JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Jingjing Chen,Chaoqun Li,Wei Chen,Xiaoyue Zhang,Xuebin Yu,Guanglin Xia
Despite of the moderate working temperature and relatively high hydrogen capacity of NaAlH 4 , the slow H 2 absorption and desorption kinetics and poor reversibility pose a major bottleneck hindering its practical application. Herein, porous NiTiO 3 nanorods is constructed to tailor reversible hydrogen storage performance of NaAlH 4 . It is theoretically and experimentally demonstrated that the building of NiTiO 3 nanorods effectively promotes the uniform distribution of catalytic Ni-based species and Ti-based species inside of NaAlH 4 matrix that are capable of synergistically weakening Al-H bonds of NaAlH 4 . As a result, under the catalysis of porous NiTiO 3 nanorods, the onset temperature for H 2 desorption from NaAlH 4 is decreased down to 89 °C, 91 °C lower than that of pure NaAlH 4 . In addition, NaAlH 4 under the catalysis of porous NiTiO 3 nanorods is capable of releasing 4.5 wt% H 2 within 60 min, 3.8 and 0.9 wt% higher than that of NaAlH 4 catalyzed by NiO and TiO 2 , respectively. More importantly, a reversible capacity of 4.6 wt% could be obtained for NaAlH 4 under the catalysis of porous NiTiO 3 nanorods after 5 cycles, corresponding to a capacity retention of 95%, while this value is significantly decreased to 42% for NaAlH 4 without the addition of NiTiO 3 nanorods. This work provides a new perspective for the development and design of high-performance catalysts for realizing reversible hydrogen storage of NaAlH 4 under moderate condition.
研究领域:
材料科学
·
氢储存技术
·
催化剂开发
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2017
·
IF 3.582
Fei Liang,Jing Lin,Yaoming Wu,Limin Wang
The Ti 1.4 V 0.6 Ni doped with NaAlH 4 composites were prepared by ball-milling method and the phase composition and electrochemical hydrogen storage properties of the composites were investigated. The phase contains icosahedral quasicrystalline (i-phase), Ti 2 Ni and V-based solid-solution phase primarily. The NaAlH 4 phase is not evident for the composite, and the NaAlH 4 phase should be decomposed to help form porous structure on the surface of the composites. The electrochemical hydrogen storage properties of composites has been enhanced with doped NaAlH 4 , and the maximum electrochemical hydrogen discharge capacity is 299.2 mAh/g, and keeps above 220 mAh/g after 80 cycles for 1 wt.% doping. The high-rate discharge ability of the composite electrode could achieve 79.8% at the discharge current density of 240 mA/g compared with that of 30 mA/g. The enhancement could be attributed to decoration of the composites surface, increase of entropy variation and improvement of H-kinetics on the strength of new porous structure in the composites.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2013
·Vol. 1
·期 34
·9752-9759
·
IF 0
Xiulin Fan,Xuezhang Xiao,Lixin Chen,Liuting Zhang,Jie Shao,Shouquan Li,Hongwei Ge,Qidong Wang
NaAlH4, a prototypical high energy density complex hydride, possesses a favorable thermodynamics and high hydrogen storage capacity. However, the poor kinetics and degradation of cycling stability retard its practical application. To ease these problems, CeB6, CeF3 and CeO2 nanoparticles with a size of about 10 nm are synthesized by the wet-chemistry method and introduced into NaAlH4 systems as additives in this work. The results show that all of the nanoparticles are effective in improving the hydriding–dehydriding kinetics of NaAlH4, and nano-CeB6 possesses the highest catalytic activity. The rehydrogenation of dehydrogenated NaAlH4 doped with nano-CeB6 can be accomplished in less than 20 min with a high capacity of 4.9 wt%, which shows a 20% increase in capacity compared to that of chloride-doped NaAlH4. Due to the structural stability and good dispersion of nano-CeB6 and nano-CeF3, a favorable cycling stability with high capacity retention is achieved for their doped samples. Moreover, hydrogen can be released from the hydrogenated sample doped with nano-CeB6 at a temperature as low as 75 °C, fulfilling the operation temperature of a PEM fuel cell. In the nano-CeO2 doped NaAlH4 system, CeO2 is first reduced to CeH2.51. In the subsequent cycles, the formed CeH2.51 gradually transforms into Ce–Al, and simultaneously the kinetics of the doped system is further enhanced. It is believed that the utilization of Ce-based nanoparticles as catalysts would substantially improve the practical applications of NaAlH4 for hydrogen storage.
研究领域:
材料科学
·
化学工程
·
纳米技术
✓ 已验证
产品关联
DOI
Frontiers in Chemistry
·
2020
·
IF 3.693
Zhang Xin,Zhang Xuelian,Ren Zhuanghe,Hu Jianjiang,Gao Mingxia,Pan Hongge,Liu Yongfeng
In this paper, we report amorphous-carbon-supported TiB2 nanoparticles having sizes of 2–4 nm (nano-TiB2@C) as highly active catalysts for hydrogen storage in NaAlH4. Nano-TiB2@C was synthesized by a simple calcination at 550°C with Cp2TiCl2 and MgB2 (molar ratio of 1:1) as precursors. The addition of 7 wt% nano-TiB2@C reduced the onset dehydrogenation temperature of NaAlH4 by 100 to 75°C. A practically available hydrogen capacity of 5.04 wt% could be desorbed at 140°C within 60 min, and completely hydrogenated at 100°C within 25 min under a hydrogen pressure of 100 bar. Notably, the hydrogen capacity was almost unchanged after 20 cycles, which shows the stable cyclability, considerably higher than those of structures catalyzed by Ti halides or TiO2. The stable catalytic function was closely related to the in-situ-formed Ti–Al alloy, which considerably facilitated the dissociation and recombination of H–H and Al–H bondings.
研究领域:
材料科学
·
能源化学
✓ 已验证
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
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
·
能源化学
·
理论计算
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Chemistry-An Asian Journal
·
2016
·Vol. 11
·期 24
·3541-3549
·
IF 4.592
Xin Zhang,Ruyan Wu,Zeyi Wang,Mingxia Gao,Hongge Pan,Yongfeng Liu
Graphical Boosting hydrogen storage : In situ-synthesized nanocrystalline ZrO 2 @C exhibits good catalytic activity for hydrogen storage in NaAlH 4 . The NaAlH 4 –7 wt % ZrO 2 @C sample releases hydrogen starting from 126 °C and reabsorbs hydrogen starting from 54 °C, and these temperatures are lower by 71 and 36 °C, respectively, than those for pristine NaAlH 4 (see figure). Sodium alanate (NaAlH 4 ) has attracted intense interest as a prototypical high-density hydrogen-storage material. However, poor reversibility and slow kinetics limit its practical applications. Herein, a nanocrystalline ZrO 2 @C catalyst was synthesized by using Uio-66(Zr) as a precursor and furfuryl alcohol (FA) as a carbon source. The as-synthesized ZrO 2 @C exhibits good catalytic activity for the dehydrogenation and hydrogenation of NaAlH 4 . The NaAlH 4 -7 wt % ZrO 2 @C sample released hydrogen starting from 126 °C and reabsorbed it starting from 54 °C, and these temperatures are lower by 71 and 36 °C, respectively, relative to pristine NaAlH 4 . At 160 °C, approximately 5.0 wt % of hydrogen was released from the NaAlH 4 -7 wt % ZrO 2 @C sample within 250 min, and the dehydrogenation product reabsorbed approximately 4.9 wt % within 35 min at 140 °C and 100 bar of hydrogen. The catalytic function of the Zr-based active species is believed to contribute to the significantly reduced operating temperatures and enhanced kinetics.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2025
·
IF 8.3
Ke Wang,Fei-teng Zhao,Sen-miao Zhao,Qi-yue Wang,Xiao-dan Mei,Jing-lan Huang,Hai-zhen Liu,Cun-ke Huang,Jin Guo
Developing efficient hydrogen storage technologies remains a critical challenge for advancing clean hydrogen energy applications. This study addresses the challenges of high dehydrogenation temperature and sluggish dehydrogenation kinetics in NaAlH 4 through the development of TiVC MXene-enhanced composite systems . In this paper, TiVC MXene was prepared by etching TiVAlC with HCl/LiF, and TiVC/NaAlH 4 composite systems were made via milling. The unit cell of NaAlH 4 expanded during milling due to M (M = Ti, V) point defects . The optimal 8 wt% TiVC-doped sample demonstrated remarkable performance: onset dehydrogenation temperature reduced to 90 °C and activation energy decreased by 41% in the 2 nd dehydrogenation step. Notably, the dehydrogenated product achieved 4.1 wt% hydrogenation capacity within 30 min at 120 °C. Structural and mechanistic analyses showed that TiVC decomposed, and its reaction products, such as M defects, Ti–Al alloy and Ti/V oxides , were the real catalysts. They enhanced NaAlH 4 's hydrogen-storage performance by offering active H and smaller Al particles . This work demonstrates the potential of MXene-derived multiphase catalysts for metal hydride storage systems.
研究领域:
材料科学
·
氢能存储
·
纳米材料
·
催化
·
能源材料
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Chen Jin,Zhenke Chen,Hang Che,Shuzhong Wang,Zhiheng Liu,Tao Chen,Li Wang,Yuyuan Zhao,Xinhua Wang,Haoyuan Zheng,Haizhen Liu,Mi Yan
Sodium alanate has a reversible hydrogen storage capacity of 5.6 wt% at relatively mild conditions, but it is limited in practical use because of low reaction rates and the phase separation of the reaction product. In this study, to enhance the hydrogen storage ability of sodium alanate, a one-step hydrogen pressure ball milling process was used to introduce the MXene-based carbonitride, Ti 3 CN, and its catalytic modification ability was compared to that of Ti 3 C 2 on sodium alanate. The onset and peak hydrogen desorption temperatures of NaAlH 4 decreased significantly from 176.9 /203.3 °C to 76.8/129.3 °C, and the activation energies for the two-step dehydrogenation process were reduced from 118/159 kJ/mol (pure NaAlH 4 ) to 42/72 kJ/mol. In an isothermal condition at 100 °C, the composite material desorbed 3.30 wt% hydrogen within one hour, and the capacity retention rate kept as high as 93.7% after ten cycles of hydrogen absorption and desorption. It can be obtained that Ti 3 CN maintained its layered structure during the process of ball milling, and there possessed multiple active sites, such as Ti 3 CN, Ti 0 and TiAl. Moreover, TiAl nanointermetallic phases were found to be in situ generated during the cycling process. TiAl displayed a reversible “hydrogen pump” property, acting as nucleation sites to promote the adsorption and desorption of hydrogen. At the same time, the MXene lattice promoted the dispersion of aluminum and the prevention of phase separation. The support stability provided by Ti 3 CN and the coupled catalytic ability of TiAl and Ti 0 phases significantly improved the hydrogen desorption rate and cycling performance of NaAlH 4 at low temperature. These results are valuable to the construction of an efficient solid hydrogen storage system.
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Shiming Xu,Jintang Duan,Lianfang Feng,Xueping Gu,Cailiang Zhang,Liu Liu
The widespread implementation of hydrogen energy is critically constrained by the challenge of storage. Aluminum hydride (α-AlH 3 ), a binary hydride stable under ambient conditions with high volumetric hydrogen density, represents a promising candidate. However, when it is traditionally prepared from lithium aluminum hydride (LiAlH 4 ) and aluminum chloride (AlCl 3 ), the process is cost-prohibitive for scale-up. This study presents a cost-effective synthesis strategy by systematically investigating the effects of different molar ratios of LiAlH 4 /NaAlH 4 /AlCl 3 (4:0:1, 1:3:1, 0.5:3.5:1, 0:4:1). Results indicate that the introduction of LiAlH 4 significantly enhances reaction efficiency and kinetics. The optimal ratio of 1:3:1 effectively compensated for the slower kinetics of NaAlH 4 , achieving over 94% conversion of AlCl 3 to AlH 3 ·nEt 2 O etherate. Desolvation studies revealed that AlH 3 ·nEt 2 O derived from NaAlH 4 required higher temperatures for complete phase transformation, whereas systems with LiAlH 4 content below 25% were insufficient to effective desolvation. The α-AlH 3 crystals produced from the 1:3:1 ratio exhibited a well-defined cubic morphology and high thermal stability, with a decomposition temperature of 165 °C. By replacing 75% of the costly LiAlH 4 with NaAlH 4 , this hybrid approach achieved an approximately 50% reduction in the material cost. These findings provide critical process parameters and a viable pathway for the cost-effective, large-scale production of high-performance α-AlH 3 for hydrogen storage applications.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2016
·
IF 3.014
Honghui Cheng,Yuan Chen,Wenpei Sun,Haoran Lou,Yanqi Liu,Qi Qi,Jiamin Zhang,Jingjing Liu,Kai Yan,Huiming Jin,Yao Zhang,Shuyi Yang
TiH 2 was introduced into the 4MgH 2 -NaAlH 4 composite by ball milling to improve the dehydrogenation and re-dehydrogenation performance of the composite. The non-isothermal dehydrogenation curve shows that the onset temperature of hydrogen release from 4MgH 2 -NaAlH 4 -TiH 2 is at around 100 °C, which is lower by 50 °C than that of 4MgH 2 -NaAlH 4 . The investigation by Kissinger's method indicates that 4MgH 2 -NaAlH 4 -TiH 2 possesses much lower activation energy (68 kJ mol −1 ) than 4MgH 2 -NaAlH 4 (159 kJ mol −1 ), indicating an enhanced dehydrogenation kinetics due to the additional TiH 2 . TiH 2 catalyzes the decomposition of MgH 2 and NaAlH 4 , respectively, and also the reaction between their products during the dehydrogenation process below 375 °C. At temperatures above 375 °C, TiH 2 will react with Mg 17 Al 12 to form Al 3 Ti and liberate contained hydrogen. TiH 2 also improved the isothermal hydrogenation kinetics of 4MgH 2 -NaAlH 4 desorbed system. The activation energy of re-hydrogenation for 4MgH 2 -NaAlH 4 -TiH 2 system was greatly reduced from 161.62 kJ mol −1 H 2 to 125.80 kJ mol −1 H 2 of 4MgH 2 -NaAlH 4 . The kinetics enhancement of hydrogen absorption is probably due to the intermediate phase Al 3 Ti, which is beneficial to the recombination of MgH 2 .
研究领域:
材料科学
·
氢气储存
·
固态化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Zhuanghe Ren,Xin Zhang,Zhenguo Huang,Jianjiang Hu,Yangzhong Li,Shiyou Zheng,Mingxia Gao,Hongge Pan,Yongfeng Liu
Nanosized titanium compounds are particularly effective in catalyzing hydrogen cycling by NaAlH 4 . Titanium hydride (TiH 2 ), as a catalyst, is highly interesting since it contributes hydrogen in addition to active Ti. However, it has been challenging to fabricate nanosized TiH 2 due to the strong affinity of Ti with oxygen. Herein, TiH 2 nanoflakes with a lateral size of ~10 nm and thickness of ~1 nm are successfully synthesized through a novel facile one-pot solvothermal process. In an anhydrous THF solution, LiH reacts with TiCl 4 rapidly at 100 °C forming TiH 2 and LiCl. The newly formed TiH 2 nucleates and grows epitaxially on the graphene surface due to the well-matched lattice parameters, giving rise to the formation of TiH 2 nanoflakes. Both theoretical calculations and experiments reveal the generation of Cl· radicals and unsaturated C C bonds when TiCl 4 reacts with THF, which promotes the formation of TiH 2 . The nanoflake-like TiH 2 on graphene enables an outstanding hydrogen storage performance of NaAlH 4 , i.e., full dehydrogenation at 80 °C and hydrogenation at 30 °C and under 100 bar H 2 , with a practical hydrogen capacity of 4.9 wt%, which has been never reported before.
研究领域:
材料科学
·
纳米化学
·
能源化学
·
固态储氢
·
催化化学
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Ning Ma,Xiaobo Ma,Ling Ma,Xiaomeng Wang,Zhijie Cao
The high desorption temperature and sluggish kinetics of NaAlH 4 limit its applications in hydrogen storage . To address these issues, a Ni nanoparticles-loaded TiN composite catalyst with excellent thermodynamic stability and catalytic activity was constructed. The addition of 5 wt% Ni 10 @TiN reduced the initial dehydrogenation temperature of NaAlH 4 to 81 °C, and a total amount of 5.4 wt% H 2 could be released within 20 min at 170 °C. The activation energies for the two-step dehydrogenations were significantly reduced to 66.3 kJ/mol and 81.4kJ/mol, respectively, which were 43 % and 36 % lower than that of pure NaAlH 4 . Experimental results and theoretical calculations suggested that these remarkable improvements were originated from the grain refinement of NaAlH 4 and multi-fold catalytic activities of Ni 10 @TiN catalyst like providing catalytic active sites, facilitating the breaking of Al-H and H-H bonds, and increasing hydrogen diffusion channels. These findings may offer new ideas for designing high-efficiency catalysts for solid-state hydrogen storage materials.
研究领域:
材料科学
·
氢存储
·
催化
·
纳米材料
·
储能
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）