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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

Excellent catalytic effect of V2C MXene on dehydrogenation performance of α-AlH3

Zhongxuan Lin,Zhenluo Yuan,Huanhuan Zhang,Shuyan Guan,Xiaojiao Wang,Shiqian Zhao,Guangxin Fan,Yanping Fan,Baozhong Liu

Lowering the dehydrogenation temperature and maintaining high dehydrogenation capacity are greatly hindering the practical application of α-AlH 3 for the hydrogen fuel cell industry. Herein, the layered accordion-like V 2 C MXene is synthesized and doped into α-AlH 3 by mild ball milling . The 1 wt.% V 2 C-catalyzed α-AlH 3 possesses excellent dehydrogenation performance with a low initial decomposition temperature of 70.5 °C and a high hydrogen release capacity of 8.1 wt.%. Furthermore, 7.8 wt.% of hydrogen could be quickly released from α-AlH 3 -1 wt.% V 2 C composite within 15 min at 120 °C, with a lower activation energy of 69.5 kJ/mol than that of as-received sample. The excellent dehydrogenation performance is attributed to the high activity of the zero valence V catalyst which is transformed from the multivalent V during ball milling and to promote dissociation and reorganization of hydrogen. This effective approach significantly enhances the dehydrogenation of α-AlH 3 , providing a hopeful approach for modifying metal hydrides .

研究领域: 材料科学 · 无机化学 · 能源化学 · 纳米材料 · 储氢材料
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

Low-temperature hydrogen release exceeding 7 wt% from LiBH4-mannitol composites

Chengguo Yan,Jiaguang Zheng,Ao Xia,Qingbo Zhang,Meiling Lv,Zhenxuan Ma,Chao Su,Zhendong Yao

Among conventional hydrogen storage materials , LiBH 4 has been regarded as one of the best hydrogen transporters due to its relatively large hydrogen capacities. However, because of its extraordinarily high dehydrogenation temperatures, LiBH 4 was not suitable for hydrogen storage due to its stable thermodynamic features. Herein, we present a novel approach to LiBH 4 that uses solid-state multi-hydroxyl mannitol as a reactant, regulating hydrogen release below 69.9 °C. More than 7 wt% H 2 could be released with ultra-fast rates at 140 °C from the LiBH 4 -mannitol composite. XRD , FTIR , and SEM tests revealed that the reaction between mannitol (H δ+ ) and LiBH 4 (H δ− ) to produce hydrogen was accompanied by the generation of large amounts of heat in situ, which further promoted the decomposition of LiBH 4 for hydrogen production , exceeding the theoretical dehydrogenation amount of H δ+ - H δ− reaction. This work indicates possibilities for the development of fast and easy high-capacity hydrogen generation systems based on complex hydrides.

研究领域: 材料科学 · 无机化学 · 能源化学 · 氢能源存储
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2016 ·Vol. 41 ·期 15 ·6362-6368 · IF 3.205

RhNi nanocatalyst: Spontaneous alloying and high activity for hydrogen generation from hydrous hydrazine

Di-Chang Zhong,Yue-Lei Mao,Xin Tan,Ping Zhong,Liang-Xian Liu

Chemical hydrogen storage, endowed with superiorities of safety and efficiency, has been regarded as one of the most promising approaches. The design and synthesis of metallic catalytic system is an key step for development of chemical hydrogen storate materials. In this paper, we report that RhNi nanocatalyst, formed by spontaneously alloying of well-dispersed Rh and Ni NPs , exhibits much higher performance in the catalytic dehydrogenation of hydrous hydrazine.

研究领域: 材料化学 · 催化化学 · 纳米科学 · 能源化学 · 氢能源
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CHEMICAL PHYSICS LETTERS · 2018 · IF 1.686

Synergic improvement on thermal dehydrogenation of the LaH3-MgH2-KBH4 system

Huaiwei Zhang,Jianbo Qi,Zhenguo Ji

Synergic effects of rare earth-magnesium based hydrides (LaH 3 -MgH 2 ) on thermal dehydrogenation of potassium borohydride (KBH 4 ) are discussed in the paper. Comparing to above 675 K for the LaH 3 -MgH 2 or KBH 4 , the dehydrogenation temperature can be decreased to 346 K for the composites (LaH 3 -MgH 2 -KBH 4 ). The apparent activation energy of desorption process for the mixture is also greatly reduced. On the other hand, the products in the temperature programmed desorption process are also illustrated.

研究领域: 材料化学 · 无机化学 · 能源材料 · 储氢材料 · 固态化学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2011 ·Vol. 36 ·期 14 ·8203-8208 · IF 4.057

Hydrogen release from sodium borohydrides at low temperature by the addition of zinc fluoride

Z.G. Zhang,H. Wang,M. Zhu

The major challenge of complex hydride for hydrogen storage is to release hydrogen at a moderate temperature with rapid kinetics. This paper reports a new composite system (NaBH 4 /ZnF 2 ) to generate hydrogen at a low temperature below 100 °C. The NaBH 4 and ZnF 2 mixture was prepared by a mechanical milling in a 2:1 M ratio. Dehydrogenation of the mixture during a heating process shows that the initial dehydrogenation temperature was below 100 °C with favorable kinetics. The structural analysis confirmed the formation of NaBF 4 and Zn in the reaction products. The study concerning the reaction mechanism reveals that ZnF 2 plays a role of reagent rather than catalyst. The produced intermediate of NaZnF 3 , however, affects the decomposition of the emitted B 2 H 6 . This work suggests that the extension of the decomposition mechanism of NaBH 4 /ZnF 2 composite system would favor the development of new catalysts for complex hydride systems.

研究领域: 材料科学 · 能源化学 · 无机化学 · 储氢技术 · 纳米催化
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RSC Advances · 2015 ·Vol. 5 ·期 50 ·39878-39883 · IF 3.84

AgPd nanoparticles supported on zeolitic imidazolate framework derived N-doped porous carbon as an efficient catalyst for formic acid dehydrogenation

Cheng Feng,Yunhui Hao,Li Zhang,Ningzhao Shang,Shutao Gao,Zhi Wang,Chun Wang

Formic acid (FA) has tremendous potential as a safe and convenient source of hydrogen for renewable energy storage, but controlled and efficient dehydrogenation of FA by a robust solid catalyst constitutes a major challenge. In this report, a metal nanoparticle functionalized zeolitic imidazolate framework (ZIF) derived N-decorated nanoporous carbon (NPC) support was fabricated and used as an efficient FA decomposition catalyst for the first time. The resultant AgPd@NPC catalyst exhibited 100% H2 selectivity and high catalytic activity (TOF = 936 h−1) toward the dehydrogenation of formic acid at 353 K. The synergetic interaction between the metal nanoparticles and NPC greatly enhances the catalytic performance of the as-prepared catalyst.

研究领域: 催化化学 · 能源材料 · 纳米材料 · 物理化学 · 氢能存储
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2011 ·Vol. 36 ·期 23 ·15266-15272 · IF 4.057

A comparative study of LiBH4-based composites with metal hydrides and fluorides for hydrogen storage

Pei Pei Yuan,Bin Hong Liu,Zhou Peng Li

A comparative study was performed on four LiBH 4 -based hydrogen storage composites 2LiBH 4  + MgX 2 and 6LiBH 4  + CaX 2 (X = H and F). The composites with fluorides and those with corresponding hydrides exhibited similar hydrogen storage properties. The dehydrogenation of 2LiBH 4  + MgF 2 demonstrated a strong dependence on the hydrogen back pressure , similar to that of 2LiBH 4  + MgH 2 . The reversible hydrogen storage of 2LiBH 4  + MgF 2 was achieved under a back pressure of 5 bar at 450 °C. Dehydrogenation under lower H 2 pressures resulted in the production of Mg and thus a partial reversibility. In contrast, both 6LiBH 4  + CaH 2 and 6LiBH 4  + CaF 2 revealed reversible hydrogen storage properties regardless of the hydrogen back pressure. The structural difference between MgB 2 and CaB 6 may account for the observed differences in hydrogen storage properties of the Mg- and Ca-containing LiBH 4 reactive composites.

研究领域: 材料科学 · 能源化学 · 固态储氢 · 无机化学 · 功能材料
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Materials Today Communications · 2021 · IF 3.383

Enhance Mg-based heat storage materials kinetics by complex oxides

Daifeng Wu,Rui Li,Tai Sun,Renheng Tang,Fangming Xiao

Mg/MgH 2 as a thermochemical energy storage (TCES) material suffers from a slow hydrogenation-dehydrogenation kinetic and poor reversibility. Addition of metal oxide is an effective way to improve the kinetic properties of Mg/MgH 2 . However, there is little study on the effects of complex oxides . Thus, the catalytic effects of complex metal oxides and its catalytic mechanism were investigated in this paper. Results show that the dehydrogenation peak temperature and apparent activation energy of MgH 2 -Ta 2 O 5 are 320.8 °C and 128.54 kJ/mol. Combined with complex metal oxide, MgH 2 -Ta 2 O 5 -Nd 2 O 3 could further reduce the dehydrogenation peak temperature (307.2 °C) and apparent activation energy (95.33 kJ/mol). MgO and NdH 2.61 are found in the dehydrogenated MgH 2 -Ta 2 O 5 -Nd 2 O 3 , indicating that n-typed oxide Ta 2 O 5 and p-typed oxide Nd 2 O 3 are formed and improved the kinetics properties of MgH 2 . Furthermore, Nd 2 O 3 /Ta 2 O 5 interface is formed and acted as “p-n junction”. When heating, the “p-n junction” is exposed to thermal radiation and produce electrons and holes, and then the kinetics properties of MgH 2 are further enhanced.

研究领域: 材料科学 · 能源化学 · 物理化学 · 无机功能材料 · 热能存储
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2022 ·Vol. 47 ·期 83 ·35352-35364 · IF 7.139

Remarkable kinetics of novel Ni@CeO2–MgH2 hydrogen storage composite

Zhichao Yu,Wei Zhang,Yongxi Zhang,Yaokun Fu,Ying Cheng,Sanyang Guo,Yuan Li,Shumin Han

Magnesium hydroxide (MgH 2 ) has excellent reversibility and high capacity, and is one of the most promising materials for hydrogen storage in practical applications. However, it suffers from high dehydrogenation temperature and slow sorption kinetics. Rare earth hydrides and transition metals can both significantly improve the de/hydrogenation kinetics of MgH 2 . In this work, MgH 2 –Mg 2 NiH 4 –CeH 2.73 is in-situ synthesized by introducing Ni@CeO 2 into MgH 2 . The unique coating structure of Ni@CeO 2 facilitates homogeneous distribution of synergetic CeH 2.73 and Mg 2 NiH 4 catalytic sites in subsequent ball milling process. The as-fabricated composite MgH 2 -10 wt% Ni@CeO 2 powders possess superior hydrogenation/dehydrogenation characteristics, absorbing 4.1 wt% hydrogen within 60 min at 100 °C and releasing 5.44 wt% H 2 within 10 min at 350 °C. The apparent activation energy of MgH 2 -10 wt% Ni@CeO 2 is determined to be 84.8 kJ/mol and it has favorable hydrogen cycling stability with almost no decay in capacity after 10 cycles.

研究领域: 材料科学 · 无机化学 · 能源化学 · 纳米催化 · 氢能源存储
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Green Energy & Environment · 2021 ·Vol. 8 ·期 2 ·589-600 · IF 8.207

Metal organic framework supported niobium pentoxide nanoparticles with exceptional catalytic effect on hydrogen storage behavior of MgH2

Liuting Zhang,Farai Michael Nyahuma,Haoyu Zhang,Changshan Cheng,Jiaguang Zheng,Fuying Wu,Lixin Chen

Nb 2 O 5 nanoparticles with an average particle size of 10 nm supported on a rhombic dodecahedral metal organic framework (MOF) were successfully synthesized by a facile one-pot hydrothermal reaction and subsequent calcination process. Experimental results demonstrated that the prepared catalyst drastically improved the hydrogen storage behavior of MgH 2 . 7 wt% Nb 2 O 5 @MOF doped MgH 2 started to desorb hydrogen at 181.9 °C and 6.2 wt% hydrogen could be released within 2.6 min and 6.3 min at 275 °C and 250 °C, respectively. The fully dehydrogenated composite also displayed excellent hydrogenation by decreasing the onset absorption temperature to 25 °C and taking up 4.9 wt% and 6.5 wt% hydrogen within 6 min at 175 °C and 150 °C, respectively. Moreover, the corresponding activation energy was calculated to be 75.57 ± 4.16 kJ mol −1 for desorption reaction and 51.38 ± 1.09 kJ mol −1 for absorption reaction. After 20 cycles, 0.5 wt% hydrogen capacity was lost for the MgH 2 +7 wt% Nb 2 O 5 @MOF composite, much lower than 1.5 wt% of the MgH 2 +7 wt% Nb 2 O 5 composite. However, the addition of Nb 2 O 5 @MOF had limited effect on reducing the dehydrogenation enthalpy of MgH 2 . Microstructure analysis revealed that Nb 2 O 5 particles were uniformly distributed on surface of the MgH 2 matrix and synergistically improved the hydrogen storage property of MgH 2  with MOF.

研究领域: 材料科学 · 无机化学 · 纳米催化 · 能源存储 · 氢能源 · 固态储氢
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Journal of Materials Chemistry A · 2013 ·Vol. 1 ·期 35 ·10184-10192 · IF 0

Enhanced hydriding–dehydriding performance of a 2LiH–MgB2 composite by the catalytic effects of Ni–B nanoparticles

Jie Shao,Xuezhang Xiao,Lixin Chen,Xiulin Fan,Leyuan Han,Shouquan Li,Hongwei Ge,Qidong Wang

A system of 2LiH–MgB2 and its hydrogenated 2LiBH4–MgH2 is an attractive candidate for hydrogen storage. However, its hydriding–dehydriding kinetics have to be further improved for practical application. In the present work, three kinds of Ni–B nanoparticles with different crystalline states and particle sizes were prepared by wet-chemical reduction and mechanochemical methods, and then introduced into a 2LiH–MgB2 composite for catalytic enhancement. The catalytic roles of Ni–B nanoparticles on the hydriding–dehydriding properties were investigated systematically. The results show that all of the Ni–B nanoparticles can significantly enhance the hydriding–dehydriding kinetics of the 2LiH–MgB2 composite, resulting in no incubation period for the formation of MgB2 during dehydrogenation. The more disordered the amorphous structure and the smaller sized the Ni–B particles are, the better the catalytic effect that is obtained. Microstructure analyses clearly reveal the formation of the MgNi3B2 phase in the dehydriding process, which acts as the nucleation agent for MgB2 formation determined by an edge-to-edge model. Directly doping with Ni–B nanoparticles in the 2LiH–MgB2 system shows a higher hydrogen desorption capacity of 9.4 wt% and obtains a better catalytic efficiency than doping with NiCl2.

研究领域: 材料科学 · 储能材料 · 无机化学 · 纳米催化 · 氢储存
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

When Pt nanoparticles meet oxygen-deficient Co3O4: Enabling superior performance towards on-demand hydrogen generation from hydrolytic dehydrogenation of dimethylamine borane

Jing Jiang,Jiayi Zhang,Baihao Wu,Sheng Tu

The regulation of the metal-support interaction in heterogeneous catalysts can promote the activation of reactants, which is beneficial for the hydrolytic dehydrogenation reaction. Herein, the hydrolytic dehydrogenation of dimethylamine borane (DMAB) is systematically studied on the oxygen vacancy (O v ) enriched Pt-Co 3 O 4 heterogeneous catalyst with the metal-support interaction. It is found that the metallic Pt site facilitates the adsorption of DMAB molecules and the O v on Co 3 O 4 support as an electron-rich center cooperates with the adjacent Pt site to dissociate water molecules. The in situ Raman and attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy reveal the effective activation and cleavage of the O-H in water and the B-H in DMAB over the Pt-Co 3 O 4 catalyst. The optimal Pt-Co 3 O 4 catalyst exhibits the extraordinary activity for the catalytic hydrolysis of DMAB at 303 K, delivering a high specific hydrogen generation rate (64063 mL min −1 g pt −1 ) and a competitive turnover frequency (TOF, 23880 mol H2 mol Pt −1 h −1 ). This performance outperforms most of the reported heterogeneous catalysts for DMAB dehydrogenation . More importantly, the Pt-Co 3 O 4 catalyst achieves the desirable on-demand hydrogen production by using special chemical switches. This finding provides the fundamental understanding of metal-oxide systems with the collaborative interfacial catalysis for boosting DMAB dehydrogenation .

研究领域: 催化化学 · 纳米材料科学 · 能源化学 · 表面科学 · 多相催化 · 氢能存储与释放
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