Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent hete...Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent heteropoly compounds to react with protonated 8-quinolinol,the title supermolecular compounds(C9H8NO)mAn[(CpTi)XW11O39]·xH2O(A=Me4N,H;X=P,Si,Co) were synthesized.The title compounds were characterized by means of elementary analysis,IR,UV,1H NMR,XRD and TG-DSC.The results indicate that the title compounds are new heteropoly compounds,and there is a charge transfer interaction between the organic cation and heteropoly anion.The results obtained from thermal analysis show that QCpTiPW,QCpTiSiW and QCpTiCoW begin to decompose at 212.4,194.2 and 171.2 ℃,respectively.The results obtained from antibacterial test reveal that QCpTiSiW has the best antibacterial activity,and the MIC values of QCpTiSiW against Escherichia coli and Staphylococcus aurous are 64.0 and 0.500 μg·mL-1,respectively.展开更多
By virtue of the crucial effect of the crystal structure and transition metal(TM)redox evolution on the performance of LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM)cathode,systematical investigation is carried out to better understa...By virtue of the crucial effect of the crystal structure and transition metal(TM)redox evolution on the performance of LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM)cathode,systematical investigation is carried out to better understand the charge mechanism upon deep charging.Based on the results of X-ray diffraction and highresolution transmission electron microscope,phase transformations existing on particle surface are promoted by high potential because of the deeper lithium vacancies,accompanied by more substantial structure instability.Soft X-ray absorption spectroscopy indicates that Ni acts as the major contributor to charge compensation while Co displays a remarkable redox activity over the deep charge range.The elevated integrated intensity of pre-edge in O K-edge spectra reveals the extensive amount of holes formed in O 2 p orbitals and the enhanced hybridization of TM 3 d-O 2 p orbitals.Considering the close relationship between thermal behavior and structural evolution,the tendency of phase transitions and O_(2) release upon heating is accelerated by voltage rise,demonstrating the aggravated instability due to deeper Li utilization.Remaining Li contents in NCM are employed to estimate the amount of oxygen released in structural transformation and its detrimental effect on stability declares Li contentdependent characteristics.Furthermore,the extended Li vacancies,higher proportion of Ni4+and stronger orbital hybridization are considered as three factors impeding the thermal stability of the highlydelithiated NCM.展开更多
基金supported by the chemical materials institute China academy of engineering physics,the doctoral innovation research assistance program of science and technology review
文摘Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent heteropoly compounds to react with protonated 8-quinolinol,the title supermolecular compounds(C9H8NO)mAn[(CpTi)XW11O39]·xH2O(A=Me4N,H;X=P,Si,Co) were synthesized.The title compounds were characterized by means of elementary analysis,IR,UV,1H NMR,XRD and TG-DSC.The results indicate that the title compounds are new heteropoly compounds,and there is a charge transfer interaction between the organic cation and heteropoly anion.The results obtained from thermal analysis show that QCpTiPW,QCpTiSiW and QCpTiCoW begin to decompose at 212.4,194.2 and 171.2 ℃,respectively.The results obtained from antibacterial test reveal that QCpTiSiW has the best antibacterial activity,and the MIC values of QCpTiSiW against Escherichia coli and Staphylococcus aurous are 64.0 and 0.500 μg·mL-1,respectively.
基金supported by the National Natural Science Foundation of China(No.51976209)the Fundamental Research Funds for the Central Universities(No.WK2320000040)+1 种基金the Synchrotron Radiation Joint Fund of University of Science and Technology of Chinasupported by Youth Innovation Promotion Association CAS(No.Y201768)。
文摘By virtue of the crucial effect of the crystal structure and transition metal(TM)redox evolution on the performance of LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM)cathode,systematical investigation is carried out to better understand the charge mechanism upon deep charging.Based on the results of X-ray diffraction and highresolution transmission electron microscope,phase transformations existing on particle surface are promoted by high potential because of the deeper lithium vacancies,accompanied by more substantial structure instability.Soft X-ray absorption spectroscopy indicates that Ni acts as the major contributor to charge compensation while Co displays a remarkable redox activity over the deep charge range.The elevated integrated intensity of pre-edge in O K-edge spectra reveals the extensive amount of holes formed in O 2 p orbitals and the enhanced hybridization of TM 3 d-O 2 p orbitals.Considering the close relationship between thermal behavior and structural evolution,the tendency of phase transitions and O_(2) release upon heating is accelerated by voltage rise,demonstrating the aggravated instability due to deeper Li utilization.Remaining Li contents in NCM are employed to estimate the amount of oxygen released in structural transformation and its detrimental effect on stability declares Li contentdependent characteristics.Furthermore,the extended Li vacancies,higher proportion of Ni4+and stronger orbital hybridization are considered as three factors impeding the thermal stability of the highlydelithiated NCM.
