Developing practical strategies for the synthesis of organophosphorus compounds(OPCs)from white phosphorus(P_(4))without the use of Cl_(2) and PCl_(3) remains a significant challenge.The first multicomponent oxidative...Developing practical strategies for the synthesis of organophosphorus compounds(OPCs)from white phosphorus(P_(4))without the use of Cl_(2) and PCl_(3) remains a significant challenge.The first multicomponent oxidative α-phosphonylation of amines with P_(4) and alcohols has been developed.With the use of copper(Ⅱ)as the catalyst and air as the safe oxidant,structurally sophisticated α-aminophosphonates have been prepared in high yields.Furthermore,this method is also suitable for selective construction of P-O-P compounds.The reaction is characterized by a complete conversion of P_(4).The activation of P_(4) with transition metals often leads to formation of complexes[M_(x)P_(y)]_(n) associated with the deactivation of transition metals.This breakthrough showcases the potential of transition-metal-catalyzed reactions in elemental phosphorus chemistry.展开更多
The activation behaviors and hydrogen storage properties of the Laves phase Ti1-xZrx(Mn0.5Cr0.5)2 (x=0, 0.1, 0.2, 0.32, 0.5) alloys were investigated by the pressure-composition-temperature (P-C-T) measurements. All t...The activation behaviors and hydrogen storage properties of the Laves phase Ti1-xZrx(Mn0.5Cr0.5)2 (x=0, 0.1, 0.2, 0.32, 0.5) alloys were investigated by the pressure-composition-temperature (P-C-T) measurements. All the studied alloys show the single C14-type Laves phase structure based on the XRD data. Except for the alloys with very low Zr content of x=0 and x=0.1, all these alloys can be fully activated. The P-C isotherms of the activated alloys show that, the introduction of Zr induces the decrease of the equilibrium pressures and the steeper plateaus. As the x increases, the maximum hydrogen absorption also increases, whereas the desorption of hydrogen decreases. These two effects result in a maximum reversible hydrogen storage capacity of H/M=3.03 for the alloy at x=0.32. Furthermore, the well-defined plateau associated with the smallest hysteresis also appears at x=0.32.展开更多
The effects of partial substitution of La by Ce and Ni by Al, Fe, or Co in LaNi_5-based alloys on hydrogen storage performance were systematically studied. All samples were prepared using vacuum arc melting in an argo...The effects of partial substitution of La by Ce and Ni by Al, Fe, or Co in LaNi_5-based alloys on hydrogen storage performance were systematically studied. All samples were prepared using vacuum arc melting in an argon atmosphere. The results showed that for LaNi_(5-x)M_x(M = Al, Fe, or Co) alloys, the lattice constants and unit cell volumes increased with an increasing amount of Al and Fe. On the other hand, these parameters decreased upon partial substitution of La by Ce. In addition, the lattice constant remained almost constant in the La_(0.6)Ce_(0.4)Ni_(5–x)Cox alloys regardless of the value of x(x = 0.3, 0.6, or 0.9), as Ce might enhance the homogeneity of the CaCu_5-type phase in Co-containing alloys. The hydrogen storage properties of the alloys were investigated using pressure, composition, and temperature isotherms. The experimental results showed that the plateau pressure decreased with an increasing content of Al, Fe, or Co, but it increased with Ce addition. Furthermore, the plateau pressures of all Co-containing alloys were almost identical upon substitution with Ce. Finally, the enthalpy(ΔH) and entropy(ΔS) values for all alloys were calculated using van't Hoff plots. The relationship between the lattice parameters and enthalpy changes for hydrogenation will be discussed.展开更多
The as-cast RE-Mg-Ni-b ased AB2-type La1-xPrxMgNi3.6Co0.4(x=0-0.4)alloys were prepared by vacuum induction melting followed by annealing treatment.The phase composition and structure were characterized by X-ray diffra...The as-cast RE-Mg-Ni-b ased AB2-type La1-xPrxMgNi3.6Co0.4(x=0-0.4)alloys were prepared by vacuum induction melting followed by annealing treatment.The phase composition and structure were characterized by X-ray diffraction(XRD)and scanning electron microscope(SEM).The results show that LaMgNi4 and LaNi5 coexist in as-cast alloys,but only LaMgNi4 is detected in the annealed alloys.The morphology of annealed alloys is more homogeneous than that of as-cast alloys.The gaseous hydrogen storage and electrochemical properties were investigated by pressure-composition isotherm(P-C-T)and electrochemical measurements.The P-C-T curves of annealed alloys show flatter and wider pressure plateaus corresponding to absorption/desorption pressure plateaus of LaMgNi4 hydride.But the maximum hydrogen storage content of annealed alloys is lower than that of as-cast alloys.In consideration of the electrochemical properties,the annealed La0.8Pr0.2MgNi3.6Co0.4alloy exhibits a maximum discharge capacity of354.2 mAh·g-1.展开更多
The effect of Mn substitution on phase structure,hydrogen hydriding/dehydriding properties(plateau pressure and slope)and reaction heat enthalpy of LaNi_(4.25-x)Al_(0.75)Mn_(x)alloys(x=0,0.25,0.35,0.45,0.55 and 0.65)w...The effect of Mn substitution on phase structure,hydrogen hydriding/dehydriding properties(plateau pressure and slope)and reaction heat enthalpy of LaNi_(4.25-x)Al_(0.75)Mn_(x)alloys(x=0,0.25,0.35,0.45,0.55 and 0.65)were studied.The experimental results show that all LaNi_(4.25-x)Al_(0.75)Mn_(x)alloys have single phase and have the same hexagonal structure as that of LaNi5 alloy(CaCu_(5)type,P6/mmm).With increasing Mn substitution content,the cell parameters of LaNi_(4.25-x)Al_(0.75)Mn_(x)alloy greatly increase,but the maximum hydrogen storage capacity and the equilibrium absorption pressure of LaNi_(4.25-x)Al_(0.75)Mn_(x)alloy decrease from 1.38 wt.%to 1.18 wt.%and from 1.61 to 0.0712 MPa,respectively.Moreover,the hydrogen pressure plateau slope factorσincreases from 0.014 to 0.18,but the hysteresis factor is nearly constant.The heat enthalpy absolute value|ΔH_(plat)|increases from 46.7 kJ·mol^(-1)H2 to 56.1 kJ·mol^(-1)H_(2)as the Mn content x increases from 0 to 0.65.展开更多
基金the National Key Research and Development Program of China(grant no.2020YFA0608300)the Space Application System of China Manned Space Program(grant no.KJZ-YY-WSM01)National Natural Science Foundation of China(grant nos.21772163,21778042,and 41876072).
文摘Developing practical strategies for the synthesis of organophosphorus compounds(OPCs)from white phosphorus(P_(4))without the use of Cl_(2) and PCl_(3) remains a significant challenge.The first multicomponent oxidative α-phosphonylation of amines with P_(4) and alcohols has been developed.With the use of copper(Ⅱ)as the catalyst and air as the safe oxidant,structurally sophisticated α-aminophosphonates have been prepared in high yields.Furthermore,this method is also suitable for selective construction of P-O-P compounds.The reaction is characterized by a complete conversion of P_(4).The activation of P_(4) with transition metals often leads to formation of complexes[M_(x)P_(y)]_(n) associated with the deactivation of transition metals.This breakthrough showcases the potential of transition-metal-catalyzed reactions in elemental phosphorus chemistry.
基金This work was supported by the National Natural Science Foundation of China (No.50371086).
文摘The activation behaviors and hydrogen storage properties of the Laves phase Ti1-xZrx(Mn0.5Cr0.5)2 (x=0, 0.1, 0.2, 0.32, 0.5) alloys were investigated by the pressure-composition-temperature (P-C-T) measurements. All the studied alloys show the single C14-type Laves phase structure based on the XRD data. Except for the alloys with very low Zr content of x=0 and x=0.1, all these alloys can be fully activated. The P-C isotherms of the activated alloys show that, the introduction of Zr induces the decrease of the equilibrium pressures and the steeper plateaus. As the x increases, the maximum hydrogen absorption also increases, whereas the desorption of hydrogen decreases. These two effects result in a maximum reversible hydrogen storage capacity of H/M=3.03 for the alloy at x=0.32. Furthermore, the well-defined plateau associated with the smallest hysteresis also appears at x=0.32.
基金partially supported by International Academic Exchange Program of Muroran Institute of Technology,Muroran(Japan)University of Science and Technology Beijing,Beijing(China)+1 种基金Environmentally Friendly Materials Education Program provided by Muroran MATERIAsupported by Beijing Key Laboratory of Energy Conservation and Emission Reduction for Metallurgical Industry,Beijing,China
文摘The effects of partial substitution of La by Ce and Ni by Al, Fe, or Co in LaNi_5-based alloys on hydrogen storage performance were systematically studied. All samples were prepared using vacuum arc melting in an argon atmosphere. The results showed that for LaNi_(5-x)M_x(M = Al, Fe, or Co) alloys, the lattice constants and unit cell volumes increased with an increasing amount of Al and Fe. On the other hand, these parameters decreased upon partial substitution of La by Ce. In addition, the lattice constant remained almost constant in the La_(0.6)Ce_(0.4)Ni_(5–x)Cox alloys regardless of the value of x(x = 0.3, 0.6, or 0.9), as Ce might enhance the homogeneity of the CaCu_5-type phase in Co-containing alloys. The hydrogen storage properties of the alloys were investigated using pressure, composition, and temperature isotherms. The experimental results showed that the plateau pressure decreased with an increasing content of Al, Fe, or Co, but it increased with Ce addition. Furthermore, the plateau pressures of all Co-containing alloys were almost identical upon substitution with Ce. Finally, the enthalpy(ΔH) and entropy(ΔS) values for all alloys were calculated using van't Hoff plots. The relationship between the lattice parameters and enthalpy changes for hydrogenation will be discussed.
基金financially supported by the National Natural Science Foundations of China(Nos.51161015 and 51371094)the Natural Science Foundation of Inner Mongolia, China (No. 2011ZD10)
文摘The as-cast RE-Mg-Ni-b ased AB2-type La1-xPrxMgNi3.6Co0.4(x=0-0.4)alloys were prepared by vacuum induction melting followed by annealing treatment.The phase composition and structure were characterized by X-ray diffraction(XRD)and scanning electron microscope(SEM).The results show that LaMgNi4 and LaNi5 coexist in as-cast alloys,but only LaMgNi4 is detected in the annealed alloys.The morphology of annealed alloys is more homogeneous than that of as-cast alloys.The gaseous hydrogen storage and electrochemical properties were investigated by pressure-composition isotherm(P-C-T)and electrochemical measurements.The P-C-T curves of annealed alloys show flatter and wider pressure plateaus corresponding to absorption/desorption pressure plateaus of LaMgNi4 hydride.But the maximum hydrogen storage content of annealed alloys is lower than that of as-cast alloys.In consideration of the electrochemical properties,the annealed La0.8Pr0.2MgNi3.6Co0.4alloy exhibits a maximum discharge capacity of354.2 mAh·g-1.
文摘The effect of Mn substitution on phase structure,hydrogen hydriding/dehydriding properties(plateau pressure and slope)and reaction heat enthalpy of LaNi_(4.25-x)Al_(0.75)Mn_(x)alloys(x=0,0.25,0.35,0.45,0.55 and 0.65)were studied.The experimental results show that all LaNi_(4.25-x)Al_(0.75)Mn_(x)alloys have single phase and have the same hexagonal structure as that of LaNi5 alloy(CaCu_(5)type,P6/mmm).With increasing Mn substitution content,the cell parameters of LaNi_(4.25-x)Al_(0.75)Mn_(x)alloy greatly increase,but the maximum hydrogen storage capacity and the equilibrium absorption pressure of LaNi_(4.25-x)Al_(0.75)Mn_(x)alloy decrease from 1.38 wt.%to 1.18 wt.%and from 1.61 to 0.0712 MPa,respectively.Moreover,the hydrogen pressure plateau slope factorσincreases from 0.014 to 0.18,but the hysteresis factor is nearly constant.The heat enthalpy absolute value|ΔH_(plat)|increases from 46.7 kJ·mol^(-1)H2 to 56.1 kJ·mol^(-1)H_(2)as the Mn content x increases from 0 to 0.65.
