INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2014
·
IF 2.93
Lina Chong,Jianxin Zou,Xiaoqin Zeng,Wenjiang Ding
In this work, the complex hydrogen sorption behaviors in a 3NaBH 4 /HoF 3 composite prepared through mechanical milling were carefully investigated, including the reactions occurred during ball milling and de-/rehydrogenation processes. Different from other rear earth fluorides, the HoF 3 can react with NaBH 4 during ball milling, leading to the formations of Na–Ho–F and Na–Ho–BH 4 complex compounds. The first dehydriding of the 3NaBH 4 /HoF 3 composite can be divided into 4 steps, including the ion exchange between H − and F − , the formation of NaHo(BH 4 ) 4 , the decomposition of NaHo(BH 4 ) 4 and reaction of NaBH 4 with Na–Ho–F compounds. The final products, HoB 4 , HoH 3 and NaF, can be rehydrogenated to generate NaBH 4 and NaHoF 4 with an absorption capacity of 2.3 wt% obtained at 400 °C. Based on the Pressure–Composition–Temperature measurements, the de-/rehydrogenation enthalpies of the 3NaBH 4 /HoF 3 composite are determined to be 88.3 kJ mol −1 H 2 and −27.1 kJ mol −1 H 2 , respectively.
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
BIOTECHNOLOGY LETTERS
·
2020
·Vol. 42
·期 3
·445-451
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IF 1.977
Zhang Lei,Xu Danyu,Kong Deyong,Ji Min,Shan Lianbin,Zhao Yongjiao
Objectives To investigate the effect of zero-valent iron and copper (Fe/Cu) micro-electrolysis on dark fermentative hydrogen production from glucose by a mixed bacterial consortium and the possible mechanisms of increasing hydrogen yield. Results Compared to zero-valent iron and activated carbon (Fe/C) micro-electrolysis, Fe/Cu micro-electrolysis could increase hydrogen yield by 32.2%, hydrogen production potential by 27.1%, and the maximum hydrogen production rate by 62.0%. Meanwhile, the number of ferrous ions released into the liquid phase with Fe/Cu micro-electrolysis was about 27.0% greater than that released by Fe/C micro-electrolysis, because the dispersion of copper on the surface of iron could markedly improve electrochemical corrosion activity. Metabolic analysis revealed that Fe/C micro-electrolysis promoted acetate formation, which may have been responsible for the observed improvement in fermentative hydrogen production. Further investigation indicated that Fe/Cu micro-electrolysis increased the activity of hydrogenases and stimulated the expression of the [FeFe]-hydrogenase gene. Conclusion Fe/Cu micro-electrolysis is better than Fe/C micro-electrolysis or Fe corrosion alone for dark fermentative hydrogen production.
研究领域:
环境工程
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微生物学
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生物技术
✓ 已验证
DOI
PubMed
高影响因子
SusMat
·
2025
·
IF 21.3
Xuechun Hu,Yuchen Pang,Chaoqun Li,Xiaoyue Zhang,Xuebin Yu,Fang Fang,Guanglin Xia
Magnesium hydride (MgH 2 ) has been regarded as an attractive candidate for solid-state hydrogen storage, yet its practical applications are limited by the requirement of elevated temperatures and sluggish hydrogen uptake and release kinetics. Herein, TiO 2 polyhedral frameworks with uniformly distributed V 2 O 5 (denoted as V 2 O 5 /TiO 2 ) are constructed to improve hydrogen storage performance of Mg/MgH 2 . During the reversible hydrogenation and dehydrogenation process, metallic V and Ti along with low-valent Ti- and V-based oxides are in situ formed. Among them, metallic V supported on TiO 2 exhibits the lowest hydrogen adsorption energy, enabling superior catalytic performance over TiO 2 and V 2 O 5 . As a result, the peak dehydrogenation temperature of MgH 2 decreases to 215°C, 105°C lower than that of pristine MgH 2 , with a decrease of the apparent activation energy from 139.50 kJ·mol −1 to 68.99 kJ·mol −1 . Moreover, electron migration from V toward TiO 2 leads to charge accumulation around Ti and O atoms, shifting the V 3 d -band center toward the Fermi level and thereby improving the catalytic function of V's d-electrons, facilitating hydrogen dissociation without energy barriers. Therefore, the V 2 O 5 /TiO 2 -catalyzed Mg absorbs 4.12 wt% H 2 under an ultralow pressure of 1 bar at 25°C. This provides a new strategy for developing advanced Ti and V-based catalysts for mild-condition hydrogen storage of MgH 2 .
研究领域:
材料科学
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氢能源存储
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催化
·
纳米材料
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固态化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Dongqiang Gao,Liuting Zhang,Mengchen Song,Fuying Wu,Jiao Wang,Hu Zhao,Hong Li
As a high-density solid-state hydrogen storage material, magnesium hydride (MgH 2 ) is promising for hydrogen transportation and storage. Yet, its stable thermodynamics and sluggish kinetics are unfavorable for that required for commercial application. Herein, nickel/vanadium trioxide (Ni/V 2 O 3 ) nanoparticles with heterostructures were successfully prepared via hydrogenating the NiV-based two-dimensional layered double hydroxide (NiV-LDH). MgH 2 + 7 wt% Ni/V 2 O 3 presented more superior hydrogen absorption and desorption performances than pure MgH 2 and MgH 2 + 7 wt% NiV-LDH. The initial discharging temperature of MgH 2 was significantly reduced to 190 °C after adding 7 wt% Ni/V 2 O 3 , which was 22 and 128 °C lower than that of 7 wt% NiV-LDH modified MgH 2 and additive-free MgH 2 , respectively. The completely dehydrogenated MgH 2 + 7 wt% Ni/V 2 O 3 charged 5.25 wt% H 2 in 20 min at 125 °C, while the hydrogen absorption capacity of pure MgH 2 only amounted to 4.82 wt% H 2 at a higher temperature of 200 °C for a longer time of 60 min. Moreover, compared with MgH 2 + 7 wt% NiV-LDH, MgH 2 + 7 wt% Ni/V 2 O 3 shows better cycling performance. The microstructure analysis indicated the heterostructural Ni/V 2 O 3 nanoparticles were uniformly distributed. Mg 2 Ni/Mg 2 NiH 4 and metallic V were formed in-situ during cycling, which synergistically tuned the hydrogen storage process in MgH 2 . Our work presents a facile interfacial engineering method to enhance the catalytic activity by constructing a heterostructure, which may provide the mentality of designing efficient catalysts for hydrogen storage.
研究领域:
材料科学
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能源存储
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纳米技术
·
化学工程
✓ 已验证
DOI
高影响因子
Journal of the American Chemical Society
·
2024
·
IF 14.4
Jiyue Zhang,Wenda Wang,Xiaowei Chen,Jinlong Jin,Xiaojun Yan,Jianmei Huang
As an efficient and clean energy carrier, hydrogen is expected to play a key role in future energy systems. However, hydrogen-storage technology must be safe with a high hydrogen-storage density, which is difficult to achieve. MgH2 is a promising solid-state hydrogen-storage material owing to its large hydrogen-storage capacity (7.6 wt %) and excellent reversibility, but its large-scale utilization is restricted by slow hydrogen-desorption kinetics. Although catalysts can improve the hydrogen-storage kinetics of MgH2, they reduce the hydrogen-storage capacity. Single-atom catalysts maximize the atom utilization ratio and the number of interfacial sites to boost the catalytic activity, while easy aggregation at high temperatures limits further application. Herein, we designed a single-atom Ni-loaded TiO2 catalyst with superior thermal stability and catalytic activity. The optimized 15wt%-Ni0.034@TiO2 catalyst reduced the onset dehydrogenation temperature of MgH2 to 200 °C. At 300 °C, the H2 released and absorbed 4.6 wt % within 5 min and 6.53 wt % within 10 s, respectively. The apparent activation energies of MgH2 dehydrogenation and hydrogenation were reduced to 64.35 and 35.17 kJ/mol of H2, respectively. Even after 100 cycles of hydrogenation and dehydrogenation, there was still a capacity retention rate of 97.26%. The superior catalytic effect is attributed to the highly synergistic catalytic activity of single-atom Ni, numerous oxygen vacancies, and multivalent Tix+ in the TiO2 support, in which the single-atom Ni plays the dominant role, accelerating electron transfer between Mg2+ and H– and weakening the Mg–H bonds. This work paves the way for superior hydrogen-storage materials for practical unitization and also extends the application of single-atom catalysis in high-temperature solid-state reactions.
研究领域:
储能技术
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催化化学
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材料科学
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纳米技术
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氢能技术
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固态化学
✓ 已验证
DOI
高影响因子
ACS Omega
·
2020
·
IF 2.87
Hao Wang,Fan Yang,Zhendong Yang,Han Yang,Yan Wu
A tetrathiotungstate-intercalated NiAl layered double hydroxide (LDH) was synthesized and then calcined under N2 at various temperatures to prepare a series of NiW presulfurized hydrotreating catalysts. Upon calcination, WS42– in the interlayer decomposes into WS3 and then WS2, releasing sulfur to sulfurize nickel in the sheets. The property and activities of catalysts for hydrodesulfurization (HDS) of dibenzothiophene and hydrodearomatization (HDA) of tetralin are dependent on the calcination temperature. At 300 °C, WS3 can be well maintained, offering highly active hydrogenation sites S22– and superior HDA activity. As the temperature increases up to 500 °C, WS3 converts into WS2, while nickel sulfides migrate to the edge of WS2 to form NiWS phases with high HDS activity. LDH-based presulfurized catalysts can achieve fully sulfurized and well-dispersed tungsten species even at high tungsten loadings and can retain more WS3 even at high temperatures because of the peculiar properties of LDHs. Therefore, they show better HDS and superior HDA activities over an oxidic NiW LDH-based catalyst (LDO) and an alumina-supported NiWS presulfurized catalyst (NiWS/Al2O3). The optimized catalyst shows 1.59 and 1.05 times higher HDS activity than LDO and NiWS/Al2O3 while 2.05 and 1.77 times higher HDA activity than LDO and NiWS/Al2O3, respectively. It also shows better HDS and HDA activity for a real diesel than a NiCoMoW/Al2O3 commercial catalyst.
研究领域:
催化化学
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材料科学
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石油加工工程
✓ 已验证
DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 15
·4763-4775
·
IF 6.177
Ting Zhu,Ran Wang,Ziteng Chen,Feng Ji,Yuan Dong,Ming Yang
The problem of safe and efficient storage and transportation of hydrogen energy limits the large-scale development of the “hydrogen economy”. The liquid organic hydrogen storage technology is based on reversible catalytic hydrogenation and dehydrogenation reactions of unsaturated compounds to achieve safe and efficient storage and release of hydrogen. Heterogeneous catalysts with excellent catalytic capacity and stability should be developed to drive the reactions. However, it is a challenge to develop these catalysts. We fabricated a series of RuPd-based and supported catalysts following two different methods, and the catalytic hydrogenation and dehydrogenation activities of these catalysts were systematically investigated. The experiment results implied that the Pd2.5Ru2.5/H2 (double reduction method) catalyst exhibited catalytic hydrogenation rates that were similar to those of Pd2.5Ru2.5/L (when reduced by NaBH4). The former exhibited much better catalytic dehydrogenation rates than the latter. The Pd2.5Ru2.5/H2 catalyst also exhibited much better catalytic recyclability than the Pd2.5Ru2.5/L catalyst, and the conclusion was arrived at by conducting 10 cycles of hydrogenation–dehydrogenation tests. The relationship between the catalytic performances and the catalyst's properties was further investigated using a combination of H2-TPR, NH3-TPD, XPS, and TEM techniques. The characterization results revealed that the double reduction process could be used to enhance the extent of electronic interaction of the RuPd active sites with the support, and more numbers of strong acidic sites and active sites could be generated. Furthermore, DFT calculations also revealed that 8H-NPCZ and 4H-NPCZ formed stable adsorption structures on the Ru3Pd3/Al2O3(100) surface, facilitating catalytic reactions. Notably, the reaction energies of Ru3Pd3/Al2O3(100) were 1.16 eV, 1.42 eV, and 1.63 eV, indicating that the dehydrogenation process (8H-NPCZ → 4H-NPCZ and 4H-NPCZ → NPCZ) occurred easily. All the above-mentioned characteristics make the Pd2.5Ru2.5/H2 catalyst an excellent catalyst for hydrogenation and dehydrogenation and endow it with outstanding catalytic capacity and recyclability.
研究领域:
材料科学
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催化化学
·
能源存储技术
✓ 已验证
DOI
高影响因子
Journal of Magnesium and Alloys
·
2024
·
IF 15.8
Jiaao Wu,Zhihao Liu,Haohua Zhang,Yongjin Zou,Bin Li,Cuili Xiang,Lixian Sun,Fen Xu,Ting Yu
Magnesium hydride (MgH 2 ) is an exceptional material for hydrogen storage, but its high desorption temperature and slow kinetics limit its applicability. In this study, the hydrogen storage performance of MgH 2 was enhanced using highly dispersed Ni-nanoparticle–doped hollow spherical vanadium nitride (Ni/VN), which was synthesized via a solvothermal process. The MgH 2 system doped with the synthesized Ni/VN exhibited an outstanding hydrogen-storage capability. Specifically, 5.6 wt.% of H 2 was released within 1 h at a relatively low temperature of 513 K, whereas 6.4 wt.% of H 2 was released within 180 s at 598 K, followed by an almost complete dehydrogenation after 10 min at 598 K. At 423 K, the developed material absorbed ∼6.0 wt.% of H 2 within 5 min. The activation energy for dehydrogenation was determined to be 78.07 ± 2.91 kJ·mol −1 , which was considerably lower than that of MgH 2 produced by ball milling (120.89 ± 5.74 kJ·mol −1 ), corresponding to a reduction of 35.4 %. It was deduced that the formation of Mg 2 Ni/Mg 2 NiH 4 (hydrogen pump) through the reaction of Ni nanoparticles during dehydrogenation/hydrogenation facilitated hydrogen transport and synergistically catalyzed hydrogen absorption and desorption by MgH 2 , improving its hydrogen storage capability. These findings offer novel perspectives for the utilization of MgH 2 in large-scale applications.
研究领域:
材料科学
·
能源存储
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Chemistry
·
2023
·
IF 7.3
C. Jiang,X. Wang,X. Xiao,M. Piao,Y. Jia,J. He,L. Hu,Y. Zou,L. Sun,L. Chen
Chemical complex borohydride is a promising hydrogen storage material due to its large gravimetric and volumetric hydrogen capacities. However, the high dehydrogenation temperature and sluggish kinetics still place strong restrictions on its practical application in the hydrogen storage field. In this work, a synergetic approach of partial cation substitution and catalysis is developed to enhance the hydrogen storage properties of LiBH 4 . The Li/Mg based dual-cation borohydride (LiMg 2 (BH 4 ) 5 , LMBH) was successfully synthesized by wet chemical ball milling of LiBH 4 and MgCl 2 . The optimal (LMBH (4.5:1) sample, LiBH 4 and MgCl 2 in molar ratios of 4.5:1, possesses a maximum hydrogen desorption capacity (11.27 wt%) and the outstanding initial decomposition temperature (∼250 °C). Importantly, the LMBH (4.5:1) doped with TiF 3 shows a remarkable onset dehydrogenation temperature as low as 97.2 °C, which is about 190 °C lower than that of pristine LiBH 4 . The LMBH (4.5:1) doped with TiF 3 system releases 7.98 wt% H 2 within 170 min below 350 °C. And the dehydrogenation product of doped composite can reversibly absorb ∼4.72 wt% H 2 at a relatively moderate temperature of 280 °C, which is substantially lower than the reversible hydrogen absorption temperature of previous modified borohydride systems. Based on the structural characteristic analyses, the TiF 3 reacts with LMBH (4.5:1) to in-situ form actual catalytic components of TiB 2 and TiH 2 as the actual catalysts for LMBH (4.5:1), resulting in the improved hydrogen re/dehydrogenation properties. The synergetic modification of Li/Mg dual-cation substitution and TiB 2 /TiH 2 catalysis may lead to the development of light-metal borohydrides with outstanding hydrogen storage properties.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
Journal of Magnesium and Alloys
·
2021
·
IF 10.088
Hui Yong,Xin Wei,Jifan Hu,Zeming Yuan,Shihai Guo,Dongliang Zhao,Yanghuan Zhang
The composites comprised of Co nanoparticle and C nanosheet were prepared though a high-temperature carbonization reaction. The catalysis of Co@C composites on the hydrogen storage behavior of Mg 90 Ce 5 Y 5 alloy was investigated in detail by XRD, SEM, TEM, PCI, and DSC method. Because of the synergistic catalytic function of C and Co in C@Co nanocomposites, the Mg 90 Ce 5 Y 5 alloy with 10 wt.% C@Co shows the excellent hydrogen absorption and desorption performances. Time for releasing hydrogen reduces from 150 min to 11 min with the addition of the C@Co composites at the temperature of 300 °C. Meanwhile, the dehydrogenation activation energy also declines from 130.3 to 81.9 kJ mol −1 H 2 after the addition of the C@Co composites. This positive effect attributes to the C layer with the high defect density and the Co nanoparticles, which reduces the energy barriers for the nucleation of Mg/MgH 2 phase and the recombination of hydrogen molecule. Besides, the C@Co composites also improve the activation property of the Mg 90 Ce 5 Y 5 alloy which was fully activated in the first cycle. Moreover, the temperature for initial dehydrogenation and the endothermic peak of the alloy hydride were also decreased. Although the addition of the C@Co composites increases the plateau pressures and decreases the value of the decomposition enthalpy, these differences are so small that the improvement on thermodynamics can hardly be seen.
研究领域:
材料科学
·
化学工程
·
能源存储
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Yangyang Zhou,Chen Chen,Qiling Li,Yanbo Liu,Ting Wei,Youzhen Liu,Zebing Zeng,Darren Bradshaw,Bing Zhang,Jia Huo
Hydrogenation of unsaturated biomass in a control manner is highly desirable but challenging, especially under mild conditions. We here report selective hydrogenation of α,β-unsaturated aldehydes (UALs), featuring a precise control of all potential products by adjustment of the role of ammonia borane (AB) in transfer and/or catalytic hydrogenation. The hydrogenation can be readily operated in neat water without using any external H 2 -source, because AB as the H 2 -source is favorable in aqueous solution. Impressively, unsaturated alcohols are prepared in 100% conversion by the room-temperature transfer hydrogenation of UALs with AB, while saturated aldehydes are obtained in 100% conversion and > 90% selectivity with high activity ( i.e ., turnover frequency = 0.98 s −1 for cinnamaldehyde), by the catalytic hydrogenation with H 2 released from AB and Pd immobilized on two-dimensional metal organic layer. On the other hand, UALs can be completely converted into the saturated alcohols through a combination of transfer and catalytic hydrogenation in one pot. This strategy can be extended to more than 8 types of UALs, and provides a facile way to fine-control the selective hydrogenation of unsaturated compounds with competing bonds.
研究领域:
化学
·
生物质能
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Magnesium and Alloys
·
2021
·
IF 10.088
Kang Chen,Hao Zhong,Liuzhang Ouyang,Fen Liu,Hui Wang,Jiangwen Liu,Huaiyu Shao,Min Zhu
LiBH 4 has been considered as one of the most promising energy storage materials with its ultrahigh hydrogen capacity, which can supply hydrogen through hydrolysis process or realize hydrogen-to-electricity conversion via anodic oxidation reaction of direct borohydride fuel cells (DBFCs). However, the realization of practical hydrogen applications heavily depends on the effective synthesis of high-purity LiBH 4 and recycling of the spent fuels (LiBO 2 ·xH 2 O). The present work demonstrates a convenient and high-efficiency solvent-free strategy for regenerating LiBH 4 with a maximum yield close to 80%, by retrieving its by-products with MgH 2 as a reducing agent under ambient conditions. Besides, the hydrogen released from the regeneration course can completely compensate the demand for consumed MgH 2 . The isotopic tracer method reveals that the hydrogen stored in LiBH 4 comes from both MgH 2 and coordinated water bound to LiBO 2 . Here, the expensive MgH 2 can be substituted with the readily available and cost-effective MgH 2 −Mg mixtures to simplify the regeneration route. Notably, LiBH 4 catalyzed by CoCl 2 can stably supply hydrogen to proton exchange membrane fuel cell (PEMFC), thus powering a portable prototype vehicle. By combining hydrogen storage, production and utilization in a closed cycle, this work offers new insights into deploying boron-based hydrides for energy applications.
研究领域:
能源化学
·
材料科学
✓ 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）