The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction...The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.展开更多
In this study,current-induced partial magnetization-based switching was realized through the spin–orbit torque(SOT)in single-layer L1_(0) FePt with a perpendicular anisotropy(K_(u⊥))of 1.19×10^(7) erg·cm^(...In this study,current-induced partial magnetization-based switching was realized through the spin–orbit torque(SOT)in single-layer L1_(0) FePt with a perpendicular anisotropy(K_(u⊥))of 1.19×10^(7) erg·cm^(-3)(1 erg·cm^(-3)=0.1 J·m^(-3)),and its corresponding SOT efficiency(βDL)was 8×10^(-6) Oe·(A·cm^(-2))^(-1)(1 Oe=79.57747 A·m^(-1)),which is several times higher than that of the traditional Ta/CoFeB/MgO structure reported in past work.The SOT in the FePt films originated from the structural inversion asymmetry in the FePt films since the dislocations and defects were inhomogeneously distributed within the samples.Furthermore,the FePt grown on MgO with a granular structure had a larger effective SOT field and effi-ciency than that grown on SrTiO_(3)(STO)with a continuous structure.The SOT efficiency was found to be considerably dependent on not only the sputtering temperature-induced chemical ordering but also the lattice mismatch-induced evolution of the microstructure.Our findings can provide a useful means of efficiently electrically controlling a magnetic bit that is highly thermally stable via SOT.展开更多
L1_(0)-FeNi hard magnetic alloy with coercivity reaching 861 Oe was synthesized through annealing Fe_(42)Ni_(41.3)Si_8 B_(4)P_(4)Cu_(0.7)amorphous alloy,and the L1_(0)-FeNi formation mechanism has been studied.It is f...L1_(0)-FeNi hard magnetic alloy with coercivity reaching 861 Oe was synthesized through annealing Fe_(42)Ni_(41.3)Si_8 B_(4)P_(4)Cu_(0.7)amorphous alloy,and the L1_(0)-FeNi formation mechanism has been studied.It is found the L1_(0)-FeNi in annealed samples at 400℃mainly originated from the residual amorphous phase during the second stage of crystallization which could take place over 600 C lower than the measured onset temperature of the second stage with a50 C/min heating rate.Annealing at 4000 C after fully crystallization still caused a slight increase of coercivity,which was probably contributed by the limited transformation from other high temperature crystalline phases towards L1_(0)phase,or the removal of B from L1_(0)lattice and improvement of the ordering quality of L1_(0)phase due to the reduced temperature from520℃to 400℃.The first stage of crystallization has hardly direct contribution to L1_(0)-FeNi formation.Ab initio simulations show that the addition of Si or Co in L1_(0)-FeNi has the effect of enhancing the thermal stability of L1_(0)phase without seriously deteriorating its magnetic hardness.The non-monotonic feature of direction dependent coercivity in ribbon segments resulted from the combination of domain wall pinning and demagnetization effects.The approaches of synthesizing L1_(0)-FeNi magnets by adding Si or Co and decreasing the onset crystallization temperature have been discussed in detail.展开更多
Super-fine L1_(0)-Fe Pt nanoparticles(NPs)with high ordering degree were successfully prepared by a modified two-step sintering method,which includes low-temperature pre-sintering,and the high magnetic field(HMF)assis...Super-fine L1_(0)-Fe Pt nanoparticles(NPs)with high ordering degree were successfully prepared by a modified two-step sintering method,which includes low-temperature pre-sintering,and the high magnetic field(HMF)assisted post-sintering processes.The particle size of the L1_(0)-FePt NPs was obviously refined by lowering the sintering temperature.By applying the HMF during the post-sintering process,the fine size characteristics of L1_(0)-Fe Pt NPs were retained,and the ordering degree was significantly improved.The L1_(0)-Fe Pt NPs with sizes of about 4.5 nm,ordering degree of 0.940,and coercivity of 22.01 k Oe were obtained by this two-step sintering under a magnetic field of 12 T.The mechanism investigation of HMF enhancing the ordering degree indicates that the HMF enhances lattice distortion and magnetization energy(Zeeman energy).The enhanced lattice distortions cause high stress existing in the lattice,which can effectively promote the disordered-order transition.When the magnetic field reaches to 3 T,the Zeeman energy of the NPs is higher than the thermal disturbing energy of the NPs,and the magnetization effect is stronger.Therefore,the HMF(higher than 3 T)can obviously improve the disorder-order transition by lowering the energy barrier and accelerating the orderly diffusions of atoms.The HMF is a promising assistant to synthesize the L1_(0)-phase NPs with both of high ordering degree and super-fine size.展开更多
The ordered Pt-based intermetallic nanoparticles(NPs)with small size show superior magnetic or catalytic properties,but the synthesis of these NPs still remains a great challenge due to the requirement of high tempera...The ordered Pt-based intermetallic nanoparticles(NPs)with small size show superior magnetic or catalytic properties,but the synthesis of these NPs still remains a great challenge due to the requirement of high temperature annealing for the formation of the ordered phase,which usually leads to sintering of the NPs.Here,we report a simple approach to directly synthesize monodisperse ordered L1_(0)-FePt NPs with average size 10.7 nm without further annealing or doping the third metal atoms,in which hexadecyltrimethylammonium chloride(CTAC)was found to be the key inducing agent for the thermodynamic growth of the Fe and Pt atoms into the ordered intermetallic structure in the synthetic process.In particular,10.7 nm L1_(0)-FePt NPs synthesized by the proper amount of CTAC show a coercivity of 3.15 kOe and saturation magnetization of 45 emu/g at room temperature.The current CTAC-assisted synthetic strategy makes it possible to deeply understand the formation of the ordered Pt-based intermetallic NP in solution phase synthesis.展开更多
基金supported by the National Key Research and Development Program of China(2021YFB4001301)the Science and Technology Commission of Shanghai Municipality(21DZ1208600)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2021ZD105)。
文摘The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.
基金supported by National Key Research and Development Program of China (2020AAA0109005)the National Natural Science Foundation of China (61674062, 51501168, 41574175, and 41204083)+3 种基金the Fundamental Research Funds for the Central Universities of the China University of Geosciences (Wuhan) (CUG150632 and CUGL160414)the Fundamental Research Funds for National Universities of the China University of Geosciences (Wuhan)the Interdisciplinary program of Wuhan National High Magnetic Field Center (WHMFC202119)Huazhong University of Science and Technology, and Fund from Shenzhen Virtual University Park (2021Szvup091)
文摘In this study,current-induced partial magnetization-based switching was realized through the spin–orbit torque(SOT)in single-layer L1_(0) FePt with a perpendicular anisotropy(K_(u⊥))of 1.19×10^(7) erg·cm^(-3)(1 erg·cm^(-3)=0.1 J·m^(-3)),and its corresponding SOT efficiency(βDL)was 8×10^(-6) Oe·(A·cm^(-2))^(-1)(1 Oe=79.57747 A·m^(-1)),which is several times higher than that of the traditional Ta/CoFeB/MgO structure reported in past work.The SOT in the FePt films originated from the structural inversion asymmetry in the FePt films since the dislocations and defects were inhomogeneously distributed within the samples.Furthermore,the FePt grown on MgO with a granular structure had a larger effective SOT field and effi-ciency than that grown on SrTiO_(3)(STO)with a continuous structure.The SOT efficiency was found to be considerably dependent on not only the sputtering temperature-induced chemical ordering but also the lattice mismatch-induced evolution of the microstructure.Our findings can provide a useful means of efficiently electrically controlling a magnetic bit that is highly thermally stable via SOT.
基金supported by the National Natural Science Foundation of China(Grant Nos.51971179 and 51971180)the Natural Science Foundation of Chongqing,China(Grant No.cstc2019jcyj-msxmX0328)+3 种基金Shaanxi Provincial Natural Science Foundation,China(Grant No.2020JM-112)Guangdong Provincial Science and Technology Program,China(Grant No.2019B090905009)the Fundamental Research Funds for the Central Universities of China(Grant No.D5000210731)Shaanxi Provincial Key R&D Program,China(Grant No.2021KWZ-13)。
文摘L1_(0)-FeNi hard magnetic alloy with coercivity reaching 861 Oe was synthesized through annealing Fe_(42)Ni_(41.3)Si_8 B_(4)P_(4)Cu_(0.7)amorphous alloy,and the L1_(0)-FeNi formation mechanism has been studied.It is found the L1_(0)-FeNi in annealed samples at 400℃mainly originated from the residual amorphous phase during the second stage of crystallization which could take place over 600 C lower than the measured onset temperature of the second stage with a50 C/min heating rate.Annealing at 4000 C after fully crystallization still caused a slight increase of coercivity,which was probably contributed by the limited transformation from other high temperature crystalline phases towards L1_(0)phase,or the removal of B from L1_(0)lattice and improvement of the ordering quality of L1_(0)phase due to the reduced temperature from520℃to 400℃.The first stage of crystallization has hardly direct contribution to L1_(0)-FeNi formation.Ab initio simulations show that the addition of Si or Co in L1_(0)-FeNi has the effect of enhancing the thermal stability of L1_(0)phase without seriously deteriorating its magnetic hardness.The non-monotonic feature of direction dependent coercivity in ribbon segments resulted from the combination of domain wall pinning and demagnetization effects.The approaches of synthesizing L1_(0)-FeNi magnets by adding Si or Co and decreasing the onset crystallization temperature have been discussed in detail.
基金financially supported by the National Natural Science Foundation of China(Grant nos.51871045,52071070,and 51690161)the Fundamental Research Funds for the Central Universities(Grant no.N2017003)the Doctoral Start-up Foundation of Liaoning Province(Grant no.2019-BS-116)。
文摘Super-fine L1_(0)-Fe Pt nanoparticles(NPs)with high ordering degree were successfully prepared by a modified two-step sintering method,which includes low-temperature pre-sintering,and the high magnetic field(HMF)assisted post-sintering processes.The particle size of the L1_(0)-FePt NPs was obviously refined by lowering the sintering temperature.By applying the HMF during the post-sintering process,the fine size characteristics of L1_(0)-Fe Pt NPs were retained,and the ordering degree was significantly improved.The L1_(0)-Fe Pt NPs with sizes of about 4.5 nm,ordering degree of 0.940,and coercivity of 22.01 k Oe were obtained by this two-step sintering under a magnetic field of 12 T.The mechanism investigation of HMF enhancing the ordering degree indicates that the HMF enhances lattice distortion and magnetization energy(Zeeman energy).The enhanced lattice distortions cause high stress existing in the lattice,which can effectively promote the disordered-order transition.When the magnetic field reaches to 3 T,the Zeeman energy of the NPs is higher than the thermal disturbing energy of the NPs,and the magnetization effect is stronger.Therefore,the HMF(higher than 3 T)can obviously improve the disorder-order transition by lowering the energy barrier and accelerating the orderly diffusions of atoms.The HMF is a promising assistant to synthesize the L1_(0)-phase NPs with both of high ordering degree and super-fine size.
基金supported by the National Natural Science Foundation of China under Grant(Nos.51871078,51631001 and 51590882)the National Key R&D Program of China(No.2016YFA0200102)Heilongjiang Science Foundation(No.E2018028).
文摘The ordered Pt-based intermetallic nanoparticles(NPs)with small size show superior magnetic or catalytic properties,but the synthesis of these NPs still remains a great challenge due to the requirement of high temperature annealing for the formation of the ordered phase,which usually leads to sintering of the NPs.Here,we report a simple approach to directly synthesize monodisperse ordered L1_(0)-FePt NPs with average size 10.7 nm without further annealing or doping the third metal atoms,in which hexadecyltrimethylammonium chloride(CTAC)was found to be the key inducing agent for the thermodynamic growth of the Fe and Pt atoms into the ordered intermetallic structure in the synthetic process.In particular,10.7 nm L1_(0)-FePt NPs synthesized by the proper amount of CTAC show a coercivity of 3.15 kOe and saturation magnetization of 45 emu/g at room temperature.The current CTAC-assisted synthetic strategy makes it possible to deeply understand the formation of the ordered Pt-based intermetallic NP in solution phase synthesis.
