INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2021
·Vol. 46
·期 66
·33186-33196
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IF 5.816
Xinjun Li,Yaokun Fu,Yichao Xie,Lian Cong,Han Yu,Lu Zhang,Yuan Li,Shumin Han
Additive doping is one of the effective methods to overcome the shortcomings of MgH 2 on the aspect of relatively high operating temperatures and slow desorption kinetics. In this paper, hollow g-C 3 N 4 (TCN) tubes with a diameter of 2 μm are synthesized through the hydrothermal and high-temperature pyrolysis methods, and then nickel is chemically reduced onto TCN to form Ni/TCN composite at 278 K. Ni/TCN is then introduced into the MgH 2 /Mg system by means of hydriding combustion and ball milling. The MgH 2 –Ni/TCN composite starts to release hydrogen at 535 K, which is 116 K lower than the as-milled MgH 2 (651 K). The MgH 2 –Ni/TCN composite absorbs 5.24 wt% H 2 within 3500 s at 423 K, and takes up 3.56 wt% H 2 within 3500 s, even at a temperature as low as 373 K. The apparent activation energy ( E a ) of the MgH 2 decreases from 161.1 to 82.6 kJ/mol by the addition of Ni/TCN. Moreover, the MgH 2 –Ni/TCN sample shows excellent cycle stability, with a dehydrogenation capacity retention rate of 98.0% after 10 cycles. The carbon material enhances sorption kinetics by dispersing and stabilizating MgH 2 . Otherwise, the phase transformation between Mg 2 NiH 4 and Mg 2 NiH 0.3 accelerates the re/dehydrogenation reaction of the composite.
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高影响因子
Journal of Physical Chemistry C
·
2015
·
IF 4.772
Liuting Zhang,Xuezhang Xiao,Chenchen Xu,Jiaguang Zheng,Xiulin Fan,Jie Shao,Shouquan Li,Hongwei Ge,Qidong Wang,Lixin Chen
Magnesium hydride is widely investigated because of its high hydrogen storage capacity. However, the unfavorable thermodynamic and kinetic barriers hinder its practical application. To ease these problems, three kinds of NbHx nanoparticles were prepared by wet-chemical methods and then introduced into MgH2 for catalytically enhancing its hydrogen storage properties in this work. The results show that all the NbHx nanoparticles are effective in promoting the de-/rehydrogenation kinetics of MgH2, and the three NbHx doped MgH2 composites can desorb 7.0 wt % H2 within 9 min at 300 °C while ball milled MgH2 only releases 0.2 wt % H2 in 9 min and 4.1 wt % H2 even in 200 min. Interestingly, the significant hydrogen absorption by NbHx doped MgH2 under lower temperature ranging from 50 to 100 °C was observed; thus, MgH2/c-NbHx sample can uptake about 4.0 wt % H2 at 100 °C. It is found that the more disordered the structure and smaller the size of the NbHx particles, the better is the catalytic effect on hydrogen storage performances of MgH2. Analyses of XRD, XPS, and TEM results indicate that the NbHx remains stable in the ball milling and following de-/rehydrogenation process and act as active catalytic species in improving hydrogen storage performance of MgH2. Moreover, a mechanism is proposed to understand how the nanosized NbHx acted as charge transfer between Mg2+ and H–, which contributes to the significantly improved hydrogen storage performances of MgH2. It is believed that the use of Nb-based nanoparticles as catalysts would greatly promote the development of the practical applications of MgH2 for hydrogen storage.
研究领域:
材料科学
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氢气储存
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纳米催化
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能量存储
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高影响因子
Journal of Magnesium and Alloys
·
2022
·
IF 11.813
Yongyang Zhu,Mili Liu,liming Zeng,Yin Wang,Daifeng Wu,Rui Li,Qing Zhou,Renheng Tang,Fangming Xiao
The hydrolysis of MgH 2 delivers high hydrogen capacity (15.2 wt%), which is very attractive for real-time hydrogen supply. However, the formation of a surface passivation Mg(OH) 2 layer and the large excess of H 2 O required to ensure complete hydrolysis are two key challenges for the MgH 2 hydrolysis systems. Now, a low-cost method is reported to synthesize MgH 2 @Mg(BH 4 ) 2 composite via ball-milling MgH 2 with cheap and widely available B 2 O 3 (or B(OH) 3 ). By adding small amounts of B 2 O 3 , the in-situ formed Mg(BH 4 ) 2 could significantly promote the hydrolysis of MgH 2 . In particular, the MgH 2 –10 wt% B 2 O 3 composite releases 1330.7 mL·g −1 H 2 (close to 80% theoretical hydrogen generation H 2 ) in H 2 O and 1520.4 mL·g −1 H 2 (about 95%) in 0.5 M MgCl 2 in 60 min at 26 °C with hydrolysis rate of 736.9 mL·g −1 ·min −1 and 960.9 mL·g −1 ·min −1 H 2 during the first minute of the hydrolysis, respectively. In addition, the MgCl 2 solution allows repeated use by filtering and exhibits high cycle stability (20 cycles), therefore leading to much reduced capacity loss caused by the excess H 2 O. We show that by introducing B 2 O 3 and recycling the 0.5 M MgCl 2 solution, the system hydrogen capacity can approach 5.9 wt%, providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.
研究领域:
材料科学
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能源化学
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无机合成
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氢能技术
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表面工程
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DOI
高影响因子
Journal of the American Chemical Society
·
2024
·
IF 14.4
Jiyue Zhang,Wenda Wang,Xiaowei Chen,Jinlong Jin,Xiaojun Yan,Jianmei Huang
As an efficient and clean energy carrier, hydrogen is expected to play a key role in future energy systems. However, hydrogen-storage technology must be safe with a high hydrogen-storage density, which is difficult to achieve. MgH2 is a promising solid-state hydrogen-storage material owing to its large hydrogen-storage capacity (7.6 wt %) and excellent reversibility, but its large-scale utilization is restricted by slow hydrogen-desorption kinetics. Although catalysts can improve the hydrogen-storage kinetics of MgH2, they reduce the hydrogen-storage capacity. Single-atom catalysts maximize the atom utilization ratio and the number of interfacial sites to boost the catalytic activity, while easy aggregation at high temperatures limits further application. Herein, we designed a single-atom Ni-loaded TiO2 catalyst with superior thermal stability and catalytic activity. The optimized 15wt%-Ni0.034@TiO2 catalyst reduced the onset dehydrogenation temperature of MgH2 to 200 °C. At 300 °C, the H2 released and absorbed 4.6 wt % within 5 min and 6.53 wt % within 10 s, respectively. The apparent activation energies of MgH2 dehydrogenation and hydrogenation were reduced to 64.35 and 35.17 kJ/mol of H2, respectively. Even after 100 cycles of hydrogenation and dehydrogenation, there was still a capacity retention rate of 97.26%. The superior catalytic effect is attributed to the highly synergistic catalytic activity of single-atom Ni, numerous oxygen vacancies, and multivalent Tix+ in the TiO2 support, in which the single-atom Ni plays the dominant role, accelerating electron transfer between Mg2+ and H– and weakening the Mg–H bonds. This work paves the way for superior hydrogen-storage materials for practical unitization and also extends the application of single-atom catalysis in high-temperature solid-state reactions.
研究领域:
储能技术
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催化化学
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材料科学
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纳米技术
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氢能技术
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固态化学
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Runyu Zhang,Yudong Sui,Lina Han,Yehua Jiang
In this work, graphene oxide (GO) was integrated into the established synthesis route of Ni-TMA MOF. The results demonstrate that the resulting Ni-TMA MOF/GO shows pronounced catalytic activity toward the hydrogen sorption behavior of MgH 2 . Morphological characterization indicates that the as-prepared Ni-TMA MOF/GO possesses a dandelion-like microspherical architecture, featuring an overall spherical profile and a hierarchically porous interior with abundant voids. This structural configuration provides enlarged specific surface area and a high density of accessible active sites. Among all investigated composites, MgH 2 -3 wt.% Ni-TMA MOF/GO delivers the best overall hydrogen-storage performance. At 573 K under 2.6 MPa H 2 , it reaches a maximum hydrogen uptake of 6.3 wt%. The composite also exhibits rapid absorption kinetics, taking up 6.0 wt% H 2 within 1 min. In addition, it maintains good cycling durability: after 100 hydrogenation/dehydrogenation cycles, the reversible capacity remains 5.8 wt%.
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产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Cheng Lv,Jiayan Huang,Yuang QI,Qingjie He,Yazhou Wang,Cuili Xiang,Yongjin Zou,Fen Xu,Lixian Sun
MgH₂ is one of the most promising materials for solid hydrogen storage and is environmentally friendly primarily owing to its high mass hydrogen storage density (7.6 %). However, the application and development of MgH₂ are limited by its sluggish kinetics, requiring high processing temperatures. In this study, we prepared Ni/Co-co-doped Ti 2 VC 2 bimetallic MXene nanosheets via etching and the hydrothermal method. These nanosheets were then doped into MgH₂, resulting in drastically improved hydrogen storage properties. The MgH₂-based composite hydrogen storage materials doped with 10 wt% Ni/Co–Ti 2 VC₂ (TVCNC) commenced hydrogen emission from 183 °C and could emit 6.65 wt% hydrogen at 300 °C. During the rehydrogenation test, the composites could still absorb hydrogen at 5.0 wt% within a 10 min window at a hydrogen pressure of 20 bar at 125 °C. Moreover, the hydrogen absorption and emission kinetics of the doped MgH₂ were considerably improved. This improvement could be ascribed to the significantly increased specific surface area of the MXene nanosheets after etching, which increased the number of active sites on the surface to accelerate the reaction, thereby accelerating hydrogen adsorption and emission. In addition, the migration of electrons between the multivalent Ti ions as well as between Ni and Co helped accelerate bond cleavage between magnesium and hydrogen, thereby enhancing the kinetic properties. Ni/Co co-doping produced Mg 2 Ni alloys with magnesium via hydrogen adsorption and emission, thus improving the reaction kinetics of the composites.
研究领域:
材料科学
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能源储存
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产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2025
·
IF 14.9
Cenyu Yang,Chen Hu,Xiaoyu Wu,Yao Pang,Xiaofang Liu,Jianglan Shui
Metallic single-atom catalysts (SACs) have demonstrated high activity and potential in enhancing the hydrogen storage properties of MgH 2 . However, previous reports primarily focus on supported SACs, which often suffer from insufficient contact between single-atom active sites and hydrogen storage materials. In this study, the precursor Mo(CO) 6 is uniformly dispersed on the surface of MgH 2 via impregnation adsorption, leading to the formation of alloy-type Mo single atoms after hydrogenation/dehydrogenation activation. This alloy structure enables zero-distance contact between catalytic sites and the hydrogen storage material, facilitating electron exchange and hydrogen transfer between the Mo sites and MgH 2 . The MgH 2 loaded with Mo single atoms (Mo 1 -MgH 2 ) exhibits excellent hydrogen absorption and desorption properties, with the initial hydrogen release temperature lowered from 323 to 218 °C. At 250 °C, Mo 1 -MgH 2 absorbs over 6.77 wt% of hydrogen within 1 min and releases over 5.85 wt% within 4 h. During 10 cycles of hydrogenation and dehydrogenation reactions, Mo 1 -MgH 2 maintains nearly 100% capacity and shows stable kinetics. This work provides new insights into the design and fabrication of catalysts for hydrogen storage materials.
研究领域:
材料科学
·
催化化学
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2022
·
IF 7.139
Chengguo Yan,Xu Lu,Jiaguang Zheng,Yan Zhang,Qinan Wu,Fuying Wu,Liuting Zhang
MgH 2 has been extensively regarded as a low-cost hydrogen storage material with high gravimetric hydrogen capacity of approximately 7.6 wt%. However, the hydrogen release and absorption kinetics in MgH 2 still needs further improving. For the first time, the catalytic impacts of a new dual-cation metal fluoride K 2 TaF 7 upon the hydrogen storage characteristics of MgH 2 have been investigated in this work. With only 1 wt% K 2 TaF 7 dopant , the initial dehydrogenation temperature of MgH 2 was lowered by about 130 °C, releasing more than 7.3 wt% hydrogen totally. The desorption activation energy of MgH 2 + 1 wt% K 2 TaF 7 composite was decreased to 107.2 ± 1.2 kJ mol −1 . Besides, at 190 °C, the dehydrogenated MgH 2 + 1 wt% K 2 TaF 7 sample could absorb 6.56 wt% H 2 , while pristine MgH 2 re-absorbed only 3.45 wt% H 2 . Further studies revealed that K 2 TaF 7 could react with MgH 2 during dehydrogenation and produce symbiotic hydrides KMgH 3 and TaH 0.8 , which could play the role of hydrogen pumps during hydrogen release and uptake. The cooperative catalysis between the hydrogen pump effect and the active interface in the multi-hydride area significantly enhanced the reversible hydrogen storage in the MgH 2 +1 wt% K 2 TaF 7 composite. This study provides new thinking for novel catalysts to elevate the hydrogen storage performance of MgH 2 .
研究领域:
材料科学
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能源工程
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DOI
高影响因子
ACS Nano
·
2026
·
IF 16
Huafeng Fu,Shiteng Long,Jia Hu,Jiehua Li,Hansong Xue,Yu’an Chen,Fusheng Pan
To address the challenges of high hydrogen release temperatures, sluggish kinetics, and inadequate cycling performance of magnesium hydride (MgH2), we developed the niobium-based bimetallic compound catalyst CuNb2O6 with excellent catalytic performance. It was found that the MgH2/CuNb2O6 composite material achieved 4.28 wt % hydrogen uptake within 10 min at 100 °C, and even at a lower temperature of 50 °C, it has 2 wt % hydrogen absorption capacity within 60 min, showing excellent hydrogen absorption performance. For hydrogen desorption, the MgH2/CuNb2O6 composite material demonstrated exceptional midtemperature hydrogen release kinetics, with 4.65 wt % hydrogen released within 20 min at 225 °C. The apparent activation energy for hydrogen release of MgH2/CuNb2O6 was determined to be 50.95 kJ/mol, which was approximately 66.4% less than that of ball-milled magnesium hydride. Cyclic testing further confirmed the stability of the MgH2/CuNb2O6 composite, with its hydrogen storage capacity stabilizing at 5.21 wt % after 50 cycles. Catalytic mechanism studies revealed that the MgH2/CuNb2O6 composite undergoes in situ reconstruction of multiple-phase catalytically active species, which effectively improved the hydrogen storage performance of MgH2. This work innovatively constructed a representative Mg2Cu@NbO2 heterojunction, and the results showed that hydrogen molecules were significantly activated at the interface, demonstrating the synergistic catalytic effect between the Cu and Nb species. This study provides a possible approach for designing high-efficiency catalysts for magnesium-based hydrogen storage materials.
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DOI
PubMed
高影响因子
TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA
·
2021
·
IF 2.917
Yan CHEN,Hao-yu ZHANG,Fu-ying WU,Ze SUN,Jia-guang ZHENG,Liu-ting ZHANG,Li-xin CHEN
Mn nanoparticles (nano-Mn) were successfully synthesized and doped into MgH 2 to improve its de/hydrogenation properties. Compared with MgH 2 , the onset desorption temperature of 10 wt.% nano-Mn modified MgH 2 was decreased to 175 °C and 6.7, 6.5 and 6.1 wt.% hydrogen could be released within 5, 10 and 25 min at 300, 275 and 250 °C, respectively. Besides, the composite started to take up hydrogen at room temperature and absorbed 2.0 wt.% hydrogen within 30 min at low temperature of 50 °C. The hydrogenation activation energy of MgH 2 was reduced from (72.5±2.7) to (18.8±0.2) kJ/mol after doping with 10 wt.% nano-Mn. In addition, the MgH 2 + 10 wt.% nano-Mn composite exhibited superior cyclic property, maintaining 92% initial capacity after 20 cycles.
研究领域:
材料科学
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能源科学
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DOI
高影响因子
Progress in Natural Science-Materials International
·
2021
·
IF 3.607
Yaokun Fu,Zhenmin Ding,Lu Zhang,Hongming Zhang,Wenfeng Wang,Yuan Li,Shumin Han
The application of magnesium hydride (MgH 2 ) is limited due to the high reaction temperature and slow kinetics during dehydrogenation. In order to ameliorate the dehydrogenation property of MgH 2 , MgC 0.5 Co 3 compound with induction and catalytic effects was introduced into the Mg/MgH 2 system via ball-milling and hydriding combustion methods in present study. Compared to the pure MgH 2 , the initial hydrogen desorption temperature of MgH 2 –MgC 0.5 Co 3 composite lowered to 237 °C, decreasing by 141 °C. At 325 °C the MgH 2 –MgC 0.5 Co 3 composite could release 4.38 wt% H 2 within 60 min, which is 4.5 times the capacity of hydrogen released by as milled-MgH 2 . Besides, the hydrogen desorption activation energy of the MgH 2 –MgC 0.5 Co 3 composite was dramatically reduced to 126.7 ± 1.4 kJ/mol. It was observed that MgC 0.5 Co 3 was chemically stable and no chemical transformation occurred after cycling, which not only inhibited the nucleation and growth of composite particles, but also had a positive effect on the hydrogen desorption reaction of MgH 2 due to its catalytic effect. This study may provide references for designing and synthesizing Mg–C–Co alloy compound for the Mg-based hydrogen storage area.
研究领域:
材料科学
·
能源存储
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产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2026
·
IF 6.3
Haotian Yu,Zeming Yuan,Qiang Han,Jiaxin Li,Tao Li
Magnesium hydride (MgH₂) is a promising solid-state hydrogen storage material for large-scale applications, owing to its high gravimetric capacity and natural abundance. However, its practical implementation is hindered by high thermodynamic stability and sluggish kinetics, originating from strong Mg–H bonds and limited hydrogen diffusion, which typically require elevated temperatures and prolonged cycling. Moreover, existing catalytic systems frequently suffer from inadequate dispersion, interfacial instability during cycling, and a lack of quantitative understanding of the cooperative effects between oxygen vacancies and multivalent Ce. To address these issues, a Co/CeO₂@C composite catalyst was synthesized through a hydrothermal–calcination method and incorporated into MgH₂ via ball milling. The microstructural characteristics, hydrogen storage properties, and underlying reaction mechanisms were systematically investigated using X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Pressure-Composition-Temperature (PCT) tests and Johnson–Mehl–Avrami–Kolmogorov (JMAK) kinetic fitting. Evaluation based on microstructure, hydrogen uptake/release capacities at varying doping levels, and corresponding activation energies revealed that the composite with 6 wt.% Co/CeO₂@C exhibited a hydrogen uptake of 5.74 wt.%. At 300 °C, the 6 wt.% composite released 5.15 wt.% H₂ within 100 min, demonstrating its superior dehydrogenation performance at this doping level. The activation energy decreased from 145.43 kJ·mol⁻¹ to 93.35 kJ·mol⁻¹, and the thickness loss due to interfacial degradation was less than 1 nm. This enhancement is ascribed to a triple synergistic mechanism of “hydrogen spillover–electron transfer–confinement stabilization”. Co offers active sites for hydrogen dissociation, oxygen vacancies in CeO₂ promote hydrogen diffusion, and the carbon matrix suppresses particle agglomeration. This study contributes to quantitatively understanding the synergy between oxygen vacancies and multivalent Ce, establishes a clear “microstructure–catalytic mechanism–macro-performance” correlation, and offers new insights for the practical deployment of Mg-based hydrogen storage materials. It is noted, however, that the key findings presented herein align closely with trends reported in prior literature, highlighting the consistent performance landscape observed for this class of catalytic modifiers.
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高影响因子
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