We studied the role of oxygen in Pr2 CuO_(4±δ) thin films fabricated by the polymer assisted deposition method. The magnetoresistance and Hall resistivity of Pr2 CuO_(4±δ) samples were systematically inves...We studied the role of oxygen in Pr2 CuO_(4±δ) thin films fabricated by the polymer assisted deposition method. The magnetoresistance and Hall resistivity of Pr2 CuO_(4±δ) samples were systematically investigated. It was found that with decreasing oxygen content, the low-temperature Hall coefficient(RH) and magnetoresistance changed from negative to positive, similar to those with the increase of Ce-doped concentration in R_(2-x)Ce_x CuO_4 (R = La, Nd, Pr, Sm, Eu). In addition, we observed that the dependence of the superconducting critical temperature Tc with RH for the Pr_(2-x) Ce_x CuO_4 perfectly overlapped with that of Pr_2 CuO_(4±δ) . These findings point to the fact that the doped electrons induced by the oxygen removal are responsible for the superconductivity of the T-phase parent compounds.展开更多
Manipulating the superconducting states of high transition temperature(high-Tc)cuprate superconductors in an efficient and reliable way is of great importance for their applications in next-generation electronics.Here...Manipulating the superconducting states of high transition temperature(high-Tc)cuprate superconductors in an efficient and reliable way is of great importance for their applications in next-generation electronics.Here,employing ionic liquid gating,a selective control of volatile and non-volatile superconductivity is achieved in pristine insulating Pr2CuO4±δ(PCO)films,based on two distinct mechanisms.Firstly,with positive electric fields,the film can be reversibly switched between superconducting and non-superconducting states,attributed to the carrier doping effect.Secondly,the film becomes more resistive by applying negative bias voltage up to-4V,but strikingly,a non-volatile superconductivity is achieved once the gate voltage is removed.Such phenomenon represents a distinctive route of manipulating superconductivity in PCO,resulting from the doping healing of oxygen vacancies in copper-oxygen planes as unravelled by high-resolution scanning transmission electron microscope and in situ X-ray diffraction experiments.The effective manipulation of volatile/non-volatile superconductivity in the same parent cuprate brings more functionalities to superconducting electronics,as well as supplies flexible samples for investigating the nature of quantum phase transitions in high-Tcsuperconductors.展开更多
The N-formylation of amines with CO_(2)and hydrosilanes is an emerging yet important reaction in fine chemical industry.Herein,we have reported a methyltrioctylammonium cation(TOMA)stabilized Nb oxocluster catalyst th...The N-formylation of amines with CO_(2)and hydrosilanes is an emerging yet important reaction in fine chemical industry.Herein,we have reported a methyltrioctylammonium cation(TOMA)stabilized Nb oxocluster catalyst that can effectively realize two electron reduction of CO_(2)and form C-N bond simultaneously,leading to the corresponding formamides.The oxocluster catalyst exhibits excellent catalytic activity to transform secondary and primary amines into the corresponding formamides,with the conversion ranging from 81.5%to 99.2%under room temperature conditions.Furthermore,the Nb oxocluster catalyst shows the unique characteristics of ionic liquids,and it is highly robust and easy to be recycled for five times with negligible loss of catalytic activity.On the basis of the activity tests and structure characterization of Nb catalysts,it was found that TOMA cation played an important role in modulating the Nb oxocluster with high stability and uniform dispersion.The mechanism studies demonstrate that the formylation reaction proceeds through the formation of silyl formate intermediate rather than carbamate,and the Lewis base site of negative oxygen atoms from polyoxoniobate anions can exert a favorable impact on activation both CO_(2)and Si-H bond of PhSiH 3,allowing that N-formylation reaction proceed smoothly under very mild reaction conditions.展开更多
基金Project supported by the National Key Basic Research Program of China(Grant Nos.2015CB921000,2016YFA0300301,2017YFA0303003,and2018YFB0704100)the National Natural Science Foundation of China(Grant Nos.11674374 and 11474338)+2 种基金the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(Grant No.QYZDB-SSW-SLH008)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grants Nos.XDB07020100 and XDB07030200)the Beijing Municipal Science and Technology Project,China(Grant No.Z161100002116011)
文摘We studied the role of oxygen in Pr2 CuO_(4±δ) thin films fabricated by the polymer assisted deposition method. The magnetoresistance and Hall resistivity of Pr2 CuO_(4±δ) samples were systematically investigated. It was found that with decreasing oxygen content, the low-temperature Hall coefficient(RH) and magnetoresistance changed from negative to positive, similar to those with the increase of Ce-doped concentration in R_(2-x)Ce_x CuO_4 (R = La, Nd, Pr, Sm, Eu). In addition, we observed that the dependence of the superconducting critical temperature Tc with RH for the Pr_(2-x) Ce_x CuO_4 perfectly overlapped with that of Pr_2 CuO_(4±δ) . These findings point to the fact that the doped electrons induced by the oxygen removal are responsible for the superconductivity of the T-phase parent compounds.
基金supported by the National Key R&D Program of China(2019YFA0308402 and 2018YFA0305604)the Innovation Program for Quantum Science and Technology(2021ZD0302403)+1 种基金the National Natural Science Foundation of China(11934001,92265106,11774010,and 11921005)Beijing Municipal Natural Science Foundation(JQ20002)。
基金supported by the National Key Basic Research Program of China(2015CB921000,2016YFA0300301,2017YFA0302902,2017YFA0303003 and 2018YFB0704102)the National Natural Science Foundation of China(11674374 and 11834016)+3 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(XDB25000000)the Key Research Program of Frontier Sciences,CAS(QYZDB-SSW-SLH008 and QYZDY-SSW-SLH001)CAS Interdisciplinary Innovation Teambenefited from the bilateral collaboration F.R.S.-FNRS/NSFC(V4/345-DeM-229)。
文摘Manipulating the superconducting states of high transition temperature(high-Tc)cuprate superconductors in an efficient and reliable way is of great importance for their applications in next-generation electronics.Here,employing ionic liquid gating,a selective control of volatile and non-volatile superconductivity is achieved in pristine insulating Pr2CuO4±δ(PCO)films,based on two distinct mechanisms.Firstly,with positive electric fields,the film can be reversibly switched between superconducting and non-superconducting states,attributed to the carrier doping effect.Secondly,the film becomes more resistive by applying negative bias voltage up to-4V,but strikingly,a non-volatile superconductivity is achieved once the gate voltage is removed.Such phenomenon represents a distinctive route of manipulating superconductivity in PCO,resulting from the doping healing of oxygen vacancies in copper-oxygen planes as unravelled by high-resolution scanning transmission electron microscope and in situ X-ray diffraction experiments.The effective manipulation of volatile/non-volatile superconductivity in the same parent cuprate brings more functionalities to superconducting electronics,as well as supplies flexible samples for investigating the nature of quantum phase transitions in high-Tcsuperconductors.
基金The authors are grateful for financial support from the National Natural Science Foundation of China(21773061,21978095).
文摘The N-formylation of amines with CO_(2)and hydrosilanes is an emerging yet important reaction in fine chemical industry.Herein,we have reported a methyltrioctylammonium cation(TOMA)stabilized Nb oxocluster catalyst that can effectively realize two electron reduction of CO_(2)and form C-N bond simultaneously,leading to the corresponding formamides.The oxocluster catalyst exhibits excellent catalytic activity to transform secondary and primary amines into the corresponding formamides,with the conversion ranging from 81.5%to 99.2%under room temperature conditions.Furthermore,the Nb oxocluster catalyst shows the unique characteristics of ionic liquids,and it is highly robust and easy to be recycled for five times with negligible loss of catalytic activity.On the basis of the activity tests and structure characterization of Nb catalysts,it was found that TOMA cation played an important role in modulating the Nb oxocluster with high stability and uniform dispersion.The mechanism studies demonstrate that the formylation reaction proceeds through the formation of silyl formate intermediate rather than carbamate,and the Lewis base site of negative oxygen atoms from polyoxoniobate anions can exert a favorable impact on activation both CO_(2)and Si-H bond of PhSiH 3,allowing that N-formylation reaction proceed smoothly under very mild reaction conditions.
