First-principles calculations based on density functional theory were performed to study the effect of alloying on the thermodynamic stability of MgH2 hydride （rutile and fluorite structures） with transitional meta...First-principles calculations based on density functional theory were performed to study the effect of alloying on the thermodynamic stability of MgH2 hydride （rutile and fluorite structures） with transitional metals （TM=Sc, Ti, Y） and group IIA elements （M=Ca, Sr, Ba）. The results indicate that fluorite structure of these hydrides are more stable than its relative rutile structure at low alloying content （less 20%）, structural destabilization of MgH2 appears in the alloying cases of Ti, Sr and Ba respectively. The structure-transition point from rutile structure to fluorite structure is at around 20% for MgH2-TM, and about 40% for MgH2-M. The formation enthalpy of fluorite Mg0.5Ba0.52 is about 0.3 eV and higher than that of fluorite MgH2, indicating that its hydrogen-desorption temperature at atmospheric pressure will be much lower than that of pure MgH2. Good consistency between experimental and calculated data suggests that above-adopted method is useful to predict structural transition and properties of MgH2 based hydrides for hydrogen storage.展开更多
Uniform-uispersed Ni nanoparticics(NPs)anchored on reduced graphene oxide(Ni@rGO)catalyzed MgH2(MH-Ni@rGO)has been fabricated by mechanical milling.The effects of milling time and Ni loading amount on the hydrogen sto...Uniform-uispersed Ni nanoparticics(NPs)anchored on reduced graphene oxide(Ni@rGO)catalyzed MgH2(MH-Ni@rGO)has been fabricated by mechanical milling.The effects of milling time and Ni loading amount on the hydrogen storage properties of MgH2 have been investigated.The initial hydrogen desorption temperature of MgH2 catalyzed by 10 wt.%Ni4@rGO6 for milling 5 h is significantly decreased from 251℃ to 190℃.The composite can absorb 5.0 wt.%hydrogen in 20 min at 100℃,while it can desorb 6.1 wt.%within 15 min at 300℃.Through the investigation of the phase transformation and dehydrogenation kinetics during hydrogen ab/desorption cycles,we found that the in-situ formed Mg2Ni/Mg2NiH4 exhibited better catalytic effect than Ni.When Ni loading amount is 45 wt.%,the rGO in Ni@rGO catalysts can prevent the reaction of Ni and Mg due to the strong interaction between rGO and Ni NPs.展开更多
A Fe modified Na2WO4 compound was synthesized by a solution impregnation method and was ball-milled with MgH2 to constitute a novel MgH2-Fe2O3/Na2WO4 composite. The effects of the Fe2O3/Na2WO4 additive on the hydrogen...A Fe modified Na2WO4 compound was synthesized by a solution impregnation method and was ball-milled with MgH2 to constitute a novel MgH2-Fe2O3/Na2WO4 composite. The effects of the Fe2O3/Na2WO4 additive on the hydrogen storage properties of MgH2 together with the corresponding mechanism were investigated. At 423 K, within the first 200 seconds, the hydrogen absorption amount of MgH2+20 wt% Fe2O3/Na2WO4 was almost 5 times that of pure MgH2. And at 573 K, its total hydrogen desorption amount was 7 times that for pure MgH2. Meanwhile, its onset dehydrogenation temperature was 110 K lower than that of pure MgH2. It was worth noting that the MgH2+20 wt% Fe/Na2WO4 presented the lower dehydrogenation reaction activation energy(Ea) of 35.9 kJ·mol^-1 compared to that of pure MgH2. The active MgWO4, Mg2 FeH6 and MgO formed during the milling process were responsible for the improvement of the hydrogen storage properties for MgH2.展开更多
MgH2 is a promising and popular hydrogen storage material.In this work,the hydrogen desorption reactions of a single Pd atom adsorbed MgH2(110)surface are investigated by using first-principles density functional theo...MgH2 is a promising and popular hydrogen storage material.In this work,the hydrogen desorption reactions of a single Pd atom adsorbed MgH2(110)surface are investigated by using first-principles density functional theory calculations.We find that a single Pd atom adsorbed on the MgH2(110)surface can significantly lower the energy barrier of the hydrogen desorption reactions from 1.802 eV for pure MgH2(110)surface to 1.154 eV for Pd adsorbed MgH2(110)surface,indicating a strong Pd single-atom catalytic effect on the hydrogen desorption reactions.Furthermore,the Pd single-atom catalysis significantly reduces the hydrogen desorption temperature from 573K to 367K,which makes the hydrogen desorption reactions occur more easily and quickly on the MgH2(110)surface.We also discuss the microscopic process of the hydrogen desorption reactions through the reverse process of hydrogen spillover mechanism on the MgH2(110)surface.This study shows that Pd/MgH2 thin films can be used as good hydrogen storage materials in future experiments.展开更多
文摘First-principles calculations based on density functional theory were performed to study the effect of alloying on the thermodynamic stability of MgH2 hydride （rutile and fluorite structures） with transitional metals （TM=Sc, Ti, Y） and group IIA elements （M=Ca, Sr, Ba）. The results indicate that fluorite structure of these hydrides are more stable than its relative rutile structure at low alloying content （less 20%）, structural destabilization of MgH2 appears in the alloying cases of Ti, Sr and Ba respectively. The structure-transition point from rutile structure to fluorite structure is at around 20% for MgH2-TM, and about 40% for MgH2-M. The formation enthalpy of fluorite Mg0.5Ba0.52 is about 0.3 eV and higher than that of fluorite MgH2, indicating that its hydrogen-desorption temperature at atmospheric pressure will be much lower than that of pure MgH2. Good consistency between experimental and calculated data suggests that above-adopted method is useful to predict structural transition and properties of MgH2 based hydrides for hydrogen storage.
基金This work was supported by the National Natural Science Foundation of China(Grant No.51671118)the research grant(No.16520721800 and No.19ZR1418400)from Science and Technology Commission of Shanghai Municipality.The authors gratefully acknowledge support for materials analysis and research from Instrumental Analysis and Research Center of Shanghai University.
文摘Uniform-uispersed Ni nanoparticics(NPs)anchored on reduced graphene oxide(Ni@rGO)catalyzed MgH2(MH-Ni@rGO)has been fabricated by mechanical milling.The effects of milling time and Ni loading amount on the hydrogen storage properties of MgH2 have been investigated.The initial hydrogen desorption temperature of MgH2 catalyzed by 10 wt.%Ni4@rGO6 for milling 5 h is significantly decreased from 251℃ to 190℃.The composite can absorb 5.0 wt.%hydrogen in 20 min at 100℃,while it can desorb 6.1 wt.%within 15 min at 300℃.Through the investigation of the phase transformation and dehydrogenation kinetics during hydrogen ab/desorption cycles,we found that the in-situ formed Mg2Ni/Mg2NiH4 exhibited better catalytic effect than Ni.When Ni loading amount is 45 wt.%,the rGO in Ni@rGO catalysts can prevent the reaction of Ni and Mg due to the strong interaction between rGO and Ni NPs.
基金Funded by the National Natural Science Foundation of China(No.51771164)Scientific Research Projects in Colleges and Universities in Hebei Province,China(No.ZD2019307)+2 种基金the Fundamental Research Funds for the Central Universities(No.3142019013)the Natural Science Foundation of Hebei Province of China(No.E2019508214)the Program for Top-notch Young Talents in University of Hebei Province(No.BJ2016043)
文摘A Fe modified Na2WO4 compound was synthesized by a solution impregnation method and was ball-milled with MgH2 to constitute a novel MgH2-Fe2O3/Na2WO4 composite. The effects of the Fe2O3/Na2WO4 additive on the hydrogen storage properties of MgH2 together with the corresponding mechanism were investigated. At 423 K, within the first 200 seconds, the hydrogen absorption amount of MgH2+20 wt% Fe2O3/Na2WO4 was almost 5 times that of pure MgH2. And at 573 K, its total hydrogen desorption amount was 7 times that for pure MgH2. Meanwhile, its onset dehydrogenation temperature was 110 K lower than that of pure MgH2. It was worth noting that the MgH2+20 wt% Fe/Na2WO4 presented the lower dehydrogenation reaction activation energy(Ea) of 35.9 kJ·mol^-1 compared to that of pure MgH2. The active MgWO4, Mg2 FeH6 and MgO formed during the milling process were responsible for the improvement of the hydrogen storage properties for MgH2.
基金supported by the National Key Basic Research Program(No.2011CB921404)National Natural Science Foundation of China(No.21421063,No.91021004,No.21233007,No.21803066)+2 种基金Strategic Priority Research Program of Chinese Academy of Sciences(No.XDC01000000)Research Start-Up Grants(No.KY2340000094)from University of Science and Technology of Chinathe Chinese Academy of Sciences Pioneer Hundred Talents Program
文摘MgH2 is a promising and popular hydrogen storage material.In this work,the hydrogen desorption reactions of a single Pd atom adsorbed MgH2(110)surface are investigated by using first-principles density functional theory calculations.We find that a single Pd atom adsorbed on the MgH2(110)surface can significantly lower the energy barrier of the hydrogen desorption reactions from 1.802 eV for pure MgH2(110)surface to 1.154 eV for Pd adsorbed MgH2(110)surface,indicating a strong Pd single-atom catalytic effect on the hydrogen desorption reactions.Furthermore,the Pd single-atom catalysis significantly reduces the hydrogen desorption temperature from 573K to 367K,which makes the hydrogen desorption reactions occur more easily and quickly on the MgH2(110)surface.We also discuss the microscopic process of the hydrogen desorption reactions through the reverse process of hydrogen spillover mechanism on the MgH2(110)surface.This study shows that Pd/MgH2 thin films can be used as good hydrogen storage materials in future experiments.
基金The project was supported by the National Natural Science Foundation of China(50971112,51001043)Scientific Research Projects in Colleges and Universities in Hebei Province,China(ZD2014004)~~
