High hydrogen desorption temperature and sluggish reaction kinetics are the major limitations for the practical application of MgH_(2).In this study,Co particles with a face centered cubic(FCC)structure and a hexagona...High hydrogen desorption temperature and sluggish reaction kinetics are the major limitations for the practical application of MgH_(2).In this study,Co particles with a face centered cubic(FCC)structure and a hexagonal close packed(HCP)structure were prepared facilely and proved to be good catalysts for magnesium hydride.Co particles with FCC structure presented better catalytic effect on MgH_(2)than that with HCP structure.Both 7%(mass)Co FCC and HCP particle modified MgH_(2)decreased the initial dehydrogenation temperature from 301.3℃ to approximately 195.0℃,but 7%(mass)Co with FCC structure modified MgH_(2)has a faster desorption rate,and around 6.5%(mass)H_(2)was desorbed in 10 min at325℃.Hydrogen uptake was detected at 70℃ under 3.25 MPa hydrogen pressure and 6.0%(mass)H_(2)was recharged in 40 min at 150℃.The hydrogen desorption and absorption activation energy for 7%(mass)FCC Co modified MgH_(2)was significantly decreased to(76.6±8.3)kJ·mol^(-1) and(68.3±6.0)kJ·mol^(-1),respectively.Thermodynamic property was also studied,the plateau pressures of MgH_(2)+7%(mass)FCC Co were determined to be 0.14,0.28,0.53 and 0.98 MPa for 300℃,325℃,350℃ and375℃.The decomposition enthalpy of hydrogen(ΔH)for MgH_(2)+7%(mass)FCC Co was(80.6±0.1)kJ·mol^(-1),5.8 kJ·mol^(-1)lower than that of as-prepared MgH_(2).Moreover,cycling performance for the first20 cycles revealed that the reaction kinetics and capacity of MgH_(2)-FCC Co composite remained almost unchanged.The result of density functional theory calculation demonstrated that cobalt could extract the Mg AH bond and reduced the decompose energy of magnesium hydride.Our paper can be presented as a reference for searching highly effective catalysts for hydrogen storage and other energy-related research fields.展开更多
基金support from the National Natural Science Foundation of China(Grant Nos.51801078 and 21701083)the Natural Science Foundation of Jiangsu Province(Grant No.BK20180986 and BK20210884)。
文摘High hydrogen desorption temperature and sluggish reaction kinetics are the major limitations for the practical application of MgH_(2).In this study,Co particles with a face centered cubic(FCC)structure and a hexagonal close packed(HCP)structure were prepared facilely and proved to be good catalysts for magnesium hydride.Co particles with FCC structure presented better catalytic effect on MgH_(2)than that with HCP structure.Both 7%(mass)Co FCC and HCP particle modified MgH_(2)decreased the initial dehydrogenation temperature from 301.3℃ to approximately 195.0℃,but 7%(mass)Co with FCC structure modified MgH_(2)has a faster desorption rate,and around 6.5%(mass)H_(2)was desorbed in 10 min at325℃.Hydrogen uptake was detected at 70℃ under 3.25 MPa hydrogen pressure and 6.0%(mass)H_(2)was recharged in 40 min at 150℃.The hydrogen desorption and absorption activation energy for 7%(mass)FCC Co modified MgH_(2)was significantly decreased to(76.6±8.3)kJ·mol^(-1) and(68.3±6.0)kJ·mol^(-1),respectively.Thermodynamic property was also studied,the plateau pressures of MgH_(2)+7%(mass)FCC Co were determined to be 0.14,0.28,0.53 and 0.98 MPa for 300℃,325℃,350℃ and375℃.The decomposition enthalpy of hydrogen(ΔH)for MgH_(2)+7%(mass)FCC Co was(80.6±0.1)kJ·mol^(-1),5.8 kJ·mol^(-1)lower than that of as-prepared MgH_(2).Moreover,cycling performance for the first20 cycles revealed that the reaction kinetics and capacity of MgH_(2)-FCC Co composite remained almost unchanged.The result of density functional theory calculation demonstrated that cobalt could extract the Mg AH bond and reduced the decompose energy of magnesium hydride.Our paper can be presented as a reference for searching highly effective catalysts for hydrogen storage and other energy-related research fields.
