INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2024
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IF 8.1
Xueqin Zhu,Minjian Yang,Chunnian Zheng,Qin Zhu,Zhili Cui,Piaopiao Zhang
Exploiting magnesium-based hydrogen storage materials faces great challenges due to their inherent thermodynamic and kinetic characteristics. However, this issue can be mitigated by employing a catalyst doping modification strategy. In this work, a composite of titanium carbide (Ti 3 C 2 T x MXene)-supported nickel fluoride (NiF 2 ) nanoparticles, known as NiF 2 @Ti 3 C 2 , was fabricated via the hydrothermal approach and utilized to reinforce the hydrogen storage performance of magnesium (Mg). It was shown that NiF 2 @Ti 3 C 2 composites have exceptional catalytic properties for Mg hydrogen storage. The Mg–NiF 2 @Ti 3 C 2 composite, containing 5 wt% of NiF 2 @Ti 3 C 2 , released 3.46 wt% of hydrogen at 300 °C, while pure Mg produced essentially little hydrogen in identical conditions. Additionally, there was a decrease in the activation energy of hydrogen desorption from 135.4 to 77.65 kJ mol −1 . Moreover, the composite offered excellent stability and reversible performance, achieving 95.8% capacity retention after 10 consecutive testing cycles. During the hydrogen uptake and release process, the NiF 2 @Ti 3 C 2 composite interacted with Mg/MgH 2 to produce the metals Ti 0 , MgF 2 , and Mg 2 Ni/Mg 2 NiH 4 , which acted as active species to boost the hydrogen storage performance of Mg.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Journal of Physical Chemistry C
·
2011
·
IF 4.524
Pei Pei Yuan,Bin Hong Liu,Bang Jie Zhang,Zhou Peng Li
In this work, we report a new reversible hydrogen storage composite based on 6LiBH4+CaF2. It has a theoretical hydrogen capacity of 9.6 wt % (0.09 g·ml−1) and a slightly reduced thermodynamic stability compared with pure LiBH4. The dehydrogenation of 6LiBH4 + CaF2 yielded CaB6 and a solid solution of LiH and LiF that can be rehydrogenated to form LiBH4 and CaF2. The composite revealed good reversibility of hydrogen storage regardless of the hydrogen back pressure applied during the dehydrogenation. Catalysts like TiF3, CeF3, and NbCl5 were found to enhance its dehydriding kinetics. XRD and FT-IR analyses revealed that hydrogen uptake of the composite proceeded through a reaction path involving CaH2 as the main intermediate.
研究领域:
材料科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
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2013
·Vol. 1
·期 12
·3983-3991
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IF 0
Lina Chong,Jianxin Zou,Xiaoqin Zeng,Wenjiang Ding
In this work, a reversible hydrogen storage composite, 3NaBH4/NdF3, has been prepared using a mechanical milling method. The de-/rehydrogenation properties as well as the mechanisms of reversible hydrogen sorption in the composite were carefully investigated. Based on the pressure–temperature–composition measurements, the de-/rehydrogenation enthalpies of the 3NaBH4/NdF3 composite are determined to be 86.4 kJ mol−1 H2 and −13.2 kJ mol−1 H2, respectively. The onset dehydriding temperature of the composite is determined to be 413 °C in 0.1 MPa Ar atmosphere and can be as low as 80 °C under vacuum conditions. Analyses revealed that NdB6, Nd2H5 and NaF were formed after the decomposition of the composite, which can be hydrogenated to produce NaBH4 and NaNdF4. The formation of NaNdF4 instead of NdF3 in the hydrogenated products is believed to be responsible for the reduced hydrogen storage capacity, while the intermediate formation of B, Nd and NdB4 during dehydrogenation accounts for the asymmetric hydriding/dehydriding behaviors in the 3NaBH4/NdF3 composite.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
CHEMISTRY-A EUROPEAN JOURNAL
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2021
·Vol. 27
·期 35
·9087-9093
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IF 5.236
Yongyang Zhu,Hao Zhong,Hui Wang,Liuzhang Ouyang,Jiangwen Liu,Zhenguo Huang,Min Zhu
Graphical A cost-effective way to produce NaBH 4 with high yield by ball milling hydrated borax (Na 2 B 4 O 7 ⋅ 10H 2 O) with cheap Al or Al 88 Si 12 at ambient condition is presented. An effective strategy was developed to facilitate mass transfer during the reaction by introducing NaH to enable the formation of loose NaAlO 2 instead of dense Al 2 O 3 on Al surface, and by using Si as a milling additive that prevents agglomeration and also breaks up passivation layers. A significant obstacle in the large-scale applications of sodium borohydride (NaBH 4 ) for hydrogen storage is its high cost. Herein, we report a new method to synthesize NaBH 4 by ball milling hydrated sodium tetraborate (Na 2 B 4 O 7 ⋅ 10H 2 O) with low-cost Al or Al 88 Si 12 , instead of Na, Mg or Ca. An effective strategy is developed to facilitate mass transfer during the reaction by introducing NaH to enable the formation of NaAlO 2 instead of dense Al 2 O 3 on Al surface, and by using Si as a milling additive to prevent agglomeration and also break up passivation layers. Another advantage of this process is that hydrogen in Na 2 B 4 O 7 ⋅ 10H 2 O serves as a hydrogen source for NaBH 4 generation. Considering the low cost of the starting materials and simplicity in operation, our studies demonstrate the potential of producing NaBH 4 in a more economical way than the commercial process.
研究领域:
材料科学
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化学工程
✓ 已验证
DOI
PubMed
高影响因子
Journal of Magnesium and Alloys
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2022
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IF 11.813
Haiguang Gao,Rui Shi,Yana Liu,Yunfeng Zhu,Jiguang Zhang,Liquan Li,Xiaohui Hu
Two-dimensional Ti 3 C 2 T x MXenes exposing different active facets are introduced into MgH 2 , and their catalytic effects are systematically investigated in depth through experimental and theoretical approaches. Excluding factors such as interlayer space, surface functional groups and experimental contingency, the exposed facets is considered to be the dominant factor for catalytic activity of Ti 3 C 2 T x towards MgH 2 . More exposed edge facets of Ti 3 C 2 T x displays higher catalytic activity than that with more exposed basal facets, which also leads to different rate-controlling steps of MgH 2 in the de/hydrogenation process. The low work function, strong hydrogen affinity and high content of in situ metallic Ti for the edge facet contribute the high catalytic activity. This work will give insights into the structural design of two-dimensional Ti 3 C 2 T x MXene used for enhancing the catalytic activity in various fields.
研究领域:
材料科学
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催化化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
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2018
·
IF 8.097
Xin Zhang,Zhuanghe Ren,Yunhao Lu,Jianhua Yao,Mingxia Gao,Yongfeng Liu,Hongge Pan
Herein, we synthesize successfully ultrafine TiN nanoparticles (<3 nm in size) embedded in N-doped carbon nanorods (nano-TiN@N–C) by a facile one-step calcination process. The prepared nano-TiN@N–C exhibits superior catalytic activity for hydrogen storage in NaAlH4. Adding 7 wt % nano-TiN@N–C induces more than 100 °C reduction in the onset dehydrogenation temperature of NaAlH4. Approximately 4.9 wt % H2 is rapidly released from the 7 wt % nano-TiN@N–C-containing NaAlH4 at 140 °C within 60 min, and the dehydrogenation product is completely hydrogenated at 100 °C within 15 min under 100 bar of hydrogen, exhibiting significantly improved desorption/absorption kinetics. No capacity loss is observed for the nano-TiN@N–C-containing sample within 25 de-/hydrogenation cycles because nano-TiN functions as an active catalyst instead of a precursor. A severe structural distortion with extended bond lengths and reduced bond strengths for Al–H bonding when the [AlH4]− group adsorbs on the TiN cluster is demonstrated for the first time by density functional theory calculations, which well-explains the reduced de-/hydrogenation temperatures of the nano-TiN@N–C-containing NaAlH4. These findings provide new insights into designing and synthesizing high-performance catalysts for hydrogen storage in complex hydrides.
研究领域:
材料科学
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能源化学
·
理论计算
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Materialia
·
2018
·
IF 0
Zhengyang Shen,Zeyi Wang,Min Zhang,Mingxia Gao,Jianjiang Hu,Fang Du,Yongfeng Liu,Hongge Pan
A novel solid-solution MXene (Ti 0.5 V 0.5 ) 3 C 2 is successfully synthesized by exfoliating a solid-solution MAX phase (Ti 0.5 V 0.5 ) 3 AlC 2 , and its catalytic effect on the hydrogen storage reaction of Mg is systemically evaluated for the first time. Typical layer morphology is observed for the prepared (Ti 0.5 V 0.5 ) 3 C 2 , which exhibits a better catalytic activity than that of Ti 3 C 2 . The addition of 10 wt% (Ti 0.5 V 0.5 ) 3 C 2 remarkably reduces the dehydrogenation onset temperature of MgH 2 by 70 °C, from 266 to 196 °C. At 250 °C, approximately 5.0 wt% H 2 is released from the 10 wt% (Ti 0.5 V 0.5 ) 3 C 2 -containing MgH 2 within 20 min. The dehydrogenated sample rapidly absorbs 4.8 wt% H 2 within 5 s at 120 °C; these hydrogenation kinetics are much more superior even to the well-studied Nb 2 O 5 catalyst. The apparent activation energy is calculated to be 77.3 kJ/mol for the MgH 2 -10 wt% (Ti 0.5 V 0.5 ) 3 C 2 sample, which is only around half of that of the pristine MgH 2 (153.8 kJ/mol). This is responsible for the remarkably reduced dehydrogenation operating temperature. Moreover, the chemical states of (Ti 0.5 V 0.5 ) 3 C 2 during dehydrogenation are also analysed and discussed.
研究领域:
材料科学
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能源存储
✓ 已验证
DOI
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
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2022
·
IF 6.76
Jiaqi Zhang,Quanhui Hou,Yanbing Liu,Xinglin Yang
The design of catalysts with excellent catalytic activity plays an important role in the field of solid-state hydrogen storage of new energy sources. Herein, a novel hydrangea-like NiO@NiMoO 4 composite catalyst was prepared through a facile hydrothermal reaction. Subsequently, NiO@NiMoO 4 was doped into MgH 2 by ball milling to solve the problems of high dehydrogenation temperature and slow desorption kinetics of MgH 2 . It can be seen from the experimental results that the MgH 2 + 10 wt% NiO@NiMoO 4 composite starts to dehydrogenate at about 190 °C, which is about 170 °C lower than that of pure MgH 2 . Meanwhile, after complete dehydrogenation, the composites can start to absorb hydrogen below 40 °C. Compared with pure MgH 2 , the activation energy of hydrogen absorption and dehydrogenation of the composite decreased by 47.6 kJ/mol and 46.5 kJ/mol, respectively. In 10th cycle tests, the MgH 2 + 10 wt% NiO@NiMoO 4 composite still has good cycle stability. After adding a small amount of biomass charcoal, the hydrogen storage capacity can even be maintained above 97%. Furthermore, the characterization results show that the in situ generated new species Mo and Mg 2 Ni/Mg 2 NiH 4 synergistically promote the adsorption and dissociation of hydrogen. This new synergistic mechanism provides new comprehensive insights for improving reversible hydrogen storage in MgH 2 .
研究领域:
材料科学
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2022
·
IF 10.319
Yaokun Fu,Lu Zhang,Yuan Li,Sanyang Guo,Zhichao Yu,Wenfeng Wang,Kailiang Ren,Qiuming Peng,Shumin Han
The introduction of the heterogeneous catalysts with high activity can significantly improve hydrogen storage performance of MgH 2 , therefore, in this paper, we synthesize a carbon-supported transition metal compound, FeCoS@C derivative from ZIF-67, by utilizing the in situ formed C dispersive multiphase Mg 2 Co, α-Fe, Co 3 Fe 7 , and MgS to implement catalysis to MgH 2 . Noteworthily, MgH 2 -FeCoS@C rapidly absorbs 6.78 wt% H 2 within 60 s at 573 K and can also absorb 4.56 wt% H 2 in 900 s at 473 K. Besides, the addition of FeCoS@C results in decreasing of the initial dehydrogenation temperatures of MgH 2 from 620 to 550 K. The dehydrogenation activation energy of MgH 2 decreases from 160.7 to 91.9 kJ mol –1 . Studies show that the Mg 2 Co, α-Fe, and Co 3 Fe 7 act as “hydrogen channels” to accelerate hydrogen transfer due to the presence of transition metals, and MgS with excellent catalytic effect formed from MgH 2 -FeCoS@C provides a strong and stable catalytic effect. Besides, the carbon skeleton obtained by the carbonization of ZIF-67 not only serves as a dispersion for the multiphase catalytic system, but also provides more active sites for the catalysts. Our study shows that the multiphase and multiscale catalytic system provides an effective strategy for improving the hydrogen storage performance of MgH 2 .
研究领域:
材料科学
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催化
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能源存储
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2020
·
IF 4.939
Xiang Gong,Zhao Jiang,Tao Fang
N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) was a promising system for hydrogen storage applications. 1.0 wt% Pt/TiO 2 was regarded as the optimal loading in Pt/TiO 2 catalyst applied in the 12H-NECZ dehydrogenation reaction. The hydrogen release amount, selectivity to NECZ and TOF of 12H-NECZ dehydrogenation are 5.75 wt %, 98% and 229.73 min −1 at 453 K. Compared with the commercial 5.0 wt% Pd and Pt-based catalysts, it exhibited very high activity, selectivity and stability for 12H-NECZ dehydrogenation with low Pt loading. Combined with the XRD , XPS , HRTEM , TPR analysis, it was indicated that the enhanced catalytic performance was due to the SMSI (strong metal-supporting interaction) between Pt and TiO 2 support, which accelerated the rate-limiting step and enhanced the whole dehydrogenation reaction. This work may be beneficial for the commercial application of Pt/TiO 2 catalysts in the Liquid Organic Hydrogen Carrier (LOHC) system.
研究领域:
化学工程
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Haizhen Liu,Chenglin Lu,Xinchun Wang,Li Xu,Xiantun Huang,Xinhua Wang,Hua Ning,Zhiqiang Lan,Jin Guo
Two-dimensional vanadium carbide (V2C) and titanium carbide (Ti3C2) MXenes were first synthesized by exfoliating V2AlC or Ti3AlC2 and then introduced jointly into magnesium hydride (MgH2) to tailor the hydrogen desorption/absorption performances of MgH2. The as-prepared MgH2–V2C–Ti3C2 composites show much better hydrogen storage performances than pure MgH2. MgH2 with addition of 10 wt % of 2V2C/Ti3C2 initiates hydrogen desorption at around 180 °C; 5.1 wt % of hydrogen was desorbed within 60 min at 225 °C, while 5.8 wt % was desorbed within 2 min at 300 °C. Under 6 MPa H2, the dehydrided MgH2–2V2C/Ti3C2 can start to recover hydrogen at room temperature, and 5.1 wt % of H2 is obtained within 20 s at a constant temperature of 40 °C. The reversible capacity (6.3 wt %) does not decline for up to 10 cycles, which shows excellent cycling stability. The addition of 2V2C/Ti3C2 can remarkably lower the activation energy for the hydrogen desorption reaction of MgH2 by 37% and slightly reduce the hydrogen desorption reaction enthalpy by 2 kJ mol–1 H2. It was demonstrated that the combination of V2C and Ti3C2 promotes the hydrogen-releasing process of MgH2 compared with addition of only V2C or Ti3C2, while Ti3C2 impacts MgH2 more significantly than V2C in the hydrogen absorption process of MgH2 at ambient temperatures. A possible mechanism in the hydrogen release and uptake of the MgH2–V2C–Ti3C2 system was proposed as follows: hydrogen atoms or molecules may preferentially transfer through the MgH2/V2C/Ti3C2 triple-grain boundaries during the desorption process and through the Mg/Ti3C2 interfaces during the absorption process. Microstructure studies indicated that V2C and Ti3C2 mainly act as efficient catalysts for MgH2. This work provides an insight into the hydrogen storage behaviors and mechanisms of MgH2 boosted by a combination of two MXenes.
研究领域:
材料科学
·
能源存储
✓ 已验证
DOI
PubMed
高影响因子
CHEMISTRY OF MATERIALS
·
2024
·
IF 7.2
Yichen Qi,Zeyang Zhang,Qinke Tang,Jiangchuan Liu,Rui Shi,Jiguang Zhang,Yana Liu,Jun Wang,Jiankun Zhang,Shihao Chen,Yunfeng Zhu
Catalysis has been demonstrated to be effective in enhancing the kinetics of MgH2, which has been widely investigated as one of the most promising solid-state hydrogen storage materials. It is essential and challenging to design catalysts with high activity and to understand the corresponding interaction mechanisms between the catalysts and MgH2, especially for multiphase catalyst systems. In this study, an elaborated VS2/NiS2 catalyst based on well-combined components and heterostructure is exploited to substantially improve the hydrogen storage performance of MgH2. Impressively, rapid dehydrogenation (3.4 wt % H2 in 900 s at 498 K) and low-temperature hydrogenation (3.7 wt % H2 in 7200 s at 348 K) properties are achieved in the MgH2–VS2/NiS2 system. The activation energies for the hydrogen absorption/desorption are calculated to be 32.1/86.7 kJ mol–1, which represents a considerable reduction of 60.9% and 43.6% compared to the as-milled MgH2, respectively. Detailed investigations reveal that the enhanced hydrogen absorption/desorption kinetics are mainly attributed to the synergistic effect induced by the in situ-formed Mg2Ni/VH2 heterostructure and the “hydrogen pump” of Mg2Ni/Mg2NiH4. The Mg2Ni/VH2 heterostructure elongate Mg–H bonds, while the “hydrogen pump” of Mg2Ni/Mg2NiH4 facilitate H transfer. This work offers a fresh perspective for application of multicomponent catalysts in the field of metal hydrides.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）