多孔Pd材料及其表面毒化问题研究现状

多孔Pd材料在氢同位素吸附、分离和转运等领域有着广泛的用途和重要的工程应用价值,受到了广泛地关注.由于O2、H2O、CO2等杂质气体会对Pd表面产生毒化作用,导致氢在Pd表面的解离与向Pd体内的扩散速率的降低,多孔Pd表面的毒化机理研究为目前该领域研究的一个重点.着重阐述了多孔Pd材料的发展过程,总结了当前Pd表面毒化问题的研究现状.     

笼型Li6Si5团簇的结构和储氢性能研究

利用密度泛函M06方法,在6-311+G(d, p)基组水平上对Si_5和Li修饰的Si_5团簇的几何结构和电子性质及储氢性能进行理论计算研究.结果表明, Si_5团簇最低能量构型为笼型结构,纯Si_5团簇不能有效吸附氢分子. Li原子的引入显著改善了Si_5团簇的储氢能力.以六个Li原子穴位修饰Si_5团簇为载体,每个Li原子周围可以有效吸附三个氢分子,其氢分子的平均吸附能为2.395 kcal/mol,储氢密度可达16.617 wt%.合适的吸附能和较高储氢密度表明Li修饰Si_5团簇有望成为理想的储氢材料.     

Hydrogen Adsorption on Metal-Organic Framework MOF-177

This review summarizes the recent literature on the synthesis, characterization, and adsorption properties of meal-organic framework MOF-177. MOF-177 is a porous crystalline material that consists of Zn4O tetrahedrons connected with benzene tribenzoate (BTB) ligands. It is an ideal adsorbent with an exceptionally high specific surface area (BET4500 m2/g), a uniform micropore size distribution with a median pore diameter of 12.7 ?, a large pore volume (2.65 cm3/g), and very promising adsorption properties for hydrogen storage and other gas separation and purification applications. A hydrogen adsorption amount of 19.6 wt.% on MOF-177 at 77 K and 100 bar was observed, and a CO2 uptake of 35 mmol/g on MOF-177 was measured at 45 bar and an ambient temperature. Other hydrogen properties (kinetics and heat of adsorption) along with adsorption of other gases including CO2, CO, CH4, and N2O on MOF-177 were also be discussed. It was observed in experiments that MOF-177 adsorbent tends to degrade or decompose when it is exposed to moisture. Thermogravimetric analysis showed that the structure of MOF-177 remains intact at temperatures below 330℃ under a flow of oxygen, but decomposes to zinc oxide at 420℃.     

Li原子修饰缺陷蓝磷单层储氢性能的第一性原理研究

本文基于第一性原理计算,系统地研究了碱金属Li原子修饰缺陷蓝磷单层体系的储氢性能. 研究结果表明,双空位缺陷DV2的引入可以有效增强Li原子与蓝磷单层间的相互作用,能够有效阻止单层表面Li团簇的形成. 单个Li原子可以稳定吸附3个H2分子,H2分子平均吸附能为0.248 eV/H2. 电子结构分析表明,H2分子主要通过极化机制和轨道杂化作用吸附在Li修饰的缺陷蓝磷单层体系上. 此外,本文还研究了温度和压强对Li/DV2体系储氢性能的影响. 结果表明,在室温和低压条件下,H2分子可以稳定吸附在Li/DV2体系表面,从而实现室温条件下的可逆储氢.     

SiLi5+团簇的结构及储氢性能理论研究

SiLi_5~+团簇由于具有高稳定特性,并且SiLi_5~+可以最多有效绑定15个氢分子,其理论质量储氢密度达到了32.3 wt%.在B3LYP理论水平上,氢分子与SiLi_5~+相互作用过程中的平均氢吸附能在1.36～2.62 kcal·mol~(-1)之间,从平均氢吸附能看,此系统满足可逆吸氢反应的热力学要求,可以作为理想储氢材料的候选物.     

第一性原理研究锂修饰的类石墨烯碳氮纳米结构的储氢性能

利用基于密度泛函理论的第一性原理方法,研究了锂修饰的类石墨烯碳氮纳米结构的储氢性能.结果表明该体系是一种理想的储氢材料,锂原子通过向衬底转移电荷而带正电,通过静电场的极化作用,每个锂原子可以吸附3个氢分子,其储氢的质量比可达11.5 wt%.氢分子的平均吸附能比较理想,可以实现在室温下可逆的储氢和放氢.     

Effects of structure and surface properties on carbon nanotubes’ hydrogen storage characteristics

Hydrogen adsorption experiments were carried out in special stainless steel vessels at room temperature (298K) and under 10 MPa using self-synthesized multi-walled carbon nanotubes. In the experiments, carbon nanotubessynthesized by the seeded catalyst method were pretreatedby being soaked in chemical reagents or annealed at hightemperature before they were used to adsorb hydrogen, but their capacity for hydrogen storage was still poor. Carbonnanotubes synthesized by the floating catalyst method were found to be able to adsorb more hydrogen. They have ahydrogen storage capacity of over 4% after they wereannealed at high temperatures, which suggested that theycould be used as a promising material for hydrogen storage.     

LaNi5＋TiF0.9Mn0．1合金的贮氢性能

用冶炼法合成LaNi5＋TiFe0.5Mn0.1复合贮氢合金，研究了LaNi5＋TiF0.5，Mn0.1合金的贮氢性能。研究结果表明：由于TiFe.9Mn0.1合金的加入，可有效地降低LaNi5的平台压力；当TiFe0.5Mn0.1的质量分数为15％左右时，放氢曲线中出现两个平台；TiFe0.9Mn0.1的质量分数趋于25％时，它的平台压力又逐渐升高，贮氢量逐渐增大，温度升高则第二个平台消失，贮氢量降低。该合金适用于低温贮氢。     

LaNi5+TiFe0.9Mn0.1合金的贮氢性能

用冶炼法合成LaNi5 TiFe0.9Mn0.1复合贮氢合金,研究了LaNi5 TiFe0.9Mn0.1合金的贮氢性能。研究结果表明:由于TiFe0.9Mn0.1合金的加入,可有效地降低LaNi5的平台压力;当TiFe0.9Mn0.1的质量分数为15%左右时,放氢曲线中出现两个平台;TiFe0.9Mn0.1的质量分数趋于25%时,它的平台压力又逐渐升高,贮氢量逐渐增大,温度升高则第二个平台消失,贮氢量降低。该合金适用于低温贮氢。     

金属氢化物吸附和脱附过程的数值分析

结合化学吸附的机理，提出圆柱筒型金属氢化物吸氢、放氢的物理和数学模型。以金属氢化物ＬａＮｉ４．７Ａｌ０．３为例进行数值模拟，计算了不同时间的金属氢化物的反应锋面位置、热流量和吸氢量等参数。还研究了不同边界条件下，金属氢化物吸氢、放氢的传质情况及金属氢化物导热系数对金属氢化物的吸附、脱附的影响，并对不同类型金属氢化物在相同条件下的吸附性质进行了对比。研究证明：利用金属氢化物贮氢，应尽量减薄反应层的厚     

Tuning clathrate hydrates for hydrogen storage

The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.     

镁基合金与碳纳米纤维复合储氢材料的制备与性能研究(Ⅰ)--以化学镀Ni碳纳米纤维为前驱物热扩散法合成Mg2Ni-CNFs复合储氢材料

利用金属Mg易热扩散制合金的特性，以化学镀Ni的碳纳米纤维(Ni-CNFs)为前驱物，制备出了Mg-Ni合金与CNFs的复合储氢材料．并测试了其电化学性能，提出了镁基储氢合金与CNFs复合储氢材料的储氢机理．     

Hydrogen absorption-desorption cycle decay mechanism of palladium nanoparticle decorated nitrogen doped graphene

As a hydrogen storage material, palladium nanoparticle decorated nitrogen doped graphene (Pd/N-rGO) has drawn much attention owing to its high absorption capacity at moderate conditions. However, its hydrogen absorption-desorption cycle performance, which is essential for their practical application, has been rarely studied. In this paper, a simple and convenient high temperature thermal reduction method was used to synthesize nitrogen-doped graphene decorated with Pd nanoparticles (Pd/N-rGO). Taken it as a representative, the hydrogen absorption-desorption cycle performance of Pd/N-rGO was investigated. The results showed that after three cycles the hydrogen storage capacity dropped from 2.9 ​wt% to 0.8 ​wt% at 25 ​°C and 4 ​MPa pressure. It was found that the palladium nanoparticles shed from Pd/N-RGO sheet after cycle performance test, and then agglomerated. These phenomena will weaken the hydrogen spillover effect, leading to the decrease of hydrogen storage capacity. Meanwhile, decreased defects reduce the hydrogen absorption sites, which will thus deteriorate the hydrogen storage capacity.     

注入增产法提高煤层气采收率的理论探讨

美国Amoco公司开发的注入增产法是一项很有前途的提高煤层气采收率的方法,为此笔者在研究煤对二元气体吸附特征的基础上,探讨了注入增产法的基本原理。结果表明,煤对常见气体的吸附能力由强到弱为：二氧化碳、甲烷、氮气、氢气;煤对二元混合气体总的吸附及对甲烷的吸附均符合Langmiur方程,但在ＣＨ４＋Ｈ２或ＣＨ４＋Ｎ２的吸附系统中,对Ｈ２或Ｎ２吸附时吸附量与压力之间不遵从此关系式,而在ＣＨ４＋ＣＯ２吸附系统中,煤对ＣＯ２的吸附量和压力之间的关系仍可用Langmuir方程定量描述;注入增产法提高煤层瓦斯抽放率是通过注入其它气体使煤对甲烷的吸附量减小来实现的,且注入Ｎ２优于ＣＯ２。     

Applying Study of Hydrogen Storage Alloy

Hydrogen is an important source of energy.The natural resouces of hydrogen is plenty and it gives us lots of heat, and it is dean. One of difficulties of developing hydrogen sources of energy is hydrogen storage. Hydrogen storage tank is either dangous or a little of capacity. Liquid hydrogen occupys small space. Liquefaction temperature of hydrogen is -253℃ and need better heat insulation protection, the volumn and weight of heat insulation layer are equal to hydrogen storage tank. Hydrogen storage utillizing hydrogen storage material is a very safety, economical and effective method. Hydrogen storage material is either a medium of sofid hydrogen storage or is negative pole active material of Ni-H battery,and is the one of key technoloy of fuel and Ni-H battery, it is an important material of new sources of energy too.Nanotechnology is introduced Mg-matrix hydrogen storage alloy and is achieved progress gteatly,but hydrogen storage alloy need be mode further improvment on applying investigation.     

基于SiC和BC5的多孔材料设计及储氢性能研究

基于金刚石结构的SiC晶体和类似金刚石结构的BC5晶体设计了多孔材料,并用分子力学方法对其进行优化得到平衡态结构.利用GCMC对其在温度为298 K和77 K,压强为0-100 bar的条件下的储氢量、氢分子密度分布和等量吸附热进行了讨论.考虑孔内壁以化学吸附的氢在内,基于SiC晶体设计的多孔材料储氢量比Si C纳米管的结果更理想.氢分子密度分布图表明氢分子在孔道中的分布距孔道边缘有一定的距离,此距离与氢分子动力学直径2.89A相当.等量吸附热表明材料在温度为298 K和77 K对氢分子的吸附都是物理吸附.     

混合稀土中锌,铁,镁杂质对贮氢电极性能的影响

研究了混合稀土中常见杂质锌，铁，镁对贮氢电极材料的贮氢性能，电化学性能等的影响。结果表明：它们的存在使合金的吸氢平台压力及吸氢量有所改变，同时电极的大电流放电特性也发生变化，但对其放电容量影响不大。     

玉米芯活性炭的制备及储气性能

天然气、氢气、二氧化碳等气体的吸附研究在洁净气体代油燃料的强化存储、温室气体减排、大气治理等方面具有重要意义,其重点内容是高效吸附材料的开发．以玉米芯为原料,采用磷酸活化法制备了含有较高中孔比例的活性炭,其比表面积达到1,610,m2/g,孔容为1.72,cm3/g,中孔体积达到1.14,cm3/g,占孔容的66％．测定了H2、N2、CH4和 CO2在该吸附剂上的吸附等温线．在0.4,MPa 时,CO2对 CH4的选择性达到2.76,对 N2的选择性达到7.63,对 H2的选择性达到42.31,具有良好的分离应用前景．测定了水存在条件下甲烷在该活性炭上的吸附等温线,由于孔尺寸有利于甲烷水合物的生成,因此甲烷吸入量较在干燥吸附剂上提高了82％．根据克劳修斯-克拉佩龙方程计算了甲烷水合物的生成焓为-64.37,kJ/mol．     

测定氢在碳质材料中吸附量的实验方法

按照容积法的原理建立了用于氢气吸附储存研究的吸附等温线测量实验装置，利用氦气、氢气在一种碳纳米纤维上的吸附评估了该实验装置的性能．从理论上分析了该实验装置的系统误差，用实验的方法验证了理想气体状态方程、SRK状态方程以及MBWR方程描述实际气体的适用性，得到了准确确定吸附槽剩余体积的方法．实验和理论分析结果说明：该测试装置和实验数据的处理方法能够准确地确定氢在碳纳米材料中的吸附量．     

热处理对多壁碳纳米管储氢性能的影响

文章采用容量法测量在常温下压力升高到10 MPa时,多壁碳纳米管的吸附储氢性能,分析了热处理对碳纳米管的结构和吸附储氢量的影响。采用透射电镜(TEM)、激光拉曼光谱(Raman)和低温N2吸附(BET)对碳纳米管的微观结构进行表征。结果发现,热处理能明显地提高碳纳米管的石墨化程度,热处理后碳纳米管的质量储氢容量从原来的1.90%升高到2.17%。