Journal of Materials Chemistry A
·
2013
·Vol. 1
·期 37
·11368-11375
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IF 0
Xiulin Fan,Xuezhang Xiao,Lixin Chen,Xinhua Wang,Shouquan Li,Hongwei Ge,Qidong Wang
LiBH4–MgH2 system in a 2 : 1 molar ratio constitutes a representative reactive hydride composite (RHC) for hydrogen storage. However, sluggish kinetics and poor reversibility hinder the practical applications. To ease these problems, amorphous TiB2 and NbB2 nanoparticles were synthesized and employed as catalysts for the 2LiBH4–MgH2 system. Isothermal de-/rehydrogenation and temperature programmed mass spectrometry (MS) measurements show that amorphous TiB2 and NbB2 nanoparticles can significantly improve the hydrogen storage performance of the 2LiBH4–MgH2 system. 9 wt% hydrogen can be released within only 6 min for nanoTiB2-doped 2LiBH4–MgH2, while for the undoped composite limited hydrogen of 3.9 wt% is released in 300 min at 400 °C. The dehydrogenation activation energies for the first and second steps are dramatically reduced by 40.4 kJ mol−1 and 35.2 kJ mol−1 after doping with nanoTiB2. It is believed that TiB2 and NbB2 nanoparticles can first catalyze the dehydrogenation of MgH2, and then induce the decomposition of LiBH4 and meanwhile act as nucleation agents for MgB2, thereby greatly enhancing the kinetics of dehydrogenation. The present study gives clear evidence for the significant performance of transition metal boride species in doped RHCs, which is critically important for understanding the mechanism and further improving the hydrogen storage properties of RHCs.
研究领域:
材料科学
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化学工程
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DOI
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2022
·
IF 7.139
Quanhui Hou,Jiaqi Zhang,XinTao Guo,Guanzhong Xu,Xinglin Yang
In this study, a low-cost biomass charcoal (BC)-based nickel catalyst (Ni/BC) was introduced into the MgH 2 system by ball-milling. The study demonstrated that the Ni/BC catalyst significantly improved the hydrogen desorption and absorption kinetics of MgH 2 . The MgH 2 + 10 wt% Ni/BC-3 composite starts to release hydrogen at 187.8 °C, which is 162.2 °C lower than the initial dehydrogenation temperature of pure MgH 2 . Besides, 6.04 wt% dehydrogenation can be achieved within 3.5 min at 300 °C. After the dehydrogenation is completed, MgH 2 + 10 wt% Ni/BC-3 can start to absorb hydrogen even at 30 °C, which achieved the absorption of 5 wt% H 2 in 60 min under the condition of 3 MPa hydrogen pressure and 125 °C. The apparent activation energies of dehydrogenation and hydrogen absorption of MgH 2 + 10 wt% Ni/BC-3 composites were 82.49 kJ/mol and 23.87 kJ/mol lower than those of pure MgH 2 , respectively, which indicated that the carbon layer wrapped around MgH 2 effectively improved the cycle stability of hydrogen storage materials. Moreover, MgH 2 + 10 wt% Ni/BC-3 can still maintain 99% hydrogen storage capacity after 20 cycles. XRD, EDS , SEM and TEM revealed that the Ni/BC catalyst evenly distributed around MgH 2 formed Mg 2 Ni/Mg 2 NiH 4 in situ, which act as a “hydrogen pump” to boost the diffusion of hydrogen along with the Mg/MgH 2 interface. Meanwhile, the carbon layer with fantastic conductivity enormously accelerated the electron transfer . Consequently, there is no denying that the synergistic effect extremely facilitated the hydrogen absorption and desorption kinetic 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
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yaokun Fu,Zhichao Yu,Sanyang Guo,Yuan Li,Qiuming Peng,Lu Zhang,Shikui Wu,Shumin Han
Catalyst doping modification has become an important strategy to solve the high desorption temperature and sluggish kinetics issues of magnesium hydride (MgH 2 ) for further commercial application. Herein, we report a novel strategy by exploiting a catalyst with the “magnesophilic” transition metal and “magnesiphobic” carbon material to construct a MgH 2 -catalysts-carbon layer hydrogen storage material, where the bimetallic NiFe nanoparticles are supported atop the bamboo-like carbon nanotubes (NiFe@CNT) via calcination. The experimental results show that the built MgH 2 -NiFe@CNT composite can absorb 4.06 and 3.25 wt% H 2 at 373 and 348 K, respectively, while the milled-MgH 2 almost no longer absorbs H 2 and takes only 0.82 wt% even at 423 K. More importantly, the initial desorption temperature of the MgH 2 -NiFe@CNT composite reduces to 498 K by 122 K in contrast to the milled-MgH 2 , and the dehydrogenation activation energy decreases from 151.8 to 49.7 kJ mol −1 . Ex situ structural characterization and theoretical calculation show that the synergistic effects of the “hydrogen pump” role of Mg 2 Ni/Mg 2 NiH 4 and “hydrogen gateway” role of α-Fe, as well as the good dispersion function of carbon nanotubes generated in situ from the NiFe@CNT, contribute the excellent hydrogen storage properties of the MgH 2 -NiFe@CNT composite. This study provides new insights into the modification of MgH 2 by carbon-supported transition metal catalysts.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2023
·
IF 10.9
Samuel Guemou,Liuting Zhang,Shuai Li,Yiqun Jiang,Tao Zhong,Zichuan Lu,Ren Zhou,Fuying Wu,Qian Li
The design of an excellent active catalyst to improve the sluggish kinetic and thermodynamic properties of magnesium hydride (MgH 2 ) remains a great challenge to achieve its practical application. In this study, a novel Ni-Nb/rGO nanocomposite catalyst was successfully prepared by one-spot hydrothermal and subsequent calcination methods. The novel Ni-Nb/rGO nanocomposite exhibits an exceptional catalytic effect on improving MgH 2 sorption properties. Specifically, the onset desorption temperature of MgH 2 + 10 wt% Ni-Nb/rGO composite is reduced to 198 °C, much lower than that of undoped MgH 2 (330 °C). Interestingly, the composite can release 5.0, 5.9, and 6.0 wt% H 2 within 10 min at 245, 260, and 275 °C, respectively. Furthermore, the dehydrogenated MgH 2 + 10 wt% Ni-Nb/rGO composite starts to absorb hydrogen even at room temperature with approximate 2.75 wt% H 2 uptake at 75 °C under 3 MPa H 2 pressure within 30 min and exhibits excellent stability by maintaining 6.0 wt% hydrogen content after 20 cycles at 300 °C. Chou's model suggests that the de/hydrogenation kinetics of Ni-Nb/rGO-modified MgH 2 switches from surface penetration model to diffusion model at lower temperatures. Additionally, the activation energies ( E a ) for the de/hydrogenation of MgH 2 + 10 wt% Ni-Nb/rGO are reduced to 57.8 kJ/mol and 33.9 kJ/mol, which are significantly lower than those of undoped MgH 2 . The work demonstrates that the addition of a novel ternary Ni-Nb/rGO catalyst is an effective strategy to not only boost the sorption kinetics of MgH 2 but also maintain its cycling property.
研究领域:
材料科学
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能源化学
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DOI
高影响因子
ChemistrySelect
·
2024
·Vol. 9
·期 29
·e202401592
·
IF 1.9
Yazhou Wang,Shunxiang Wang,Qingjie He,Weiqi Sun,Jiaao Wu,Yongpeng Xia,Cuili Xiang,Yongjin Zou,Fen Xu,Lixian Sun
Graphical We employ a hydrothermal method and high-temperature calcination to prepare well-dispersed NiTiO 3 nanoparticles with smaller than 20 nm. The NiTiO 3 nanoparticles show good catalytic effect on hydrogen storage of MgH 2 . The further structural analysis shows that the excellent hydrogen storage performance of MgH 2 -NiTiO 3 benefits from multivalent state of titanium and Mg 2 Ni/Mg 2 NiH 4 . Magnesium hydride (MgH 2 ) has gained significant consideration as a cost-effective solid-state hydrogen-storage material with a substantial hydrogen capacity. However, its practical applications are impeded by its poor kinetics and high thermal stability. In this study, we employed a hydrothermal method and high-temperature calcination to prepare well-dispersed NiTiO 3 nanoparticles smaller than 20 nm. Next, we investigated the effect of the NiTiO 3 nanoparticles for educating the hydrogen storage performance of MgH 2 . The synergistic catalytic effect of multivalent titanium and Mg 2 Ni/Mg 2 NiH 4 enhanced hydrogen storage performance of the MgH 2 system. The addition of 5 wt % NiTiO 3 lowered the initial hydrogen evolution temperature of MgH 2 to 194 °C. After 12 minutes at 275 °C, the 5 wt % NiTiO 3 -MgH 2 composites released 6.1 wt % of hydrogen. The dehydrogenation activation energy ( E a ) of the 5 wt % NiTiO 3 -MgH 2 composites decreased significantly to 38.78±2.1 kJ/mol. Furthermore, hydrogen uptake of 5 wt % NiTiO 3 -MgH 2 at 125 °C reaches 5.1 wt % in 300 s under hydrogen pressure of 20 bar. These findings introduce an innovative concept for preparing high active catalysts for improving the dehydrogenation/hydrogenation kinetics of MgH 2 .
研究领域:
材料科学
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能源存储
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Fei Li,Zhuonan Huang,Yuqi Wang,Le Wu,Sinan Guan,Yue Wang,Ying Liu,Shuang Cheng,Jinlei Wu,Jun Hu,Xin Ding
Magnesium hydride (MgH 2 ) has garnered substantial consideration mainly due to its high gravimetric density and reliable resource, whereas its poor thermodynamics and kinetics for absorbing/releasing hydrogen restricts the largescale application. Certain catalysts have demonstrated remarkable activity in enhancing the hydrogen storage capabilities of MgH 2 . In this work, the nanoparticle-cumulated flower-like CoFe@C coated catalysts (denoted as CoFe@C) are controllably synthesized as expected by the MOF (Metal-Organic Farmwork) in-suit decomposition method at 800 °C, which exhibits an average pore size of 18.63 nm. Meanwhile, the particle size for the as-prepared CoFe alloy coated in carbon layer are approximately 10–20 nm, and the as-prepared samples are introduced to promote the de/rehydrogenation properties of MgH 2 at relatively lower temperatures. Due to the synergistic interaction of CoFe alloy nanoparticles serving as active sites and agglomeration resistance of carbon layers, the MgH 2 composites doped with CoFe@C-800 could initialize its decomposition process at 175.9 °C, and may desorb 6.0 wt% H 2 at 300 °C in 400 s. Additionally, the peak temperature and apparent activation energy during dehydrogenation decline significantly (with 35 % and 38 %, respectively). Furthermore, theoretical analysis results indicate a higher catalytic activity for the carbon-coated CoFe alloy owing to the synergetic effect between CoFe nanocomposite & carbon layer, which can facilitate the bond extension and strength decrease of Mg-H bonding. In brief, using MOF may derive transition metal and carbon layer, which could be a promising approach to stimulating the hydrogen storage properties of MgH 2 .
研究领域:
材料科学
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能源存储与转换
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Tengyu Zhang,Meijia Liu,Can Li,Jiwei Zhang,Hui Gao,Fangong Kong,Xuezhang Xiao
Magnesium hydride (MgH 2 ) emerges as a cost-effective and high-capacity hydrogen storage candidate. Despite these advantages, its utilization is constrained by sluggish reaction kinetics and the requirement for elevated operating temperatures. In this study, we aim to address these limitations by investigating the synergistic catalytic effect of yttrium fluoride (YF 3 ) and nickel-loaded nitrogen self-doped porous carbon (Ni/C) as catalysts for MgH 2 . Co-doping with YF 3 and Ni/C reduces the dehydrogenation activation energy to 74.56 kJ/mol, enabling 5.22 wt% H 2 desorption within 5 min at 300 °C. Notably, the system exhibits enhanced low-temperature reaction kinetics, with the MgH 2 -YF 3 + Ni/C composite releasing 5.74 wt% H 2 at 250 °C within 30 min. At 50 °C, the co-doped composite achieves a hydrogen storage capacity of 5.18 wt% within 4 h, whereas the composite with Ni/C only absorbs 3.72 wt% H 2 . Moreover, the MgH 2 -YF 3 + Ni/C shows 98.4 % capacity retention after 30 cycles, indicating excellent reversibility. Mechanistic analysis reveals that the outstanding catalytic performance originates from the synergistic effect among YH 2 /YH 3 , MgF 2 , Mg 2 Ni/Mg 2 NiH 4 , and nitrogen-doped carbon. YH 2 /YH 3 and Mg 2 Ni/Mg 2 NiH 4 act as “hydrogen pump”, providing more active sites for the reaction. Additionally, MgF 2 functions as an electron transfer medium, weakening the Mg-H bond. The introduction of nitrogen self-doped porous carbon improves the dispersion of the catalyst and prevents aggregation, enhancing the dissociation of hydrogen molecules. This work demonstrates a promising strategy for improving the low-temperature hydrogen storage performance of MgH 2 and offers insights into the design of rare-earth fluoride-based catalysts.
研究领域:
材料科学
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能源化学
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催化化学
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DOI
高影响因子
Journal of Magnesium and Alloys
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2025
·
IF 13.8
Zexuan Yang,Yazhou Wang,Xia Lin,Yongjin Zou,Cuili Xiang,Fen Xu,Lixian Sun,Yong Shen Chua
Magnesium-based hydrogen storage materials, such as MgH 2 , have attracted considerable attention because of its superior hydrogen storage capacities, inexpensive, and excellent reversibility. However, their high thermodynamic stabilities and slow kinetics lead to relatively high desorption temperatures, which severely limit the wide application of MgH 2 . In this study, the inclusion of vanadium induced the formation Ni-Co metal–organic frameworks (MOF) from a NiCo layered double hydroxide (LDH), thereby increasing the number of defects and vacancies, and improving the hydrogen storage properties of MgH 2 . The synthesized NiCo-MOF/V-O-doped MgH 2 system demonstrates excellent hydrogen storage capacity. More specifically, 5 wt.% of H 2 was released over 20 min at a relatively low dehydrogenation temperature of 250 °C, and almost complete dehydrogenation was achieved at 300 °C for 5 min. In addition, at 125 °C, the hydrogen storage material absorbed 5.5 wt.% H 2 in 10 min. Furthermore, the activation energy of dehydrogenation was determined to be 69.588 ± 6.302 kJ ·mol −1 which is significantly lower than that of the ball-milled MgH 2 (i.e., 118.649 ± 2.825 kJ ·mol −1 ). It was therefore inferred that during dehydrogenation process, a Mg 2 Ni/Mg 2 NiH 4 hydrogen pump is formed by Ni, while the V-H and Co-H bonds formed by Co and V during the reaction act synergistically to catalyze the absorption and desorption of hydrogen, thereby increasing the hydrogen storage capacity of MgH 2 . These experiments provide new perspectives on the commercial application of MgH 2 .
研究领域:
材料科学
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化学工程
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DOI
高影响因子
International Journal of Minerals Metallurgy and Materials
·
2022
·Vol. 30
·期 1
·44-53
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IF 3.85
Lu Zhiyu,He Jiahuan,Song Mengchen,Zhang Yan,Wu Fuying,Zheng Jiaguang,Zhang Liuting,Chen Lixin
The practical application of magnesium hydride (MgH 2 ) was seriously limited by its high desorption temperature and slow desorption kinetics. In this study, a bullet-like catalyst based on vanadium related MOFs (MOFs-V) was successfully synthesized and doped with MgH 2 by ball milling to improve its hydrogen storage performance. Microstructure analysis demonstrated that the as-synthesized MOFs was consisted of V 2 O 3 with a bullet-like structure. After adding 7wt% MOFs-V, the initial desorption temperature of MgH 2 was reduced from 340.0 to 190.6°C. Besides, the MgH 2 +7wt%MOFs-V composite released 6.4wt% H 2 within 5 min at 300°C. Hydrogen uptake was started at 60°C under 3200 kPa hydrogen pressure for the 7wt% MOFs-V containing sample. The desorption and absorption apparent activity energies of the MgH 2 +7wt%MOFs-V composite were calculated to be (98.4 ± 2.9) and (30.3 ± 2.1) kJ·mol −1 , much lower than (157.5 ± 3.3) and (78.2 ± 3.4) kJ·mol −1 for the as-prepared MgH 2 . The MgH 2 +7wt%MOFs-V composite exhibited superior cyclic property. During the 20 cycles isothermal dehydrogenation and hydrogenation experiments, the hydrogen storage capacity stayed almost unchanged. X-ray diffraction (XRD) and X-ray photoelectron spectrometer (XPS) measurements confirmed the presence of metallic vanadium in the MgH 2 +7wt%MOFs-V composite, which served as catalytic unit to markedly improve the hydrogen storage properties of Mg/MgH 2 system.
研究领域:
材料科学
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氢能
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纳米催化
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金属有机框架材料
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DOI
高影响因子
ACS Applied Energy Materials
·
2018
·
IF 0
Zhongliang Ma,Jiguang Zhang,Yunfeng Zhu,Huaijun Lin,Yana Liu,Yao Zhang,Delong Zhu,Liquan Li
Metal nanocatalysis is an effective method to enhance the hydrogen storage properties of magnesium hydride (MgH2), and the catalytic effect can be further improved by a matrix material supported nanometal. In this work, carbon supported nano-Ni (Ni@C) was synthesized by calcination of dimethylglyoxime dinickel chelate, and then it was doped into MgH2 to improve the de/rehydrogenation kinetics. This shows that the homogeneously distributed Ni with refined particle size in carbon base leads to superior catalytic effects on hydrogen absorption/desorption of MgH2-5 wt % Ni@C. The MgH2-5 wt % Ni@C starts to desorb hydrogen at 187 °C, which is 113 °C lower than that of as-milled MgH2. Moreover, it takes only 500 s to thoroughly desorb hydrogen at 300 °C, which is 3000 s faster than as-milled MgH2 under the same dehydrogenation conditions. According to the Kissinger’s method, the apparent activation energy for desorption of the MgH2-5 wt % Ni@C is 66.5 ± 1.8 kJ mol–1, which is about 79.9 kJ mol–1 lower than that of as-milled MgH2. Cycling experiments show that the capacity retentions of hydrogen absorption and desorption after 10 cycles at 275 °C are 91% and 93%, respectively. Transmission electron microscope analysis shows that part of Ni transformed to Mg2NiH4/Mg2Ni during hydrogen absorption/desorption cycles.
研究领域:
材料科学
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化学工程
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DOI
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2025
·
IF 8.3
Yi Liu,Weiqi Sun,Zhicheng Yang,Ruoyang Zhang,Bin Li,Lixian Sun,Fen Xu,Wenwei Guo,Conglong Shi,Ting Yu,Zhengyi Liang,Qingjie He
Magnesium hydride (MgH 2 ), recognized as a promising alternative energy material to replace fossil fuels, possesses distinct advantages, including higher stability and hydrogen storage capacity. Nevertheless, its widespread application remains limits due to intrinsic drawbacks such as high thermodynamic stability and sluggish hydrogen adsorption-desorption kinetics. Coral-like NiO/NiFe 2 O 4 heterojunction catalysts were efficaciously synthesized through a conventional hydrothermal-calcination method in our work. These catalysts were subsequently ball-milled with MgH 2 to obtain the MgH 2 –NiO/NiFe 2 O 4 composite. A comprehensive series of hydrogen storage performance (HSP) evaluations demonstrated that the composite exhibits markedly enhanced hydrogen adsorption-desorption characteristics. Specifically, MgH 2 –NiO/NiFe 2 O 4 initiated hydrogen release at 188 °C, which represents a 133 °C decrease compared with ball-milled MgH 2 . At 275 °C, its composite released 6.2 wt% H 2 within 20 min, while at a hydrogen absorption temperature of 100 °C, it absorbed 4.4 wt% H 2 within 30 min. Besides, the composite dehydrogenation activation energy was declined to 86.97 kJ/mol, a decrease of 62.17 kJ/mol relative to ball-milled MgH 2 . Mechanistic investigations revealed that NiO/NiFe 2 O 4 underwent in situ transformation into Mg 2 Ni and FeO during hydrogen adsorption-desorption process. Simultaneously, the reversible “Mg 2 NiH 4 /Mg 2 Ni” phase functioned as hydrogen pump, thereby accelerating the kinetics. First-principles calculations further demonstrated that Fe atoms in the in situ-generated FeO acquired electrons from the MgH 2 interface, which weakened the Mg–H bonds and facilitated hydrogen desorption. This electronic modulation of MgH 2 effectively enhanced its hydrogen adsorption-desorption dynamics and substantially lowered hydrogen desorption activation energy. To sum up, our study reports successful preparation of a binary transition-metal heterojunction catalyst, NiO/NiFe 2 O 4 , derived from Ni and Fe. The outcomes offer new thoughts into design and classification of transition-metal-based catalysts for hydrogen storage applications.
研究领域:
材料科学
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能源化学
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纳米催化
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氢储能
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固态储氢
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产品关联
DOI
高影响因子
Advanced Energy Materials
·
2026
·
IF 25.5
Xue Ke,Yuanyuan Zhang,Fulai Qi,Qian Zhang,Xinqiang Wang,Yanxia Liu,Ke Wang,Jindou Shi,Zichao Shen,Mingchang Zhang,Yuanchao Yang,Fan Gao,Wengang Cui,Zhenglong Li,Yaxiong Yang,Lixian Sun,Jian Chen,Hongge Pan
Magnesium hydride (MgH 2 ) is widely regarded as a highly promising solid-state hydrogen storage material. However, its practical application is severely constrained by high operating temperatures and sluggish hydrogen absorption/desorption kinetics arising from multistep reaction energy barriers. Here, we rationally tailor a quinary Ti-based rutile-type high-entropy oxide to overcome these intrinsic limitations for the first time. The onset dehydrogenation temperature of the hybrid reduces to 195°C, which is 163°C lower than that of pristine MgH 2 . The composite releases 5.88 wt.% H 2 within 10 min at 250°C, accompanied by a 58% reduction in the apparent dehydrogenation activation energy. Moreover, a 1.84 wt.% H 2 uptake can be achieved within only 20 s at room temperature. The coexistence of various multivalent metal cations, lattice distortions, abundant defects, and oxygen vacancies in (TiNbCrTaFe)O 2 substantially reduces the multi-step reaction energy barriers during MgH 2 de/hydrogenation, enabling the overall kinetics to surpass those of all previously reported high-entropy catalyst-modified MgH 2 systems. This work expands the compositional design space and application scope of high-entropy oxides and provides a viable strategy for advanced hydrogen storage and catalytic systems.
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高影响因子
危险品化学品经营许可证（带存储）