Nano-confined ammonia borane for chemical hydrogen storage

There is a great demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. In this regard, ammonia borane (NH₃BH₃, AB) containing 19.6 wt-% hydrogen has been considered as a promising material for hydrogen storage applications to realize the “hydrogen economy”, but with limits from slow kinetics of hydrogen release and by-product of trace gases such as ammonia and borazine. In this review, we introduce the recent research on AB, regarding to the nanoconfinement effect on improving the kinetics at a relatively low temperature and the prevention/reduction of undesirable gas formation.     

氨硼烷水解制氢研究进展

氢能是替代传统化石能源的重要清洁能源,然而实现氢能的高质量密度储存与温和条件下快速释放仍是一大瓶颈。氨硼烷储氢密度高达19.6%（质量）,在室温下水解即可制得氢气,是最有发展前景的储氢材料之一。然而氨硼烷在水中放氢速度缓慢,因此开发加速其水解过程的催化剂至关重要。对氨硼烷的水解催化剂的研究主要集中在金属单质、金属化合物与光催化剂三类材料。本文从实践方面,介绍了氨硼烷水解制氢的研究方法,从理论方面,通过介绍催化剂的发展,综述了氨硼烷水解反应的步骤与机理。通过对产氢过程的深入描述,介绍了对氨硼烷水解制氢反应正面调控的方法,并依据已有的研究提出了未来该类催化剂的设计策略。     

氨硼烷分解制氢及其再生的研究进展

氨硼烷具有储氢密度高（152.9g/L）、放氢条件温和、无毒以及常温下为稳定的固体而易于储运等特点而成为最有前景的储氢材料之一。本文综述了近年来氨硼烷在不同催化剂作用下,通过热解、醇解和水解这3种方式制氢以及分解后的副产物循环再生氨硼烷的研究进展。分析讨论了氨硼烷的热解制氢研究主要集中在降低温度和抑制气态副产物的生成这两方面,而水解或醇解制氢的研究热点是二元或三元非贵金属纳米核壳或负载型催化剂。与氨硼烷的热解相比,水解或醇解由于条件温和、制氢速度快而更具实用性。指出氨硼烷作为储氢材料最大的挑战是其再生问题,氨硼烷分解脱氢后的副产物不能直接氢化而再生氨硼烷,需要通过一系列反应来进行间接的离线再生,因此氨硼烷的再生将是今后的重点研究方向。     

膨润土负载钌催化剂制备及其催化氨硼烷水解产氢研究

采用浸渍-化学还原法制备了钌/膨润土（Ru/Ben）催化剂,考察了钌含量、还原剂硼氢化钠用量、还原温度以及反应条件等对Ru/Ben催化氨硼烷（NH₃BH₃）水解产氢的影响。结果表明,在钌负载量为0.3%（质量分数）、钌与还原剂硼氢化钠物质的量比为1∶2.5、还原温度为303 K条件下,制备的Ru/Ben中Ru微晶尺寸为3.8 nm,Ru/Ben催化NH₃BH₃水解产氢的转化频率（TOF）为145 mol/（mol·min）;搅拌转速为450 r/min时,外扩散限制消除,产氢速率最大;产氢速率与Ru/Ben浓度成正比,催化剂界面反应是氨硼烷水解产氢反应的控速步骤,Ru/Ben催化NH₃BH₃水解产氢反应对催化剂浓度的反应级数为0.7;反应温度越高,氨硼烷向催化剂表面的传质速率越高、产物氢气及副产物偏硼酸钠从催化剂表面越易脱附,产氢速率越大。动力学计算表明,Ru/Ben催化NH₃BH₃水解产氢反应的产氢速率与氨硼烷浓度无关,活化能为15 kJ/mol。     

铁、钴、镍、铜和锌催化剂催化氨硼烷水解产氢性能研究

采用浸渍-还原法制备了铁、钴、镍、铜和锌催化剂,考察了其催化氨硼烷水解产氢性能,并优化了钴催化剂的制备条件和反应条件。结果发现,铁催化剂中铁以Fe₂B合金相存在,钴催化剂中钴以金属钴存在,镍催化剂中镍以金属镍和Ni（OH）₂·2H₂O存在,铜催化剂中铜以金属铜和氧化亚铜存在,锌催化剂中锌以Zn₄SO₄（OH）₆·4H₂O存在。铁、钴、镍、铜和锌催化剂催化氨硼烷水解产氢活性由大到小顺序为钴催化剂、镍催化剂、铜催化剂、铁催化剂、锌催化剂。显然,具有金属钴相的钴催化剂、金属镍相的镍催化剂和金属铜相的铜催化剂催化氨硼烷产氢活性高于具有Fe₂B合金相的铁催化剂。锌催化剂在制备条件下不能被还原为金属相,它几乎没有催化氨硼烷产氢活性。氯化钴与还原剂硼氢化钠的物质的量比为1∶1.3、还原温度为303 K时制备的钴催化剂催化BH₃NH₃水解产氢性能最佳。反应动力学计算表明钴催化剂催化BH₃NH₃水解产氢反应对氨硼烷浓度的反应级数为零级,对钴催化剂浓度的反应级数为一级,活化能为58 kJ/mol。     

Effect of boric acid on thermal dehydrogenation of ammonia borane: H2 yield and process characteristics

We have recently demonstrated that boric acid (H₃BO₃, BA) is a promising additive to decrease onset temperature as well as to enhance hydrogen release kinetics for thermolysis of ammonia borane (NH₃BH₃, AB). The observations suggest that tetrahydroxyborate ion released by heating BA serves as Lewis acid and catalyzes AB dehydrogenation. Using this approach, we obtained high H₂ yield at 85°C, along with rapid kinetics. Various operating conditions were investigated, such as reactor temperature, AB wt %, and particle size of BA. Even in the presence of 10 wt % BA, high H₂ yield (13 wt %) and trace amount of ammonia (10–20 ppm) were obtained at 80°C, proton exchange membrane (PEM) fuel cell operating temperature. To our knowledge, such H₂ yield value is higher than from any other method using AB with additive or catalyst at PEM fuel cell operating temperatures. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3359–3364, 2013     

静电纺丝技术在氨硼烷水解脱氢催化剂制备中的应用

氨硼烷由于其氢质量分数高达19.6%,在环境条件下稳定性高,无毒,在普通溶剂中溶解度高,因此被视为是一种极具潜力的固体储氢材料。但是传统纳米金属催化剂颗粒容易出现团聚、损失、二次污染、难回收的问题。高压静电纺丝技术将微纳米纤维作为纳米金属颗粒的载体,制备出的催化剂可以有效弥补传统纳米金属催化剂的缺点。本文从静电纺丝技术、纳米纤维的分类、催化剂的分类3个角度重点介绍了静电纺丝法制备应用于氨硼烷水解的纳米催化剂。在纳米纤维的分类中详细介绍了应用电纺技术制备不同种类纤维的制作步骤和关键技术点;在催化剂的分类中全面详细介绍了贵金属以及非贵金属催化剂的制备工艺,对比两种催化剂制备的优缺点,总结出了催化剂颗粒以及载体的选择依据。最后分别提出通过技术设备的升级优化、催化颗粒与载体的合理设计、“三步”化学反应的方法来解决电纺技术效率低、催化性能差、氨硼烷再生难的问题。     

Reaction mechanism and kinetics for hydrolytic dehydrogenation of ammonia borane on a Pt/CNT catalyst

A reaction mechanism is proposed for hydrolytic dehydrogenation of ammonia borane on a Pt/CNT catalyst. A combination of thermodynamic analysis and FTIR measurement reveals that B‐containing byproducts are mainly in the form of an NH₄B(OH)₄‐B(OH)₃ mixture rather than NH₄BO₂ reported previously. The revised main reaction is , involving the B–H, B–N, and O–H bond cleavages. Isotopic experiments using D₂O instead of H₂O as reactant or introducing D₂ into the reaction atmosphere suggest the O–H bond cleavage being in the rate‐determining step, and an unfavorable occurrence of the chemisorbed H₂O dissociation (i.e., the direct O–H bond cleavage), respectively. Different reaction pathways with indirect O–H bond cleavages are analyzed, and then is suggested as the rate‐determining step. Subsequently, a Langmuir–Hinshelwood kinetic model is developed, which fits well with the experimental data. © 2016 American Institute of Chemical Engineers AIChE J, 63: 60–65, 2017     

Production of silica aerogel microparticles loaded with ammonia borane by batch and semicontinuous supercritical drying techniques

Silica aerogel microparticles were prepared by supercritical drying and used as support for hydrogen-storing ammonia borane (AB). The formation of aerogel microparticles was done using two different processes: batch supercritical fluid extraction and a semicontinuous drying process. Silica aerogel microparticles with a surface area ranging from 400 to 800 m²/g, a volume of pores of 1 cm³/g, and a mean particle diameter ranging from 12 to 27 μm were produced using the two drying techniques. The particle size distribution (PSD) of the microparticles was influenced by shear rate, amount of catalyst, hydrophilic–hydrophobic solvent ratio and hydrophobic surface modification. In particular, irregular aerogel particles were obtained from hydrophilic gels, while regular, spherical particles with smooth surfaces were obtained from hydrophobic gels. AB was loaded into silica aerogel microparticles in concentrations ranging from 1% till 5% wt. Hydrogen release kinetics from the hydride-loaded aerogel was analyzed with a volumetric cell at 80 °C. By stabilization of AB into the silica aerogel microparticles, an improvement of the release rate of hydrogen from AB was observed.     

氨分解制氢催化剂研究进展

随着环保法规日趋严格,清洁氢能的生产和应用引起关注,氨分解制氢是其中重要途径之一。综述Ru、Ni和Fe等氨分解催化剂的研究进展,Ru催化剂具有较高的催化活性,但由于资源有限和价格昂贵等因素使其在工业应用方面受到限制。以Fe和Ni为代表的非贵金属催化剂资源丰富,价格低廉,氨分解反应转化率高,具有潜在的工业应用前景。我国独创的新一代Fe_(1-x)O基新型熔铁催化剂是目前世界上活性最高的氨合成催化剂,根据微观可逆性原理,新型熔铁催化剂也是氨分解反应活性最好的制氢催化剂。     

Catalytic ammonia decomposition: COx-free hydrogen production for fuel cell applications

Catalytic decomposition of ammonia has been investigated as a method to produce hydrogen for fuel cell applications. The absence of any undesirable by-products (unlike, e.g., CO_x, formed during reforming of hydrocarbons and alcohols) makes this process an ideal source of hydrogen for fuel cells. In this study a variety of supported metal catalysts have been studied. Supported Ru catalysts were found to be the most active, whereas supported Ni catalysts were the least active. The supports were found to play a profound role in the ammonia decomposition process. The activation energies for the ammonia decomposition process varied from 17 to 22 kcal/mol depending upon the catalyst employed. The activation energies of the supported Ir catalysts were found to be in excellent agreement with our recent studies addressing ammonia decomposition on single crystal Ir.     

氯碱化工电解氢气用于氨合成

分析了电解氢用于氨合成的可行性 ,介绍了电解氢用于氨合成改造中输送设备和输送管道的选择及其实际运行情况。实践证明 ,电解氢用于氨合成是完全可行的 ,经济效益十分显著。     

储氢功能材料的研究进展

综述了各种不同储氢材料的分类、储氢机理、研究进展,指出未来应用于质子交换膜燃料电池（PEMFC）车用氢燃料电池中的储氢材料,最具发展潜力的是大容量储氢合金、锂-铝及锂-硼金属配位氢化物和有机液体储氢。     

Progress and prospects in thermolytic dehydrogenation of ammonia borane for mobile applications

Using hydrogen as a transportation fuel has been attracting considerable interest due to zero carbon emissions from vehicles. Storing hydrogen compactly, safely and affordably remains a major scientific and technological challenge in on-board applications. Over the past decade, significant efforts have been made in developing solid-state hydrogen storage techniques. Among the chemical storage materials, ammonia borane is one most promising candidate because it has a high hydrogen density of 19.6 wt% and it is a non-flammable and non-explosive crystalline compound at ambient conditions. Hydrogen can be extracted from ammonia borane via thermolysis, hydrolysis, hydrothermolysis, and methanolysis. This review covers various approaches and prospects of facilitating thermolysis, along with a brief discussion of the nature of ammonia borane and the regeneration of spent fuel.     

二氧化硅负载钌催化剂催化氨硼烷水解产氢研究

采用浸渍-还原法制备了Ru/SiO₂催化剂,并考察了钌负载量、还原剂硼氢化钠的用量、还原温度以及反应条件对催化剂Ru/SiO₂催化BH₃NH₃水解产氢的影响。结果表明,在钌的负载量为0.1%（质量分数）、还原剂硼氢化钠与钌的物质的量比为2.2∶1、还原温度为303 K时制备的催化剂,催化BH₃NH₃水解产氢速率最快[转化频率TOF为140.8 L H₂/（mol Ru·min）]。搅拌转速为450 r/min时,氨硼烷向催化剂表面传质最快,产氢速率最大。氨硼烷水解反应由催化剂界面反应控制,产氢速率与催化剂用量成正比。随着反应温度的升高,Ru活化的氨硼烷分子能量增加,反应速率逐渐增加。反应动力学计算表明Ru/SiO₂催化剂催化BH₃NH₃水解产氢反应对氨硼烷浓度为零级反应,活化能为45 kJ/mol。     

合成氨弛放气膜分离氢回收与氨蒸馏的集成应用

合成氨弛放气中含有价值较高的氢气与氨气,传统的处理方法是将弛放气回收氨气后送燃烧系统,造成了氢气的极大浪费.将膜分离氢回收与氨蒸馏集成一个系统,在回收氢气的同时回收氨,使膜分离技术具有更强的兼容性和灵活性,从投资与回报方面分析也能体现出此集成方法的经济性与合理性.     

氨催化分解制备无COx的氢气催化剂研究进展

介绍了国内外氨催化分解催化剂的研究进展,评述了理想的活性组分、载体和助剂及其具有的一些规律;总结了氨催化分解的反应机理、氨催化分解的动力学模型,认为氨N—H断裂和催化剂表面吸附的氮原子的再结合是氨催化分解的速率控制步骤;讨论了该催化剂体系的改进途径。     

氢能的制备、存储与应用

综述了氢能研究的重要意义,对氢气的各种制备方法和国内外有关储氢材料的研究工作进行了详细介绍。同时简述了氢能在各个工业领域的广泛应用,对未来氢能的研究工作进行了展望。     

利用吸收-水合耦合法从氨弛放气中回收氢气的研究(英文)

In this work, the absorption-hydration hybrid method was used to recover (hydrogen + nitrogen) from (hydrogen + nitrogen + methane + argon) tail gas mixtures of synthetic ammonia plant through hydrate forma-tion/dissociation. A high-pressure reactor with magnetic stirrer was used to study the separation efficiency. The in-fluences of the concentration of anti-agglomerant, temperature, pressure, initial gas-liquid volume ratio, and oil-water volume ratio on the separation efficiency were systematically investigated in the presence of tetrahydro-furan (THF). Anti-agglomerant was used to disperse hydrate particles into the condensate phase for water-in-oil emulsion system. Since nitrogen is the material for ammonia production, the objective production in our separation process is (hydrogen + nitrogen). Our experimental results show that by adopting appropriate operating conditions, high concentration of (hydrogen + nitrogen) can be obtained using the proposed technology based on forming hydrate.     

Propionitrile formation from ethene and ammonia over Rh/Y-zeolite

The Rh/Y-zeolite has been found to be more active and selective for propionitrile formation from ethene and ammonia than other transition metal supported Y-zeolites. A reaction between ethene and hydrogen cyanide has been proposed as a reaction route for propionitrile formation.