The melting behavior,solid state phase transformation and structure of pseudo-ternary compounds Nd_2(Fe_(1-x)Ni_x)_(14)B and Pr_2(Co_(1-y)Ni_y)_(14)B were studied using differential thermal analysis,optical microscopy...The melting behavior,solid state phase transformation and structure of pseudo-ternary compounds Nd_2(Fe_(1-x)Ni_x)_(14)B and Pr_2(Co_(1-y)Ni_y)_(14)B were studied using differential thermal analysis,optical microscopy X-ray diffraction,and electron probe micro-analysis techniques.At high temperature,eutectoid decomposition R_2(Ni,M)_(17)→R(Ni,M)_5+x-Ni(M) takes place in these two pseudo-ternary compounds,in the composition range x=0.6～1.0 and y=0.3～1.0,respectively.When x(or y)≤0.2,both Nd_2(Fe_(1-x)Ni_x)_(14)B and Pr_2(Co_(1-y)Ni_y)_(14)B are single phase tetragonal.The phase constitutents of these two systems at room tempera- ture are similar in the composition range 0.6≤x(or y)≤1.0.展开更多
Strongly ordered B2 compounds exist in many alloy systems. This paper presented an overview of their mechanical properties, which depend strongly on the concentrations of constitutional defects, that is, on the consti...Strongly ordered B2 compounds exist in many alloy systems. This paper presented an overview of their mechanical properties, which depend strongly on the concentrations of constitutional defects, that is, on the constitutional vacancies and antisite atoms, and, hence, on composition.展开更多
Easy and hard magnetization curves of Nd_2Co_(14)B compound have been measured with extracting-sample-magnetometer(μ_0H_(max)=6T)at 10～300 K.Magnetic anisotropy constants K_1 and K_2 have been determined by fitting ...Easy and hard magnetization curves of Nd_2Co_(14)B compound have been measured with extracting-sample-magnetometer(μ_0H_(max)=6T)at 10～300 K.Magnetic anisotropy constants K_1 and K_2 have been determined by fitting the hard magnetization curves,in which only K_1 ,K_2 and misalignment angle have been taken as fitting parameters.The values of K_1 and K_2 at 4.2 K were derived by extrapolation. Anisotropy coefficients,x_2~° and x_4~°were derived from the anisotropy constants.The anisotropy constant K_2 increases rapidly with increasing temperature when T<T_(sr)and slowly when T>T_(sr).The temperature depen- dence of the magnetic anisotropy coefficient x_2~° was fitted with the formula.The anisotropy coefficients x_2~° can be well described by the tenth-power law from 4.2 K to T_(sr)and by the sixth-power law from T_(sr_ to 300 K.展开更多
The results of SCF CNDO-CO calculation on polymeric [(η5,μ-2,3-dihydro-1 , 3-di-borolyl)M](M= Cr, Mn, Fe, Co, Ni) indicate that polydecker sandwich compounds with odd valence electrons in each stacking unit (C3B2H5)...The results of SCF CNDO-CO calculation on polymeric [(η5,μ-2,3-dihydro-1 , 3-di-borolyl)M](M= Cr, Mn, Fe, Co, Ni) indicate that polydecker sandwich compounds with odd valence electrons in each stacking unit (C3B2H5)M have Peierls distorted structures, while those with even valence electrons are favorable to the formation of regular structures. The Band structures show that both LU and HO bands are d-bands for all of the polydecker sandwich compounds studied.展开更多
C100H78, (A: C36H28, B: C28H22) Mr = 1279. 74, monoclinic, P21/a, a=17. 282(3), b=10. 669(4), c= 19, 927(3) A , β =102. 99(1)°,V = 3580. 1(2) A3, Z=2, μ(MoKα) = 0. 623cm-1, F(000) = 1356, Dc=1. 187g/cm3, room ...C100H78, (A: C36H28, B: C28H22) Mr = 1279. 74, monoclinic, P21/a, a=17. 282(3), b=10. 669(4), c= 19, 927(3) A , β =102. 99(1)°,V = 3580. 1(2) A3, Z=2, μ(MoKα) = 0. 623cm-1, F(000) = 1356, Dc=1. 187g/cm3, room temperature. The final R=0. 084, Rw = 0. 086 for 1255 independent observed reflections (I≥3σ(I)). Owing to the existence of 1,6,7, 8-Tetraphenyl (3,4-benzo)-bicyclo[4, 2, 0]octa-7-ene(A) , cis, cts-1, 2, 3, 4-Tetraphenylbutadiene (B) in A2B can take the different conformation from the one in the pure B crystal. The reason of the formation of this molecular compound crystal is put forward.展开更多
杂原子掺杂可以调节电子结构以调整中间体吸附并优化反应路径,是设计高效CO_(2)还原反应(CO_(2)RR)催化剂的有应用前景的方法.B原子是常用的掺杂剂,引入B原子可以有效打破*COOH和OCHO*中间体的吉布斯自由能线性关系,并且可以通过与CO_(2...杂原子掺杂可以调节电子结构以调整中间体吸附并优化反应路径,是设计高效CO_(2)还原反应(CO_(2)RR)催化剂的有应用前景的方法.B原子是常用的掺杂剂,引入B原子可以有效打破*COOH和OCHO*中间体的吉布斯自由能线性关系,并且可以通过与CO_(2)中O原子结合来增强CO_(2)吸附能力.B掺杂碳材料、单金属和金属氧化物的研究结果表明,B原子掺杂催化剂的CO_(2)RR活性和/或选择性有明显提高,然而多数报道的单个活性位点的B掺杂催化剂仅表现出在相对狭窄的电位范围内的CO_(2)RR高性能,设计制备CO_(2)RR的宽电位高选择性催化剂仍是巨大挑战.研究表明,合金化是提供多种类的活性位点相互协调和增强催化剂固有活性,进而改善CO_(2)RR性能并调节产物分布的可行策略.引入B原子到合金中以调节电子结构,最终优化关键中间体吸附的活性位点,对于寻找具有宽电位窗口的先进催化剂具有重要意义.本文提出了一种通过B掺杂调节CuIn合金电子结构以实现宽电位高选择性的电子工程策略.所制得的B掺杂CuIn合金(CuIn(B))在–0.6 V(vs.RHE)时表现出99%的CO法拉第效率(FECO),并在一个宽的阴极电化学窗口(400 m V)内保持了超过90%的较高FECO.同时,采用X射线光电子能谱(XPS)和CO_(2)吸附实验等手段研究了CuIn(B)性能提升的原因,结果表明,B原子与CuIn之间存在强烈的相互作用,改变了CuIn的电子结构.CO_(2)吸附结果表明,CuIn(B)比CuIn拥有更强的CO_(2)吸附能力,证明它具有潜在的快速CO_(2)RR反应动力学.进一步通过密度泛函理论(DFT)模拟研究了催化剂的热力学反应能量学以揭示CO_(2)RR机制,结果表明,*COOH更倾向于在CuIn(B)上形成,且*CO与CuIn(B)催化位点的结合强度最佳,更利于CO_(2)还原反应为CO,而CuIn更利于作为HER的活性位点;决速步骤是*CO中间体向CO转移,以实现高CO选择性;热力学限制电位研究表明,CuIn(B)大大提高了CO_(2)到CO转化的选择性.随后通过差分电荷密度研究也进一步证明了电荷转移过程是从CuIn位点到B位点.此外,根据d带理论,催化剂中Cu和In原子的投影态密度和d带中心(Ed)研究进一步证明了催化剂结构中的电子价态的变化,与XPS结果相符;引入B可以优化催化剂的电子结构,从而调节催化剂和中间体之间的结合能力,实现了CO_(2)RR在宽电位范围内的高活性和选择性.综上,本文对于电化学CO_(2)RR机理的基础理解和其实际应用具有促进作用.展开更多
基金the National Natural Science Fundation of China.
文摘The melting behavior,solid state phase transformation and structure of pseudo-ternary compounds Nd_2(Fe_(1-x)Ni_x)_(14)B and Pr_2(Co_(1-y)Ni_y)_(14)B were studied using differential thermal analysis,optical microscopy X-ray diffraction,and electron probe micro-analysis techniques.At high temperature,eutectoid decomposition R_2(Ni,M)_(17)→R(Ni,M)_5+x-Ni(M) takes place in these two pseudo-ternary compounds,in the composition range x=0.6～1.0 and y=0.3～1.0,respectively.When x(or y)≤0.2,both Nd_2(Fe_(1-x)Ni_x)_(14)B and Pr_2(Co_(1-y)Ni_y)_(14)B are single phase tetragonal.The phase constitutents of these two systems at room tempera- ture are similar in the composition range 0.6≤x(or y)≤1.0.
文摘Strongly ordered B2 compounds exist in many alloy systems. This paper presented an overview of their mechanical properties, which depend strongly on the concentrations of constitutional defects, that is, on the constitutional vacancies and antisite atoms, and, hence, on composition.
基金This work has been supported by the National Natural Science Foundation of P.R.China(5870025)Magnetism Laboratory of Institute of Physics,Beijing,P.R.China.
文摘Easy and hard magnetization curves of Nd_2Co_(14)B compound have been measured with extracting-sample-magnetometer(μ_0H_(max)=6T)at 10～300 K.Magnetic anisotropy constants K_1 and K_2 have been determined by fitting the hard magnetization curves,in which only K_1 ,K_2 and misalignment angle have been taken as fitting parameters.The values of K_1 and K_2 at 4.2 K were derived by extrapolation. Anisotropy coefficients,x_2~° and x_4~°were derived from the anisotropy constants.The anisotropy constant K_2 increases rapidly with increasing temperature when T<T_(sr)and slowly when T>T_(sr).The temperature depen- dence of the magnetic anisotropy coefficient x_2~° was fitted with the formula.The anisotropy coefficients x_2~° can be well described by the tenth-power law from 4.2 K to T_(sr)and by the sixth-power law from T_(sr_ to 300 K.
基金Supported by the National Natural Science Foundation of China the Young Teacher's Foundation of the State Education Commission of China
文摘The results of SCF CNDO-CO calculation on polymeric [(η5,μ-2,3-dihydro-1 , 3-di-borolyl)M](M= Cr, Mn, Fe, Co, Ni) indicate that polydecker sandwich compounds with odd valence electrons in each stacking unit (C3B2H5)M have Peierls distorted structures, while those with even valence electrons are favorable to the formation of regular structures. The Band structures show that both LU and HO bands are d-bands for all of the polydecker sandwich compounds studied.
基金The Project was supported by the National Science Foundation of China
文摘C100H78, (A: C36H28, B: C28H22) Mr = 1279. 74, monoclinic, P21/a, a=17. 282(3), b=10. 669(4), c= 19, 927(3) A , β =102. 99(1)°,V = 3580. 1(2) A3, Z=2, μ(MoKα) = 0. 623cm-1, F(000) = 1356, Dc=1. 187g/cm3, room temperature. The final R=0. 084, Rw = 0. 086 for 1255 independent observed reflections (I≥3σ(I)). Owing to the existence of 1,6,7, 8-Tetraphenyl (3,4-benzo)-bicyclo[4, 2, 0]octa-7-ene(A) , cis, cts-1, 2, 3, 4-Tetraphenylbutadiene (B) in A2B can take the different conformation from the one in the pure B crystal. The reason of the formation of this molecular compound crystal is put forward.
文摘杂原子掺杂可以调节电子结构以调整中间体吸附并优化反应路径,是设计高效CO_(2)还原反应(CO_(2)RR)催化剂的有应用前景的方法.B原子是常用的掺杂剂,引入B原子可以有效打破*COOH和OCHO*中间体的吉布斯自由能线性关系,并且可以通过与CO_(2)中O原子结合来增强CO_(2)吸附能力.B掺杂碳材料、单金属和金属氧化物的研究结果表明,B原子掺杂催化剂的CO_(2)RR活性和/或选择性有明显提高,然而多数报道的单个活性位点的B掺杂催化剂仅表现出在相对狭窄的电位范围内的CO_(2)RR高性能,设计制备CO_(2)RR的宽电位高选择性催化剂仍是巨大挑战.研究表明,合金化是提供多种类的活性位点相互协调和增强催化剂固有活性,进而改善CO_(2)RR性能并调节产物分布的可行策略.引入B原子到合金中以调节电子结构,最终优化关键中间体吸附的活性位点,对于寻找具有宽电位窗口的先进催化剂具有重要意义.本文提出了一种通过B掺杂调节CuIn合金电子结构以实现宽电位高选择性的电子工程策略.所制得的B掺杂CuIn合金(CuIn(B))在–0.6 V(vs.RHE)时表现出99%的CO法拉第效率(FECO),并在一个宽的阴极电化学窗口(400 m V)内保持了超过90%的较高FECO.同时,采用X射线光电子能谱(XPS)和CO_(2)吸附实验等手段研究了CuIn(B)性能提升的原因,结果表明,B原子与CuIn之间存在强烈的相互作用,改变了CuIn的电子结构.CO_(2)吸附结果表明,CuIn(B)比CuIn拥有更强的CO_(2)吸附能力,证明它具有潜在的快速CO_(2)RR反应动力学.进一步通过密度泛函理论(DFT)模拟研究了催化剂的热力学反应能量学以揭示CO_(2)RR机制,结果表明,*COOH更倾向于在CuIn(B)上形成,且*CO与CuIn(B)催化位点的结合强度最佳,更利于CO_(2)还原反应为CO,而CuIn更利于作为HER的活性位点;决速步骤是*CO中间体向CO转移,以实现高CO选择性;热力学限制电位研究表明,CuIn(B)大大提高了CO_(2)到CO转化的选择性.随后通过差分电荷密度研究也进一步证明了电荷转移过程是从CuIn位点到B位点.此外,根据d带理论,催化剂中Cu和In原子的投影态密度和d带中心(Ed)研究进一步证明了催化剂结构中的电子价态的变化,与XPS结果相符;引入B可以优化催化剂的电子结构,从而调节催化剂和中间体之间的结合能力,实现了CO_(2)RR在宽电位范围内的高活性和选择性.综上,本文对于电化学CO_(2)RR机理的基础理解和其实际应用具有促进作用.
