Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 17
·10723-10728
·
IF 10.733
Hao Zhong,Liuzhang Ouyang,Meiqin Zeng,Jiangwen Liu,Hui Wang,Huaiyu Shao,Michael Felderhoff,Min Zhu
The regeneration of sodium borohydride (NaBH4) is crucial to form a closed cycle after it either supplies hydrogen energy via a hydrolysis process or provides energy through electron transfer at the anode of direct borohydride fuel cells (DBFCs). In both of these cases, the spent fuels are NaB(OH)4 from NaBO2 aqueous solution. However, the current regeneration process from (NaB(OH)4)·xH2O to form NaBH4 by reduction reaction and calcination at high temperature with metal hydrides as reducing agents is very expensive. In this work, we developed a simple regeneration process via ball milling with Mg–Al alloys as the reducing agent for NaB(OH)4 under an argon atmosphere. Under optimized conditions, a high yield of about 72% of NaBH4 could be obtained. Mechanistic study showed that all the hydrogen atoms from NaB(OH)4 remain in NaBH4 and no additional hydrogen sources are needed for the reduction process. The inexpensive Mg–Al alloy works as a reducing agent transforming the H+ to H− in NaBH4. This approach demonstrates a ∼20-fold cost reduction compared with the method using metal hydrides. This opens the door to the commercial implementation of simple ball milling processes for the regeneration of spent NaBH4 from NaB(OH)4 with cheap reducing agents.
研究领域:
化学工程
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能源材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2013
·
IF 2.39
Pei Pei Yuan,Bin Hong Liu,He Peng Zhu,Wei Yuan Pan,Zhou Peng Li
In this work, the composites of LiBH 4 and AlF 3 were prepared and their hydrogen storage properties were investigated. The AlF 3 addition to LiBH 4 resulted in significant decreases in dehydrogenation temperature. All the x LiBH 4 + AlF 3 ( x = 1, 2, 3, 5) composites started to release hydrogen from about 100 °C. The dehydrogenation of the composites was accomplished through several steps, depending on the molar ratio of LiBH 4 to AlF 3 . A new phase Li 3 AlF 6 was formed during the first dehydrogenation step, which further reacted with LiBH 4 . AlB 2 was formed only at temperatures higher than 300 °C. Li 2 B 12 H 12 was detected as an intermediate. The dehydrogenation reactions have significantly reduced and thus favorable enthalpy changes. However, the reversibility of the composites needs to be improved.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Kang Chen,Mili Liu,Liuzhang Ouyang,Hui Wang,Jiangwen Liu,Min Zhu
Hydrolysis of LiBH 4 (LB in short) is considered as a potential means of releasing the hydrogen stored in the hydride and the water. However, the hydrolysis of LB occurs only above 0 °C and efficient catalysts are required to accelerate the hydrogen kinetics. Here, we demonstrate an efficient non-catalytical hydrogen generation system that enables H 2 production of LB over a wide range of temperatures with methanol (referred to MeOH), ethylene glycol, and MeOH/water mixtures as reaction solvents. The results indicate that the hydrogen kinetics of LB is controllable by MeOH dose, MeOH species, reaction temperature, and solution components. For instance, the hydrogen evolution rate could be accelerated from 266 to 515 mL H2 min −1 g −1 (per unit weight of LB) with a H 2 yield up to 93% by tailoring the dose of methanol at 25 °C. Notably, the glycolysis kinetics is much faster than that for the methanolysis of LB, delivering a hydrogen rate varying from 523 to 10,125 mL H2 min −1 g −1 . By optimizing reaction conditions, a gravimetric hydrogen density of ~4.6 wt% H 2 was realized in the LB-MeOH system. Interestingly, the methanolysis/glycolysis products of LB can spontaneously convert into MeOH and hydrated byproduct (LiBO 2 ‧2H 2 O) by reacting with water, and MeOH may be separated and reused as an intermediate. Here, LiBO 2 ‧2H 2 O can be easily regenerated back to LB by ball milling with Mg under ambient conditions. Thus, a hydrogen cycle combining hydrogen generation and storage in a closed material cycle is achieved, which may lay the foundation for developing practical hydrogen sources for mobile/portable applications.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Yongyang Zhu,Shaoyang Shen,Xu-Sheng Yang,Liming Zeng,Gary Tsui,Zheng-Long Xu,Qing Zhou,Renheng Tang,K.C. Chan
Lithium borohydride (LiBH4) is a promising hydrogen storage material, but the irreversibility of hydrolysis and the high cost of regeneration have severely restrained its commercial applications. Herein, we reported a cost-effective method to regenerate LiBH4 by ball milling hydrous lithium metaborate (LiBO2·2H2O) with low-cost Mg-based alloys, instead of MgH2, under ambient conditions. An effective strategy is developed to improve the regeneration kinetics of LiBH4 by introducing the light rare-earth metals into Mg to facilitate the breakage of B–O and conversion of H+ into H–. A yield of 40% can be achieved for a relatively short ball milling duration (10 h) for the LiBO2·2H2O-CeMg12 system. The optimized regeneration of LiBH4 is believed to be efficient and economical since it utilizes an intrinsic hydrogen source in LiBO2·2H2O and cheap reducing agents. Our finding is expected to enable a wide deployment of LiBH4 for hydrogen storage.
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
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2013
·
IF 2.206
Chenhua Shu,Tonghua Sun,Jinping Jia,Ziyang Lou
A novel integrated process was proposed for reductive desulfurization of diesel fuel, in which the reductant sodium borohydride (NaBH4) was in situ generated via sodium metaborate (NaBO2) electroreduction. In order to improve the conversion rate of BO2– into BH4–, NaBO2 electroreduction was fulfilled by applying pulse voltage and using a boron-doped diamond (BDD) thin film electrode. The NaBO2 electroreduction process was analyzed by cyclic voltammetry and 11boron nuclear magnetic resonance (11B NMR) and the factors that influenced desulfurization efficiency were investigated. Under the optimal conditions desulfurization efficiency reached more than 93% for model diesel fuel. The components of model diesel fuel after desulfurization were analyzed by gas chromatography/mass spectrometry (GC/MS) and the electrolyte and digestion solution of precipitate were analyzed by inductively coupled plasma (ICP). Results indicated that B recycle was realized at the same time as desulfurization. Finally, the desulfurization of real diesel fuel was investigated. This work showed that the integrated process may be a new option for desulfurization of diesel fuel due to its mild conditions.
研究领域:
化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2016
·
IF 3.205
Jiaguang Zheng,Xuezhang Xiao,Liuting Zhang,Yan He,Shouquan Li,Hongwei Ge,Lixin Chen
Mg(BH 4 ) 2 has been considered as one of the promising light metal complex hydrides due to its high hydrogen capacity and low cost. But its higher thermal stability (dehydrogenation at above 300 °C) needs to be improved for the practical application. In this study, the aluminum hydride AlH 3 was introduced into complex borohydride Mg(BH 4 ) 2 to synthesize a new Mg(BH 4 ) 2 AlH 3 composite by ball milling method. It is found that the active Al ∗ formed from the self-decomposition of AlH 3 can effectively improve the dehydrogenation properties of Mg(BH 4 ) 2 , the Mg(BH 4 ) 2 AlH 3 composite starts to release hydrogen at 130.8 °C with a total hydrogen capacity of 11.9 wt.%. The dehydrogenated products of the composite is composed of Mg 2 Al 3 and B at 350 °C, resulting in the improved hydrogen desorption properties of Mg(BH 4 ) 2 AlH 3 composite. The Mg 2 Al 3 and B products would be further transformed into MgAlB 4 and Al at 500 °C. Moreover, the Mg 2 Al 3 and B dehydrogenated products show better reversible hydrogen storage property than that of the MgAlB 4 and Al products. This research shows a way to alter hydrogen de/hydrogenation route and reversibility of Mg(BH 4 ) 2 complex hydride by compositing with AlH 3 and controlling the dehydrogenation temperature.
研究领域:
材料科学
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能源化学
✓ 已验证
DOI
高影响因子
CHEMICAL PHYSICS LETTERS
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2020
·
IF 2.029
Chunhui Yue,Pan Yang,Jingchuan Wang,Xiaochong Zhao,Yuqi Wang,Lijun Yang
Development of low-cost and high-efficiency catalysts for hydrogen generation represents the significant challenge for realizing hydrogen economy. NiCo and nano-Pd loaded NiCo microfibers with high surface area has been successfully developed by electrospinning and following vacuum thermal treatment. Towards hydrogen generation, the catalyst exhibits efficient TOF as high as 350 and 680 mL min −1 gcat −1 for NiCo and nano-Pd loaded NiCo microfibers, providing superior performance compared with the most promising reported catalysts. The excellent catalytic activity remain above 90% confirming the remarkable durability. The insights uncovered here inspire and guide the rational design of advanced catalysts for the rapidly developing hydrogen energy applications.
研究领域:
材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Hao Zhong,Kang Chen,Chenglei Qin,Chengguang Lang,Jiangwen Liu,Hui Wang,Junrui Zhang,Liuzhang Ouyang
Onsite hydrogen generation by sodium borohydride hydrolysis resolves hydrogen energy supply system challenges. However, the spent-NaBH 4 regeneration is still a problem in the closed loop of this irreversible reaction. As the by-product is the key to the problem, NaB(OH) 4 is regarded as not the boron source but the hydrogen source of NaBH 4 regeneration. Therefore, in this study, inexpensive Al metal and NaB(OH) 4 are ball milled under argon to regenerate NaBH 4 without additional hydrogen input. However, the ball-milling reaction is hindered by the flexible Al and impact oxide layer, and the NaBH 4 yield is only approximately 22 %. Therefore, a brittle intermetallic compound Mg 2 Al 3 is reacted with NaB(OH) 4 by ball milling, achieving a NaBH 4 yield of over 42 %. The mechanism study shows that the brittleness of the raw material plays an important role in promoting the ball-milling reaction. This study achieves NaBH 4 regeneration using only Al as the reducing agent and provides a promising method to promote the mechanochemical regeneration of NaBH 4 .
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2013
·Vol. 4
·期 5
·2550-2556
·
IF 2.562
Liuting Zhang,Xuezhang Xiao,Xiulin Fan,Shouquan Li,Hongwei Ge,Qidong Wang,Lixin Chen
A simple approach to dramatically enhance the dehydrogenation properties of sodium borohydride is achieved by ball milling NaBH4 with fluorographite (FGi). It was found that the ball-milled NaBH4–FGi composite starts to release hydrogen without impurity gas at a lower temperature of 125 °C, and obtains a hydrogen desorption capacity of ca. 4.8 wt% below 130 °C in seconds, which is improved markedly compared to the ball-milled pristine NaBH4. The significant thermodynamic and kinetic improvement of the NaBH4–FGi composite can be ascribed to the reaction between NaBH4 and FGi as well as the formation of micro-scale NaBH4. Moreover, since the dehydrogenation process of NaBH4–FGi composite is exothermal, the fully reverse reaction is not feasible. In-depth investigations show that the partial rehydrogenation is due to the formation of Na2B12H12 and another new borohydride.
研究领域:
材料科学
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能源化学
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纳米科技
·
物理化学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Yongyang Zhu,Liuzhang Ouyang,Hao Zhong,Jiangwen Liu,Hui Wang,Huaiyu Shao,Zhenguo Huang,Min Zhu
Sodium borohydride (NaBH4) has been identified as one of the most promising hydrogen storage materials; however, it is still challenging to produce NaBH4 with low cost and high efficiency, which are largely determined by the sources of boron and hydrogen and reducing agents used. Herein, we report an economical method to produce NaBH4 by ball milling hydrated borax (Na2B4O7·10H2O and/or Na2B4O7·5H2O) with different reducing agents such as MgH2, Mg, and NaH under ambient conditions. The direct use of natural hydrated borax avoids the dehydration process (at 600 °C) and consequently reduces cost and improves overall energy efficiency. A high yield of 93.1% can be achieved for a short ball mill duration (3.5 h) for Na2B4O7·5H2O-NaH-MgH2 system. In this system, H2 is generated in situ which subsequently reacts with Mg forming MgH2. Low cost Mg is therefore employed to replace the majority of MgH2, leading to an attractive yield of 78.6%. To further reduce the cost of raw materials and improve the utilization of hydrogen source in the hydrated borax, Na2B4O7·10H2O is used to partially substitute for Na2B4O7·5H2O, leading to a complete replacement of MgH2. Compared with literature results, the optimized recipe features low cost and high efficiency since it utilizes hydrogen from the hydrated water in natural borax and avoids high temperatures. Our finding is expected to facilitate applications of NaBH4 for hydrogen storage.
研究领域:
材料科学
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能源化学
✓ 已验证
DOI
高影响因子
Chemistry-An Asian Journal
·
2018
·Vol. 13
·期 15
·1932-1940
·
IF 3.692
Nianming Jiao,Yanqiang Zhang,Hao Li,Long Liu,Suojiang Zhang
Graphical Yes, it is rocket science ! Both the cations and the anions of hypergolic ionic liquids, [bis(imidazolyl)–BH 2 ] + [bis(triazolyl)–BH 2 ] − (see figure), were functionalized with B−H groups and azoles, which play the roles of ‘hypergolic triggers’ and ‘regulators’, respectively. These ionic liquids show great promise as sustainable rocket fuels. [Bis(imidazolyl)–BH 2 ] + [bis(triazolyl)–BH 2 ] − and [bis(imidazolyl)–BH 2 ] + [tris(triazolyl)–BH] − were synthesized, the cations and anions of which were functionalized with B−H groups and azoles. As B−H groups contribute to the hypergolic activity and azole groups improve the energy output, the resulting ionic liquids exhibited ignition delay times as low as 20 ms and energy outputs as high as 461.1 kJ mol −1 . In addition, densities (1.07–1.22 g cm −3 ) and density-specific impulse (≈360 s g cm −3 ) values reached a relatively high level. These ionic liquids show great promise as sustainable rocket fuels.
研究领域:
化学
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材料科学
·
航天工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Xin Zhang,Wenxuan Zhang,Lingchao Zhang,Zhenguo Huang,Jianjiang Hu,Mingxia Gao,Hongge Pan,Yongfeng Liu
Lithium borohydride (LiBH 4 ) exhibits poor hydrogen storage reversibility because of phase separation between LiH and B due to foaming during thermal dehydrogenation. Herein, we report that by synthesizing nanostructured LiBH 4 without any supports, the foaming and phase separation can be effectively suppressed, and consequently, the hydrogen storage reversibility of LiBH 4 can be considerably improved. Using a facile single-pot solvothermal approach, a hierarchical porous nanostructured LiBH 4 composed of 50–60 nm-sized primary nanoparticles is synthesized. The resulting neat nano-LiBH 4 reversibly desorbs and absorbs approximately 12 wt% of H at 400 °C and under 100 bar H 2 . The superior hydrogen storage performance is attributed to the effective inhibition of foaming upon heating. The formation of LiH and B prior to melting, which can be associated with the largely reduced particle sizes and porous agglomeration structure, plays a crucial role in suppressing foaming. Our findings offer a new strategy for the preparation of nanoscaled freestanding borohydrides, and also important insights into the development of highly reversible metal borohydrides for hydrogen storage applications.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）