Hydrogen storage in low silica type X zeolites

Low silica type X zeolites (LSX, Si/Al = 1) fully exchanged by alkali-metal cations (Li(+), Na(+), and K(+)) were studied for their hydrogen storage capacities. Hydrogen adsorption isotherms were measured separately at 77 K and <1 atm, and at 298 K and <10 MPa. It was found that the hydrogen adsorption capacity of LSX zeolite depended strongly on the cationic radius and the density of the cations that are located on the exposed sites. The interaction energies between H(2) and the cations follow the order Li(+) > Na(+) > K(+), as predicted based on the ionic radii. Oxygen anions on zeolite framework were minor adsorption sites. Li-LSX had an H(2) capacity of 1.5 wt % at 77 K and 1 atm, and a capacity of 0.6 wt % at 298 K and 10 MPa, among the highest of known sorbents. The hydrogen capacity in LSX zeolite by bridged hydrogen spillover was also investigated. A simple and effective technique was employed to build carbon bridges between the H(2) dissociation catalyst and the zeolite to facilitate spillover of hydrogen atoms. Thus, the hydrogen storage capacity of Li-LSX zeolite was enhanced to 1.6 wt % (by a factor of 2.6) at 298 K and 10 MPa. This is by far the highest hydrogen storage capacity obtained on a zeolite material at room temperature. Furthermore, the adsorption rates were fast, and the storages were shown to be fully reversible and rechargeable. Further optimization of the bridge building technique would lead to an additional enhancement of hydrogen storage.     

Modified lithium borohydrides for reversible hydrogen storage

In an attempt to develop lithium borohydrides as reversible hydrogen storage materials with high hydrogen storage capacities, the feasibility of reducing the dehydrogenation temperature of the lithium borohydride and moderating rehydrogenation conditions was explored. The lithium borohydride was modified by ball milling with metal oxides and metal chlorides as additives. The modified lithium borohydrides released 9 wt % hydrogen starting from 473 K. The dehydrided modified lithium borohydrides absorbed 7-9 wt % hydrogen at 873 K and 7 MPa. The modification with additives reduced the dehydriding starting temperature from 673 to 473 K and moderated the rehydrogenation conditions from 923 K/15 MPa to 873 K/7 MPa. XRD and SEM analysis revealed the formation of an intermediate compound that might play a key role in changing the reaction path, resulting in the lower dehydriding temperature and reversibility. The reversible hydrogen storage capacity of the oxide-modified lithium borohydrides decreased gradually during hydriding/dehydriding cycling. One of the possible reasons for this effect might be the loss of boron during dehydrogenation, but this can be prevented by changing the dehydriding path using appropriate additives. The additives reduced the dehydriding temperature and improved the reversibility, but they also reduced the hydrogen storage capacity. The best compromise can be reached by selecting appropriate additives, optimizing the additive loading, and using new synthesis processes other than ball milling.     

Design Rules for Metal-Organic Framework Stability in High-Pressure Hydrogen Environments

Stability of metal-organic frameworks (MOFs) under hydrogen is of particular importance for a diverse range of applications, including catalysis, gas separations, and hydrogen storage. Hydrogen in gaseous form is known to be a strong reducing agent and can potentially react with the secondary building units of a MOF and decompose the porous framework structure. Moreover, rapid pressure swings expected in vehicular hydrogen storage could create significant mechanical stresses within MOF crystals that cause partial or complete pore collapse. In this work, we examined the stability of a structurally representative suite of MOFs by testing them under both static (70 MPa) and dynamic hydrogen exposure (0.5 to 10 MPa, 1000 pressure cycles) at room temperature. We aim to provide stability information for development of near room-temperature hydrogen storage media based on MOFs and suggest framework design rules to avoid materials unstable for hydrogen storage under relevant technical conditions.     

Significantly enhanced hydrogen storage in metal-organic frameworks via spillover

The utilization of hydrogen in fuel-cell powered vehicles is limited by the lack of a safe and effective system for hydrogen storage. At the present time, there is no viable storage technology capable of meeting the DOE targets. Porous metal-organic frameworks (MOFs) are novel and potential candidates for hydrogen storage. Until now it is still not possible to achieve any significant hydrogen storage capacity in MOFs at ambient temperature. Here, we report, for the first time, significant amounts of hydrogen storage in MOF-5 and IRMOF-8 at ambient temperature by using a very simple technique via hydrogen dissociation and spillover. Thus, hydrogen uptakes for MOF-5 and IRMOF-8 can be enhanced by a factor of 3.3 and 3.1, respectively (to nearly 2 wt % at 10 MPa and 298 K). Furthermore, the isotherms are totally reversible. These findings suggest that our technique is suitable for hydrogen storage in a variety of MOF materials because of their similar structures as MOF-5 and IRMOF-8.     

Multiple H2 occupancy of cages of clathrate hydrate under mild conditions

Experiments were carried out by reacting H(2) gas with N(2) hydrate at a temperature of 243 K and a pressure of 15 MPa. The characterizations of the reaction products indicated that multiple H(2) molecules can be loaded into both large and small cages of structure II clathrate hydrates. The realization of multiple H(2) occupancy of hydrate cages under moderate conditions not only brings new insights into hydrogen clathrates but also refreshes the perspective of clathrate hydrates as hydrogen storage media.     

3NaBH4/ErF3复合储氢材料的制备及吸放氢特性

采用高能球磨法制备了3NaBH4/ErF3复合储氢材料, 并研究了其相结构和储氢性能. X射线衍射(XRD)显示, NaBH4和ErF3在球磨过程中未发生反应; 同步热分析(TG-DSC)测试结果表明, 3NaBH4/ErF3体系在420℃开始放氢, 比相同测试条件下纯NaBH4的放氢温度降低了约100℃, 放氢量为3.06%(质量分数). 压力-成分-温度(Pressure-Composition-Temperature, PCT)性能测试结果显示, 3NaBH4/ErF3复合储氢材料在较低的温度(355~413℃)及平台氢压(<1 MPa)下即拥有良好的可逆吸放氢性能, 最高可逆吸氢量可达到2.78%(质量分数), 吸氢后体系重新生成了NaBH4相. 计算得吸氢焓变仅为-36.8 kJ/mol H2; 而放氢焓变为-180.8 kJ/mol H2. NaBH4在ErF3的作用下提高了热动力学性能, 并实现了可逆吸放氢.     

Application of clathrate compounds for hydrogen storage

The review considers current works on clathrate hydrogen compounds, aimed at creating hydrogen accumulators suitable for practical application. Analysis of published data showed that clathrate hydrates formed by pure hydrogen are unsuitable for this purpose in view of their fairly low limiting hydrogen content and the necessity for their synthesis of extremely high pressures (>100 MPa) that are still industrially unfeasible. The possibilities for hydrogen storage in double (including auxiliary guest molecules along with hydrogen) clathrate hydrates are considered. It is concluded from published data that sorbents on the basis of the so-called “metal-organic frameworks” (MOFs) with a pore size of 1–2 nm hold a greater promise for hydrogen storage at temperatures of about 100 and moderately (up to 10 MPa) high pressures, but the development of all the considered methods of hydrogen storage has not yet grown out of laboratory experiments.     

Hydrogen uptake in boron nitride nanotubes at room temperature

Hydrogen uptake capacities of 1.8 and 2.6 wt % were obtained on BN multiwalled nanotubes and bamboo-like nanotubes, respectively, under approximately 10 MPa at room temperature. The preliminary results show that chemical interactions mainly take place between hydrogen and BN. Taking into consideration the uniform semiconducting electronic property and ultimate stable chemical and thermal stability, BN nanotubes may exhibit some interesting possibilities in storing hydrogen. This will also provide some viewpoints on designing the carbon-based hydrogen storage system.     

氢气在碳纳米管基材料上的吸附-脱附特性

利用高压容积法测定多壁碳纳米管(MWCNTs)及钾盐修饰的相应体系(K＋-MWCNTs)的储氢容量,并用程序升温脱附(TPD)方法表征研究氢气在MWCNTs基材料上的吸附-脱附特性.结果表明,在经纯化MWCNTs上,室温、9.0 MPa实验条件下氢的储量可达1.51％（质量分数）;K＋盐对MWCNTs的修饰对增加其储氢容量并无促进效应,但相应化学吸附氢物种的脱附温度有所升高;K＋的修饰也改变了MWCNTs表面原有的疏水性质.在低于723 K的温度下,H2/MWCNTs体系的脱附产物几乎全为氢气;773 K以上高温脱附产物不仅含H2,也含有CH4、C2H4、C2H2等C1/C2烃混合物;H2/K＋-MWCNTs储氢试样的脱附产物除占主体量的H2及少量C1/C2烃混合物外,还含水汽,其量与吸附质H2源水汽含量密切相关.H2在碳纳米管基材料上吸附兼具非解离 (即分子态) 和解离(即原子态)两种形式.     

氢气在单壁碳纳米管束的吸附的密度泛函研究

作者利用密度泛函理论（DFT）计算了氢气在单壁碳纳米管束（SWNTs)中管内 和管间的吸附。考察了温度,孔径以及压力对吸附的分子数密度,重量百分比,单 位体积储存能力以及超额吸附量的影响。DFT计算发现,较大的孔径有利于氢气在 SWNTs中的吸附且氢气在管隙中的吸附不可忽略。计算表明在77 K和6 MPa时,氢气 在2.719 mm的SWNTs的总的吸附的重量百分比分别可达到13.2 wt%,这约是美国能 源部（DOE）目标值的两倍,而单位体积储存能力在DOE目标值附近,而在300 K和 6 MPa时,氢气在2.719 nm的SWNTs的总的吸附的重量百分比仅为1.5 wt%。通过实 验结果与计算结果的比较表明,密度泛函理论的计算结果支持SWNTs有较高的吸附 储氢能力的实验结论。     

配位聚合物{[Cu_2(nbdo)_2·(H_2O)_2]·2(H_2O)}_n的热稳定性以及荧光性能和储氢性能(英文)

合成了一种新的以柔性羧酸为配体的铜配位聚合物,考察了其热稳定性能、荧光性能及储氢能力.结果表明,配体2-硝基-苯-1,4-二(氧乙酸)表现出较好的柔韧性;该结构在温度低于541 K的环境中比较稳定,当温度高于541 K迅速发生分解并伴随着轻微的爆轰.配合物的荧光光谱与配体的相比有所蓝移.与此同时,该配合物的储氢能力随着氢气压力的增加而提高;当氢气压力为5.0 MPa时储氢能力可达0.42%.     

钾掺杂多壁纳米碳管储氢性能研究

使用自制的钴催化裂解碳氢气法制备多壁纳米碳管,并对其进行退火、掺杂等一系列预处理,然后使用高压高纯氢源,在中压(12 MPa)和室温条件下,进行钾掺杂多壁纳米碳管的储氢性能实验.结果表明:预处理对纳米碳管的储氢性能有很大影响.实验条件下,经过氮气退火,并在1.0 mol/L硝酸钾溶液中掺杂的多壁纳米碳管吸氢量最大(H/C质量分数为3.2%).上述样品在室温下的放氢量一般不超过其吸氢量的50.8%.     

氢在活性炭、石墨烯和金属有机骨架上的吸附平衡

为比较不同物理吸附材料的结构参数对其储氢性能的影响,制备和选取了具有超高比表面积的活性炭、石墨烯以及金属有机骨架（MOFs）作为低温吸附储氢的典型材料。首先,利用77 K下氮气在材料上的吸附数据确定了其BET比表面积以及孔径分布的主要结构参数。其次,利用3Flex全自动微孔吸附仪在77-87 K测试了0-0.1 MPa低压下氢在各材料上的吸附量,而后在0.1-8 MPa高压条件下利用PCTPro测试了氢在各材料上的过剩吸附量。最后,分析了各材料的储氢量与其结构参数间的关系。结果表明,在低压下,影响物理吸附材料储氢量的主要因素为孔径分布小于1 nm的微孔;而高压下,氢在多孔材料上的最大过剩吸附量与材料的BET比表面积呈正相关关系,斜率为0.0059 mmol/m²。     

Preparation of platinum-decorated porous graphite nanofibers, and their hydrogen storage behaviors

In this work, the hydrogen storage behaviors of porous graphite nanofibers (GNFs) decorated by Pt nanoparticles were investigated. The Pt nanoparticles were introduced onto the GNF surfaces using a well-known chemical reduction method. We investigated the hydrogen storage capacity of the Pt-doped GNFs for the platinum content range of 1.3-7.5 mass%. The microstructure of the Pt/porous GNFs was characterized by X-ray diffraction and transmission electron microscopy. The hydrogen storage behaviors of the Pt/GNFs were studied using a PCT apparatus at 298 K and 10 MPa. It was found that amount of hydrogen stored increased with increasing Pt content to 3.4 mass%, and then decreased. This result indicates that the hydrogen storage capacity of porous carbons is based on both their metal content and dispersion rate.     

高容量的Ti-V基BCC相储氢合金

储氢合金是有希望成为燃料电池供氢源的方式之一,在各类储氢合金中,以LaNi5为代表的AB5和以TiMn2为代表的AB5发展已较成熟,但由于其储氢量小于2％(质量百分比)而制约了其应用,Mg基合金具有较大的储氢量(3％左右),但由于其吸放氢条件(温度在473K以上)苛刻难以满足燃料     

络合氢化物Ti-NaAlH4的制备与储氢特性

采用Ti粉为催化剂前驱体、预处理Al粉和NaH为合成原料, 通过机械球磨-加氢方法合成出络合氢化物Ti-NaAlH4, 系统研究了球磨保护气氛、球磨时间和氢化加氢压力等制备参数对其储氢性能的影响. 结果表明, 制备方法对Ti-NaAlH4储氢特性有很大影响. 与氩气保护气氛相比, 在氢气气氛中球磨制备的复合物具有更高的吸放氢性能. 在氢气保护气氛下, 随着球磨时间从6 h增至24 h, 复合物的吸氢容量和吸氢速率先增后减, 12 h时达到最佳值, 而复合物的放氢容量和放氢速率则逐渐增高; 进一步延长球磨时间会使颗粒发生团聚, 从而导致吸氢性能下降. 随着氢化加氢压力从7.5 MPa升至13.5 MPa, 复合物的吸氢容量(质量分数)由2.83%逐渐增至4.21%. 复合物球磨后出现的Na3AlH6中间氢化物相表明, 在氢气下掺Ti球磨对NaH和Al的氢化反应起到很好的促进作用.     

A comparative study of the radial distribution of hydrogen on C<Subscript>20</Subscript>, C<Subscript>19</Subscript>Si,and C<Subscript>19</Subscript>B cage fullerenes: a Monte Carlo simulation

The radial distribution of hydrogen on C_20(cage) and C₁₉Si_(cage), and C₁₉B_(cage) fullerene structures is investigated at different temperatures (273 K, 293 K, 320 K, and 400 K) for the pressure range between 1 MPa and 30 MPa using the (N,V,T) Monte Carlo simulation. The gravimetric storage capacity and radial distribution function parameters show that, under the identical temperature and pressure conditions, the magnitude of the hydrogen radial distribution on the C₁₉B surface is larger than that on C₁₉Si and C₂₀. The calculated maximum of the gravimetric storage capacity for C₁₉B at 273 K and 30 MPa is 7.6%.     

Synthesis, characterization and hydrogen storage capacity of MS2 (M = Mo, Ti) nanotubes

The structure, morphology and hydrogen-storage capacity of MS₂ (M = Mo, Ti) nanotubes prepared by different experimental methods were studied. It was found that the MoS₂ nanotubes treated by KOH displayed the gaseous storage capacity of 1.2 wt% hydrogen (under the hydrogen pressure of 3 MPa and 25°C) and the electrochemical discharge capacity of 262 mAh/g (at the discharge current density of 50 mA/g and 25°C) that corresponds to about 1.0 wt % hydrogen. In comparison, TiS₂ nanotubes can store 2.5 wt% hydrogen under the hydrogen pressure of 4 MPa and 25°C. The results show that MS₂ compound nanotubes are promising materials for hydrogen storage. __________ Translated from Acta Scientiarum Naturalium Universitatis Nankaiensis, 2005, 38(4) (in Chinese)     

Hydrogen storage in nanostructured carbons by spillover: bridge-building enhancement

The hydrogen storage capacity in nanostructured carbon materials can be increased by atomic hydrogen spillover from a supported catalyst. A simple and effective technique was developed to build carbon bridges that serve to improve contact between a spillover source and a secondary receptor. In this work, a supported catalyst (Pd-C) served as the source of hydrogen atoms via dissociation and primary spillover and AX-21 or single-walled carbon nanotubes (SWNTs) were secondary spillover receptors. By carbonizing a bridge-forming precursor in the presence of the components, the hydrogen adsorption amount was increased by a factor of 2.9 for the AX-21 receptor and 1.6 for the SWNT receptor at 298 K and 100 kPa. Similar results were obtained at 10 MPa, indicating that the enhancement factor is a weak function of pressure. The AX-21 receptor with carbon bridges had the highest absolute capacity of 1.8 wt % at 298 K and 10 MPa. Reversibility was demonstrated through desorption and readsorption at 298 K. The bridge-building process appears to be receptor specific, and optimization may yield even greater enhancement. Using this technique, enhancements in storage of up to 17-fold on other carbon-based materials have been observed and will be reported elsewhere shortly.     

Gas adsorption process in activated carbon over a wide temperature range above the critical point. Part 1: modified Dubinin-Astakhov model

Simulations of the thermal effects during adsorption cycles are valuable tools for the design of efficient adsorption-based systems such as gas storage, gas separation and adsorption-based heat pumps. An analytical representation of the measured adsorption data over the wide operating pressure and temperature swing of the system is necessary for the calculation of complete mass and energy conservation equations. In Part 1, the Dubinin-Astakhov (D-A) model is adapted to model hydrogen, nitrogen, and methane adsorption isotherms on activated carbon at high pressures and supercritical temperatures assuming a constant microporous adsorption volume. The five parameter D-A type adsorption model is shown to fit the experimental data for hydrogen (30 to 293 K, up to 6 MPa), nitrogen (93 to 298 K, up to 6 MPa), and for methane (243 to 333 K, up to 9 MPa). The quality of the fit of the multiple experimental adsorption isotherms is excellent over the large temperature and pressure ranges involved. The model’s parameters could be determined as well from only the 77 K and 298 K hydrogen isotherms without much reducing the quality of the fit.