首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 335 毫秒
1.
Indole derivatives have been considered as promising liquid organic hydrogen carriers (LOHCs) for onboard hydrogen storage applications. Here a new member of indole family, 1,2-dimethylindole (1,2-DMID), was reported as a potential liquid organic hydrogen carrier with a hydrogen storage content of 5.23 wt%, a meting point of 55 °C and a boiling point of 260 °C. Full hydrogenation and dehydrogenation of 1,2-DMID can be achieved with fast kinetics under mild conditions. The hydrogenation of 1,2-DMID followed the first order kinetics with an apparent activation energy of 85.1 kJ/mol. Dehydrogenation of fully hydrogenated product, octahydro-1,2-DMID was conducted over 5 wt% Pd/Al2O3 at 170–200 °C. The stored hydrogen can be completely released at 180 °C in 3 h and at 200 °C in 1 h. The energy barrier of dehydrogenation of octahydro-1,2-DMID was calculated to be 111.9 kJ/mol 3 times cycles of hydrogenation and dehydrogenation were employed to test the recycle ability of 1,2-DMID. The structures of intermediates were also discussed by means of Material Studio calculations.  相似文献   

2.
The Mg-3.9 wt% Ni2Al3 nanocomposite is produced by hydrogen plasma-metal reaction method. The particle size of Mg is in range of 40–160 nm with an average size of 90 nm. The Ni2Al3 nanoparticles (NPs) of about 9 nm uniformly disperse on the surface of Mg NPs and in situ transform to Mg2NiH0.3 and Al after hydrogen absorption process. Surprisingly, the Mg2NiH0.3 and Al can recover to the initial state of Ni2Al3 after hydrogenation/dehydrogenation cycle. The Mg-Ni2Al3 nanocomposite shows enhanced hydrogen sorption rate and storage capacity. It can quickly uptake 6.4 wt% H2 within only 10 min at 573 K, and release 6.1 wt% H2 within 10 min at 623 K. The apparent activation energies for hydrogenation and dehydrogenation are calculated to be 55.4 and 115.7 kJ mol?1 H2. The enhanced hydrogen storage performances of the Mg-Ni2Al3 nanocomposite are attributed to both the nanostructure of Mg and the catalytic effects of Ni2Al3 NPs.  相似文献   

3.
The catalytic effects of K2NbF7 on the hydrogen storage properties of MgH2 have been studied for the first time. MgH2 + 5 wt% K2NbF7 has reduced the onset dehydrogenation temperature to 255 °C, which is 75 °C lower than the as-milled MgH2. For the rehydrogenation kinetic, at 150 °C, MgH2 + 5 wt% K2NbF7 absorbs 4.7 wt% of hydrogen in 30 min whereas the as-milled MgH2 only absorbs 0.7 wt% of hydrogen under similar condition. For the dehydrogenation kinetic, at 320 °C, the MgH2 + 5 wt% K2NbF7 is able to release 5.2 wt% of hydrogen in 5.6 min as compared to 0.3 wt% by the as-milled MgH2 under similar condition. Comparatively, the Ea value of MgH2 + 5 wt% K2NbF7 is 96.3 kJ/mol, which is 39 kJ/mol lower compared to the as-milled MgH2. The MgF2, the KH and the Nb that are found after the heating process are believed to be the active species that have improved the system properties. It is concluded that the K2NbF7 is a good catalyst to improve the hydrogen storage properties of MgH2.  相似文献   

4.
Mesoporous MoO3 shows an apparent activity in the catalytic hydrogenation of N-ethylcarbazole (NEC), where a significant amount of tetrahydro-N-ethylcarbazole (4H-NEC) and perhydro-N-ethylcarbazole (PNEC) are detected with the hydrogen uptake of 0.97 wt% after 6 h when the temperature rises to 220 °C. 0.5 wt% Pd/MoO3 catalyst shows a superior catalytic efficiency than the traditional precious metal catalysts 0.5 wt% Ru/Al2O3 and 0.5 wt% Pd/Al2O3, especially in the conversion of Octahydro-N-ethylcarbazole (8H-NEC) to PNEC. The hydrogenation mechanism of MoO3 is completely different from the traditional precious metal catalysts. With the presence of a small amount of Pd, the breaking of HH bond is greatly accelerated, result in the promotion of hydrogen spillover rate and the increase of the concentration of hydrogen molybdenum bronze HxMoO3, which improves the catalytic efficiency of the MoO3 catalyst. Rise the temperature also helps increasing the concentration of H in HxMoO3.  相似文献   

5.
A Mg17Al12 alloy was synthesized via sintering, and the catalytic effects of V and V2O5 on the hydrogen (H2)-storage properties of this alloy were investigated. The results revealed that the hydrogenation/dehydrogenation temperature of Mg17Al12 decreased markedly and the reversible hydrogen storage properties improved with the addition of V or V2O5. For example, at 250 °C, the Mg17Al12 alloy underwent hydrogenation only and a hydrogen absorption capacity of 2.22 wt.% was realized. However, with the addition of V and V2O5, (i) reversible hydrogen absorption/desorption occurred, (ii) the hydrogen absorption capacity increased to 2.95 wt.% and 3.35 wt.%, and (iii) the hydrogenation/dehydrogenation enthalpy of the Mg17Al12alloy decreased from 65.7/83.1 kJ·mol?1 to 62.6/69.3 kJ·mol?1 and 59.9/68.1 kJ·mol?1, respectively.  相似文献   

6.
Two-dimensional Mo2C (2D-Mo2C) is reported for the first time as an effective promoter of a Pt/Al2O3 catalyst for both the hydrogenation and dehydrogenation of the liquid organic hydrogen carrier (LOHC) pair, dibenzyltoluene (DBT) and perhydro-dibenzyltoluene (H18-DBT), respectively. Addition of 6.2 wt% 2D-Mo2C to a Pt/Al2O3 catalyst resulted in a significant increase in both the degree of hydrogenation and dehydrogenation compared to the unpromoted catalyst. An analysis of the initial (120 min) perhydro-DBT dehydrogenation kinetics in the temperature range of 270–330 °C, resulted in a reduction in apparent activation energy from 119.5 ± 3.8 kJ/mol for the Pt/Al2O3 catalyst to 110.4 ± 5.6 kJ/mol for the 6.2 wt% 2D-Mo2C/Pt/Al2O3 catalyst. The 6.2 wt% 2D-Mo2C/Pt/Al2O3 catalyst was also more stable than the unpromoted catalyst over several consecutive cycles of hydrogenation and dehydrogenation. Catalyst characterization showed that addition of 2D-Mo2C resulted in an increase in particle size and electron density of the Pt, which enhanced both the hydrogenation and dehydrogenation reactions, despite the fact that the 2D-Mo2C alone was inactive for both reactions.  相似文献   

7.
Carbon aerogel (CA) microspheres with highly crumpled graphene–like sheets surface and network internal structure have been successfully prepared by an inverse emulsion polymerization routine, subsequently ball milled with Mg powder to fabricate Mg@CA. The Mg change into MgH2 phases, decorating on the surface of the CA forming MgH2@CA microspheres composite after the hydrogenation process at 400 °C. The MgH2@CA microspheres composite displays MgH2–CA shell–core structure and shows enhanced hydrogenation and dehydrogenation rates. It can quickly uptake 6.2 wt% H2 within 5 min at 275 °C and release 4.9 wt% H2 within 100 min at 350 °C, and the apparent activation energy for the dehydrogenation is decreased to 114.8 kJ mol?1. The enhanced sorption kinetics of the composite is attributed to the effects of the in situ formed MgH2 NPs during the hydrogenation process and the presence of CA. The nanosized MgH2 could reduce the hydrogen diffusion distance, and the CA provides the sites for nucleation and prevents the grains from agglomerating. This novel method of in situ producing MgH2 NPs on zero–dimensional architecture can offer a new horizon for obtaining high performance materials in the hydrogen energy storage field.  相似文献   

8.
Transition metal-based oxides have been proven to have a substantial catalytic influence on boosting the hydrogen sorption performance of MgH2. Herein, the catalytic action of Ni6MnO8@rGO nanocomposite in accelerating the hydrogen sorption properties of MgH2 was investigated. The MgH2 + 5 wt% Ni6MnO8@rGO composites began delivering H2 at 218 °C, with about 2.7 wt%, 5.4 wt%, and 6.6 wt% H2 released within 10 min at 265 °C, 275 °C, and 300 °C, respectively. For isothermal hydrogenation at 75 °C and 100 °C, the dehydrogenated MgH2 + 5 wt% Ni6MnO8@rGO sample could absorb 1.0 wt% and 3.3 wt% H2 in 30 min, respectively. Moreover, as compared to addition-free MgH2, the de/rehydrogenation activation energies for doped MgH2 composites were lowered to 115 ± 11 kJ/mol and 38 ± 7 kJ/mol, and remarkable cyclic stability was reported after 20 cycles. Microstructure analysis revealed that the in-situ formed Mg2Ni/Mg2NiH4, Mn, MnO2, and reduced graphene oxide synergically enhanced the hydrogen de/absorption properties of the Mg/MgH2 system.  相似文献   

9.
Herein, we demonstrate the successful preparation of a novel complex transition metal oxide (TiVO3.5) by oxidizing a solid-solution MXene (Ti0.5V0.5)3C2 at 300 °C and its high activity as a catalyst precursor in the hydrogen storage reaction of MgH2. The prepared TiVO3.5 inherits the layered morphology of its MXene precursor, but the layer surface becomes very coarse because of the presence of numerous nanoparticles. Adding a minor amount of TiVO3.5 remarkably reduces the dehydrogenation and hydrogenation temperatures of MgH2 and enhances the reaction kinetics. The 10 wt% TiVO3.5-containing sample exhibits optimal hydrogen storage properties, as it desorbs approximately 5.0 wt% H2 in 10 min at 250 °C and re-absorbs 3.9 wt% H2 in 5 s at 100 °C and under 50 bar of hydrogen pressure. The apparent activation energy is calculated to be approximately 62.4 kJ/mol for the MgH2-10 wt% TiVO3.5 sample, representing a 59% reduction in comparison with pristine MgH2 (153.8 kJ/mol), which reasonably explains the remarkably reduced dehydrogenation operating temperature. Metallic Ti and V are detected after ball milling with MgH2; they are uniformly dispersed on the MgH2 matrix and act as actual catalytic species for the improvement of the hydrogen storage properties of MgH2.  相似文献   

10.
Catalytic effects of TiH2 on hydrogenation/dehydrogenation kinetics of MgH2 were investigated in this study. The TG analysis showed that the addition of the x wt% TiH2 exhibited lower onset temperature of 160°C which is 100°C and 190°C lower than as‐milled and as‐received MgH2. The dehydrogenation and hydrogenation kinetics were significantly improved compared with the pure MgH2. The activation energy for the hydrogen desorption of MgH2 was reduced from ?137.13 to ?77.58 kJ/mol by the addition of TiH2. XRD and XPS results showed that the phase of TiH2 remained same during the dehydrogenation without any intermediate formation confirming its role as catalyst.  相似文献   

11.
An alloy with nominal composition V85Ni15 was prepared in a vacuum induction melting apparatus. The chemical analysis of the sample showed a V (Ni) content of 82.63 (15.68) at% and small contaminations by carbon and aluminum. XRD measurements confirmed that the bcc Ni-V solid solution phase is the main constituent of the sample. However, a minor impurity (approximately 6.5 wt%) due to the precipitation of the sigma NiV3-x phase is present in the sample.Hydrogen sorption measurements extending from 150 °C up to 400 °C in a wide pressure range (up to 90 bar) were performed. Upon hydrogenation below 250 °C, one observes the subsequent presence of an α phase and of two hydride phases with different values of dehydrogenation enthalpy: ΔHdehydr = 21 ± 1 kJ/mol for 0.15 ≤ H/M ≤ 0.30 and ΔHdehydr = 26 ± 2 kJ/mol for 0.53 ≤ H/M ≤ 0.59. Above 300 °C, there is no evidence of the formation of hydrides and only an α phase is present up to the maximum measured composition, with a hydrogenation enthalpy ΔHhydr = 10.0 ± 0.5 kJ/mol.  相似文献   

12.
The dehydrogenation reaction pathway of a 0.91 (0.62LiBH4-0.38NaBH4)-0.09Ni mixture in the temperature range of 25–650 °C in flowing Ar and the cycling stability in H2 are presented. No H2 is released immediately after melting at 225 °C. The major dehydrogenation occurs above 350 °C. Adding nano-sized Ni reduces the dehydrogenation peak temperatures by 20–25 °C, leading to three decomposition steps where Ni4B3 and Li1.2Ni2.5B2 are found in the major dehydrogenation products for the 1st and the 3rd step; whilst the Ni-free mixture decomposes through a two-step decomposition pathway. A total of 8.1 wt% of hydrogen release from the 0.91 (0.62LiBH4-0.38NaBH4)-0.09Ni mixture is achieved at 650 °C in Ar. This mixture has a poor hydrogen cycling stability as its reversible hydrogen content decreases from 5.1 wt% to 1.1 wt% and 0.6 wt% during three complete desorption-absorption-cycles. However, the addition of nano-sized Ni facilitates the reformation of LiBH4.  相似文献   

13.
This paper presents the results from experimental study of syngas production by catalytic cracking of tar in wastewater under supercritical condition. Ni/Al2O3 catalysts were prepared via the ultrasonic assisted incipient wetness impregnation on activated alumina, and calcined at 600 °C for 4 h. All catalysts showed mesoporous structure with specific surface area in a range of 146.6–215.3 m2/g. The effect of Ni loading (5–30 wt%), reaction temperature (400–500 °C), and tar concentration (0.5–7 wt%) were systematically investigated. The overall reaction efficiency and the gas yields, especially for H2, were significantly enhanced with an addition of Ni/Al2O3 catalysts. With 20%Ni/Al2O3, the H2 yield increased by 146% compared to the non-catalytic experiment. It is noteworthy that the reaction at 450 °C with the addition of 20%Ni/Al2O3 had a comparable efficiency to the reaction without catalyst at 500 °C. The maximum H2 yield of 46.8 mol/kgtar was achieved with 20%Ni/Al2O3 at 500 °C and 0.5 wt% tar concentration. The catalytic performance of the catalysts gradually decreased as the reuse cycle increased, and could be recovered to 88% of the fresh catalyst after regeneration. 20%Ni/Al2O3 has a potential to improve H2 production, as well as a good reusability. Thus, it is considered a promising catalyst for energy conversion of tar in wastewater.  相似文献   

14.
Hydrogen being a dynamically impending energy transporter is widely used in hydrogenation reactions for the synthesis of various value added chemicals. It can be obtained from dehydrogenation reactions and the acquired hydrogen molecule can directly be utilized in hydrogenation reactions. This correspondingly avoids external pumping of hydrogen making it an economical process. We have for the first time tried to carryout 1,4-butanediol dehydrogenation and benzaldehyde hydrogenation simultaneously over ceria-alumina supported copper (Cu/CeO2–Al2O3) catalyst. In this concern, 10 wt% of Cu supported on CeO2–Al2O3 (3:1 ratio) was synthesized using wet impregnation method. The synthesized catalyst was then characterized by various analytical methods such as BET, powder XRD, FE-SEM, H2-TPR, NH3 and CO2-TPD, FT-IR and TGA. The catalytic activity towards simultaneous 1,4-butanediol dehydrogenation and benzaldehyde hydrogenation along with their individual reactions was tested for temperature range of 240 °C–300 °C. The physicochemical properties enhanced the catalytic activity as clearly interpreted from the results obtained from the respective characterization data. The best results were obtained with 10 wt% of Cu supported on CeO2–Al2O3 (3:1 ratio) catalyst with benzaldehyde conversion of 34% and 84% selectivity of benzyl alcohol. The conversion of 1,4-butanediol was seen to be 90% with around 95% selectivity of γ-butyrolactone. The catalyst also featured physicochemical properties namely increased surface area, higher dispersion and its highly basic nature, for the simultaneous reaction towards a positive direction. In terms of permanence, the Cu/CeO2–Al2O3 (10CCA) catalyst was quite steady and showed stable activity up to 24 h in time on stream profile.  相似文献   

15.
The de-/rehydrogenation features of the 6LiBH4/SrF2 reactive hydride system have been systematically investigated. It was found that the thermal stability of LiBH4 can be reduced markedly by combining it with SrF2. Dehydrogenation of the 6LiBH4/SrF2 system proceeds via the 6LiBH4 + SrF2 → SrB6 + 2LiF + 4LiH + 10H2 reaction, which involves SrH2 as the intermediate product. The dehydrogenation enthalpy change was experimentally determined to be 52 kJ/mol H2 based on the P–C isotherm analysis. For rehydrogenation, LiBH4 and SrF2 were regenerated along with LiSrH3 at 450 °C under ~8 MPa hydrogen pressure; thus, approximately 5.2 wt% of hydrogen can be released during the second dehydrogenation process.  相似文献   

16.
In order to improve the hydrogenation/dehydrogenation properties of the Mg/MgH2 system, the nickel hydride complex NiHCl(P(C6H11)3)2 has been added in different amounts to MgH2 by planetary ball milling. The hydrogen storage properties of the formed composites were studied by different thermal analyses methods (temperature programmed desorption, calorimetric and pressure-composition-temperature analyses). The optimal amount of the nickel complex precursor was found to be of 20 wt%. It allows to homogeneously disperse 1.8 wt% of nickel active species at the surface of the Mg/MgH2 particles. After the decomposition of the complex during MgH2 dehydrogenation, the formed composite is stable upon cycling at low temperature. It can release hydrogen at 200 °C and absorb 6.3 wt% of H2 at 100 °C in less than 1 h. The significantly enhanced H2 storage properties are due to the impact of the highly dispersed nickel on both the kinetics and thermodynamics of the Mg/MgH2 system. The hydrogenation and dehydrogenation enthalpies were found to be of −65 and 63 kJ/mol H2 respectively (±75 kJ/mol H2 for pure Mg/MgH2) and the calculated apparent activation energies of the hydrogen uptake and release processes are of 22 and 127 kJ/mol H2 respectively (88 and 176 kJ/mol H2 for pure Mg/MgH2). The change in the thermodynamics observed in the formed composite is likely to be due to the formation of a Mg0.992Ni0.008 phase during dehydrogenation/hydrogenation cycling. The impact of another hydride nickel precursor in which chloride has been replaced by a borohydride ligand, namely NiH(BH4)(P(C6H11)3)2, is also reported.  相似文献   

17.
Resin catalysts have the advantage of having various properties and long lifetime due to their ability to be regenerated easily, which makes them attractive supports. In this paper, a comparative study was conducted to optimize the dehydrogenation reaction condition using two different types of support materials: alumina (Al2O3), and Amberlyst-15 and to improve the catalytic activity as well as preparing an efficient and low-cost system for practical application, ruthenium metal catalyst was incorporated on Amberlyst-15 resin (a sulfonic acid type based upon a styrene-divinylbenzene copolymer) to release H2 via hydrolytic dehydrogenation of ammonia borane. Using ruthenium (Ru) catalysts based on Amberlyst-15 support material and comparing the results with Al2O3 as the common supporting material is considered to be studied for the first time. The effect of temperature (20–50 °C), the initial ammonia borane concentration (0.05–0.5 %wt), and catalyst amount (0.2–0.5 g) on the produced H2 yield was also investigated. Ru@Amberlyst-15 nanoparticle was discovered to be an effective catalyst for hydrogen evolution via the hydrolysis of ammonia borane with a turnover frequency value (TOF) of 343.3 min?1, while Ru@Al2O3 yielded a TOF of 87.5 min?1 at the room temperature. Therefore, it can be concluded that the Amberlyst-15 supporting effect on ruthenium metal leads an increase in the hydrogen production rate.  相似文献   

18.
Organic liquid heteroaromatic compounds, e.g. 9-ethylcarbazole, are potentially promising hydrogen storage materials because they can be catalytically hydrogenated and dehydrogenated at relatively moderate temperatures. In the present work, the cyclic hydrogenation of 9-ethylcarbazole and the temperature controlled stage-wise dehydrogenation of perhydro-9-ethylcarbazole were investigated. Full hydrogenation of 9-ethylcarbazole was realized over a 5 wt% Ru/Al2O3 catalyst at 180 °C and 80 bar, yielding a gravimetric density of 5.79 wt%. The catalytic dehydrogenation of perhydro-9-ethylcarbazole over a 5 wt% Pd/Al2O3 catalyst was found to undergo a three-stage process, i.e. perhydro-9-ethylcarbazole → octahydro-9-ethylcarbazole, octahydro-9-ethylcarbazole → tetrahydro-9-ethylcarbazole, and tetrahydro-9-ethylcarbazole → 9-ethylcarbazole with the initial reaction temperatures of 128 °C, 145 °C and 178 °C, respectively. Our results indicate that 9-ethylcarbazole displays an excellent cycle performance with very little capacity degradation after 10 cycles of catalytic hydrogenation and dehydrogenation. The hydrogen gas produced from the dehydrogenation possesses a high purity of over 99.99% with no carbon monoxide or other poisonous gases for fuel cells.  相似文献   

19.
Thermal dehydrogenation of Ca(BH4)2 and Ca(BH4)22MgH2 composite has been investigated, and the results were compared. The Ca((BH4)2 dehydrogenated in two steps between 325 °C and 500 °C as per the reactions Ca(BH4)2 = CaH2 + 2B + 3H2, and Ca(BH4)2 = 1/3CaB6 + 2/3CaH2 + 10/3H2. The partial dehydrogenation of CaH2 also takes place during the second step dehydrogenation according to the reaction CaH2 + 6B = CaB6 + H2. The completion of second step dehydrogenation requires a temperature of higher than 500 °C. The activation energies corresponding to these steps were found to be 149 ± 8 kJ/mol and 162 ± 10 kJ/mol, respectively. The Ca(BH4)22MgH2 composite dehydrogenates in a single step as per the reaction: Ca(BH4)2 + 3MgH2 = CaMg2 + 2B + 7H2 + Mg. The dehydrogenation of Ca(BH4)22MgH2 started at 340 °C and completed before 450 °C. The activation energy of Ca(BH4)22MgH2 dehydrogenation was found to be 180 ± 8 kJ/mol.  相似文献   

20.
Magnesium hydroxide (MgH2) 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 MgH2. In this work, MgH2–Mg2NiH4–CeH2.73 is in-situ synthesized by introducing Ni@CeO2 into MgH2. The unique coating structure of Ni@CeO2 facilitates homogeneous distribution of synergetic CeH2.73 and Mg2NiH4 catalytic sites in subsequent ball milling process. The as-fabricated composite MgH2-10 wt% Ni@CeO2 powders possess superior hydrogenation/dehydrogenation characteristics, absorbing 4.1 wt% hydrogen within 60 min at 100 °C and releasing 5.44 wt% H2 within 10 min at 350 °C. The apparent activation energy of MgH2-10 wt% Ni@CeO2 is determined to be 84.8 kJ/mol and it has favorable hydrogen cycling stability with almost no decay in capacity after 10 cycles.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号