate the oxygen mobility and enhance the redox pairs of Mn^4+/Mn^3+ and Co^2+/Co^3+.Moreover,the result of in situ diffuse reflectance infrared Fourier transform spectroscopy suggests that the gaseous oxygen could be more easily activated to adsorbed oxygen species on the surface of α-MnO2@Co3O4 than on that of α-MnO2.The catalytic reaction route of toluene oxidation over theα-MnO2@Co3O4 catalyst is as follows:toluene→benzoate species→alkanes containing oxygen functional group→CO2 and H2O.In addition,the α-MnO2@Co3O4 catalyst shows excellent stability and good water resistance for toluene oxidation.Furthermore,the preparation method can be extended to other 1D MnO2 materials.A new strategy for the development of high-performance catalysts of practical significance is provided.展开更多
How to trigger strong anti-tumor immune responses has become a focus for tumor therapy.Here,we report the human-induced pluripotent stem cells(iPSs)to deliver MnO2@Ce6 nanoprobes into tumors for simultaneous photodyna...How to trigger strong anti-tumor immune responses has become a focus for tumor therapy.Here,we report the human-induced pluripotent stem cells(iPSs)to deliver MnO2@Ce6 nanoprobes into tumors for simultaneous photodynamic therapy(PDT)and enhanced immunotherapy.Ce6 photosensitizer was attached on manganese dioxide(MnO2)nanoparticles,and resultant MnO2@Ce6 nanoprobes were delivered into mitomycin-treated iPSs to form iPS-MnO2@Ce6 nanoprobes.The iPS-MnO2@Ce6 actively targeted in vivo tumors,the acidic microenvironment triggered interaction between MnO2 and H2O2,released large quantities of oxygen,alleviated hypoxia in tumor.Upon PDT,singlet oxygen formed,broken iPSs released tumor-shared antigens,which evoked an intensive innate and adaptive immune response against the tumor,improving dendritic cells matured,effector T cells,and natural killer cells were activated.Meanwhile,regulatory T cells were reduced,and then the immune response induced by iPS-MnO2@Ce6 was markedly stronger than the immune reaction induced by MnO2@Ce6(P<0.05).The iPS-MnO2@Ce6 markedly inhibited tumor growth and metastasis and reduced mortality in mice models with tumor.Human iPS s loaded with MnO2-based nanoprobes are a promising strategy for simultaneous PDT and enhanced immunotherapy against tumor and own clinical translational prospect.展开更多
MnO2/MnO cathode material with superior Zn^2+storage performance is prepared through a simple physical mixing method.The MnO2/MnO nanocomposite with a mixed mass ratio of 12:1 exhibits the highest specific capacity(36...MnO2/MnO cathode material with superior Zn^2+storage performance is prepared through a simple physical mixing method.The MnO2/MnO nanocomposite with a mixed mass ratio of 12:1 exhibits the highest specific capacity(364.2 mA·h/g at 0.2C),good cycle performance(170.4 mA·h/g after 100 cycles)and excellent rate performance(205.7 mA·h/g at 2C).Analysis of cyclic voltammetry(CV)data at various scan rates shows that both diffusioncontrolled insertion behavior and surface capacitive behavior contribute to the Zn2+storage performance of MnO2/MnO cathodes.And the capacitive behavior contributes more at high discharge rates,due to the short paths of ion diffusion and the rapid transfer of electrons.展开更多
基金the financial support from the International Science & Technology Cooperation Program of China (No. 2016YFE0102200)Shenzhen Technical Plan Project (No. JCYJ20160301154114273)+1 种基金National Key Basic Research(973) Program of China (No. 2014CB932400)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01N111)
摘要Aqueous rechargeable Zn/MnO2 zinc-ion batteries(ZIBs)are reviving recently due to their low cost,non-toxicity,and natural abundance.However,their energy storage mechanism remains controversial due to their complicated electrochemical reactions.Meanwhile,to achieve satisfactory cyclic stability and rate performance of the Zn/MnO2 ZIBs,Mn2+ is introduced in the electrolyte(e.g.,ZnSO4 solution),which leads to more complicated reactions inside the ZIBs systems.Herein,based on comprehensive analysis methods including electrochemical analysis and Pourbaix diagram,we provide novel insights into the energy storage mechanism of Zn/MnO2 batteries in the presence of Mn2+.A complex series of electrochemical reactions with the coparticipation of Zn2+,H+,Mn2+,SO42-,and OH-were revealed.During the first discharge process,co-insertion of Zn2+ and H+ promotes the transformation of MnO2 into ZnxMnO4,MnOOH,and Mn2O3,accompanying with increased electrolyte pH and the formation of ZnSO4·3 Zn(OH)2-5 H2O.During the subsequent charge process,ZnxMnO4,MnOOH,and Mn2O3 revert to a-MnO2 with the extraction of Zn2+ and H+,while ZnSO4·3Zn(OH)2·5H2O reacts with Mn2+ to form ZnMn3O7·3 H2O.In the following charge/discharge processes,besides aforementioned electrochemical reactions,Zn2+ reversibly insert into/extract from α-MnO2,ZnxMnO4,and ZnMn3O7·3H2O hosts;ZnSO4·3Zn(OH)2·5 H2O,Zn2Mn3O8,and ZnMn2O4 convert mutually with the participation of Mn2+.This work is believed to provide theoretical guidance for further research on high-performance ZIBs.
摘要Herein,a bottom-down design is presented to successfully fabricate ZIF-derived Co3O4,grown in situ on a one-dimensional(1D)α-MnO2 material,denoted as α-MnO2@Co3O4.The synergistic effect derived from the coupled interface constructed betweenα-MnO2 and Co3O4 is responsible for the enhanced catalytic activity.The resultantα-MnO2@Co3O4 catalyst exhibits excellent catalytic activity at a T90%(temperature required to achieve a toluene conversion of 90%)of approximately 229℃,which is 47 and 28℃ lower than those of the pureα-MnO2 nanowire and Co3O4-b obtained via pyrolysis of ZIF-67,respectively.This activity is attributed to the increase in the number of surface-adsorbed oxygen species,which accelerate the oxygen mobility and enhance the redox pairs of Mn^4+/Mn^3+ and Co^2+/Co^3+.Moreover,the result of in situ diffuse reflectance infrared Fourier transform spectroscopy suggests that the gaseous oxygen could be more easily activated to adsorbed oxygen species on the surface of α-MnO2@Co3O4 than on that of α-MnO2.The catalytic reaction route of toluene oxidation over theα-MnO2@Co3O4 catalyst is as follows:toluene→benzoate species→alkanes containing oxygen functional group→CO2 and H2O.In addition,the α-MnO2@Co3O4 catalyst shows excellent stability and good water resistance for toluene oxidation.Furthermore,the preparation method can be extended to other 1D MnO2 materials.A new strategy for the development of high-performance catalysts of practical significance is provided.
基金financially supported by National Nature Scientific foundation(81803094,81802979 and 81921002)the National Foundational Basic Research Project of China(2017YFA0205301 and 2015CB931802)+3 种基金Shanghai Municipal Commission of Economy and Information Technology Fund(No.XC-ZXSJ-02-2016-05)the medical engineering cross project of Shanghai Jiao Tong university(YG2017ZD05,YG2016ZD10 and YG2017Z D05)the Project of Thousand Youth Talents from Chinathe National Key Research and Development Program of China(2017YFC1200904 and 2017YFE0124400)。
摘要How to trigger strong anti-tumor immune responses has become a focus for tumor therapy.Here,we report the human-induced pluripotent stem cells(iPSs)to deliver MnO2@Ce6 nanoprobes into tumors for simultaneous photodynamic therapy(PDT)and enhanced immunotherapy.Ce6 photosensitizer was attached on manganese dioxide(MnO2)nanoparticles,and resultant MnO2@Ce6 nanoprobes were delivered into mitomycin-treated iPSs to form iPS-MnO2@Ce6 nanoprobes.The iPS-MnO2@Ce6 actively targeted in vivo tumors,the acidic microenvironment triggered interaction between MnO2 and H2O2,released large quantities of oxygen,alleviated hypoxia in tumor.Upon PDT,singlet oxygen formed,broken iPSs released tumor-shared antigens,which evoked an intensive innate and adaptive immune response against the tumor,improving dendritic cells matured,effector T cells,and natural killer cells were activated.Meanwhile,regulatory T cells were reduced,and then the immune response induced by iPS-MnO2@Ce6 was markedly stronger than the immune reaction induced by MnO2@Ce6(P<0.05).The iPS-MnO2@Ce6 markedly inhibited tumor growth and metastasis and reduced mortality in mice models with tumor.Human iPS s loaded with MnO2-based nanoprobes are a promising strategy for simultaneous PDT and enhanced immunotherapy against tumor and own clinical translational prospect.
基金Project(21905304)supported by the National Natural Science Foundation of ChinaProject(ZR2019BEM031)supported by the Natural Science Foundation of Shandong Province,ChinaProjects(18CX02158A,19CX05001A)supported by the Fundamental Research Funds for the Central Universities,China。
摘要MnO2/MnO cathode material with superior Zn^2+storage performance is prepared through a simple physical mixing method.The MnO2/MnO nanocomposite with a mixed mass ratio of 12:1 exhibits the highest specific capacity(364.2 mA·h/g at 0.2C),good cycle performance(170.4 mA·h/g after 100 cycles)and excellent rate performance(205.7 mA·h/g at 2C).Analysis of cyclic voltammetry(CV)data at various scan rates shows that both diffusioncontrolled insertion behavior and surface capacitive behavior contribute to the Zn2+storage performance of MnO2/MnO cathodes.And the capacitive behavior contributes more at high discharge rates,due to the short paths of ion diffusion and the rapid transfer of electrons.