Rubidium hydrazinidoborane: Synthesis,characterization and hydrogen release properties

In this work we present rubidium hydrazinidoborane RbN₂H₃BH₃ (RbHB), the newest and last member of the alkali metal derivatives of hydrazine borane N₂H₄BH₃ (HB). It is shown that HB readily reacts with metallic rubidium in THF at room temperature to form RbHB under argon atmosphere. The molecular and crystal structures of this new compound are discussed on the basis of FTIR spectroscopy, ¹¹B MAS NMR spectroscopy, and powder X-ray diffraction analyses. RbHB crystallizes in a monoclinic P2₁ (No. 4) unit cell where each Rb⁺ cation adopts octahedral coordination surrounded by six [N₂H₃BH₃]⁻ anions, which are two more than for e.g. LiN₂H₃BH₃ (with tetrahedral coordination) in accordance with the larger size of Rb⁺. RbHB is isostructural to potassium hydrazinidoborane KN₂H₃BH₃. Its dehydrogenation properties, evaluated by using thermogravimetric analysis, differential scanning calorimetry, and isothermal analysis, are compared to those of the parent HB as well as to analogous compounds in order to evaluate the potential of RbHB as hydrogen storage material. According to the presented data, the dehydrogenation properties of RbHB are much better than those of HB and are comparable to those of the lithium derivative. Our main results are reported therein.     

Ammonia decomposition kinetics over LiOH-promoted, α-Al2O3-supported Ru catalyst

A LiOH-promoted Ru-based catalyst was recently reported to have a high TOF of 17.7 s⁻¹ at 623 K, compared to 2.7 s⁻¹ for an un-promoted Ru-based catalyst, and has been reproduced for this study to develop further understanding of the catalyst activity under a range of conditions. The kinetic values were calculated using a Temkin-Pyzhev-like power law rate expression model. Reaction orders, pre-exponential factors (A) and activation energies (E) were calculated for two temperature ranges, 623–748 K, and 748–873 K. The TOF of this catalyst at 623 K is not similar to that previously reported, being only 1.6 s⁻¹ in this study. A follow-up CFD analysis supports the fact that the kinetic model effectively describes performance of the catalyst at a range of temperatures and pressures, and can be used in the future on similar catalysts. H₂ partial pressure has an inhibitory effect on the rate of decomposition of NH₃ at all temperatures, not just near or below 673 K as previously proposed in the literature, however equilibrium decomposition is still possible with sufficient catalyst loading.     

Monodisperse rutheniumcopper alloy nanoparticles decorated on reduced graphene oxide for dehydrogenation of DMAB

In this study, we report a superior dehydrogenation catalyst for dimethylamine borane, which exhibited one of the best catalytic activities. The newly formed catalyst system contains well dispersed ruthenium-copper nanomaterials on reduced graphene oxide (3.86 ± 0.47 nm), which was prepared by using the ultrasonic double reduction technique. The characterization of monodisperse ruthenium-copper alloy nanoparticles was performed using some advanced analytical methods such as TEM, HRTEM, XPS, Raman spectroscopic analysis. The experiments results revealed that the monodisperse ruthenium-copper alloy catalyst (RuCu@rGO) has one of the highest catalytic activity compared to previous studies, having a high turnover frequency value (256.70 h⁻¹). The detailed kinetic parameters such as activation energy, enthalpy, and entropy values were also calculated for the dehydrogenation of dimethylamine borane at room temperature. Also, the results showed that the monodisperse RuCu@rGO catalyst has high durability and reusability as retained its 81% initial catalytic activity even after 4th runs for the dehydrogenation of dimethylamine borane.     

Facile and eco-friendly synthesis of porous carbon nanosheets as ideal platform for stabilizing rhodium nanoparticles in efficient hydrolysis of ammonia borane

Carbon materials have been demonstrated as excellent carriers for preparing supported metal nanocatalysts in catalytic applications. However, numerous chemical activators including strong acids and bases were applied, leading to the entire process dangerous and hazardous. Eco-friendly, economic, and convenient synthesis of carbon materials with desired properties as supports for metal nanoparticle (NP) stabilization to boost performance is important but remains challenging. Here, we developed a facile and eco-friendly strategy to synthesize porous carbon nanosheets (PCNs) with ultrahigh specific surface area (2575.1 m²/g) via pyrolysis the mixture of potassium oxalate and glucose. The resultant PCNs can be used as ideal platform for in-situ distribution of small Rh NPs (Rh/PCNs) as efficient catalysts in hydrogen production from ammonia borane (AB) under ambient conditions. Specifically, Rh/PCNs displayed high activity for AB hydrolysis, with a turnover frequency (TOF) of 513.2 min⁻¹. Small and well-distributed Rh NPs on PCNs with large catalytically active surface atoms are contributed to the high catalytic property of Rh/PCNs for the reaction. Present study has demonstrated that the PCNs is a superior catalyst support for preparing a series of metal NPs in other catalytic applications beyond hydrolysis reaction.     

An experimental investigation on hydroxy (HHO) enriched ammonia as alternative fuel in gas turbine

Today, the important challenges with the utilization of hydrogen in power-producing applications (internal combustion engines and fuel cells) are its delivery and storage and these create a big hesitation regarding the application safety. Ammonia, which can be regarded as the most promising alternative fuel to hydrogen, provides the possibility of storage in liquid form at low pressures and high temperatures. This study was carried out to investigate how to compensate the drawbacks of using ammonia as the main fuel in a gas turbine by hydrogen and hydroxy-gas enrichment. During the experiments, propane that is standard working fuel of the gas turbine, neat ammonia, as well as a 10 L/min ammonia fuel enriched with 3 L/min, 5 L/min, and 7 L/min hydroxy gas, were utilized. The results show that hydroxy enrichments cause improvements in the performance data as well as emission values due to the absence of any carbon emissions. When the performance outputs are examined, it has been shown that the power values of NH₃ + 3 HHO and NH₃ + 5 HHO fuels are 10.98% and 3.65% lower than propane, whereas NH₃ + 7 HHO fuel produces 4.12% more power, and the desired performance values are reached. It has been also fund that NO_x emissions should be kept under control in addition to the increase in the performance and elimination of the carbon emissions.     

Development of a novel combined energy plant for multigeneration with hydrogen and ammonia production

In order to meet the energy and fuel needs of societies in a sustainable way and hence preserve the environment, there is a strong need for clean, efficient and low-emission energy systems. In this regard, it is aimed to generate cleaner energy outputs, such as electricity, hydrogen and ammonia as well as some additional useful commodities by utilizing both methane gas and the waste heat of an integrated unit to the whole system. In this paper, a novel multi-generation plant is proposed to generate power, hydrogen and ammonia as a chemical fuel, drying, freshwater, heating, and cooling. For this reason, the Brayton cycle as prime unit using methane gas is integrated into the s-CO₂ power cycle, organic Rankine cycle, PEM electrolyzer, freshwater production unit, cooling cycle and dryer unit. In order then to evaluate the designed integrated multigeneration system, thermodynamic analyses and parametric studies are performed, revealing that the energy and exergy efficiencies of the whole plant are found to be 69.08% and 65.42%. In addition, ammonia and hydrogen production rates have been found to be 0.2462 kg/s and 0.0631 kg/s for the methane fuel mass flow rate of 1.51 kg/s. Also, the effects of the reference temperature, pinch point temperature of superheater, combustion chamber temperature, gas turbine input pressure, and mass flow rate of fuel on numerous parameters and performance of the plant are investigated.     

合成氨空压机的运行维护管理

从合成氨装置新空压机在运行中的日常运行维护、停机保护和机组常见故障几个方面进行阐述，对故障发生的原因进行了分析，提出了解决方法，以实现机组的安全、稳定运行。     

Amino-group and space-confinement assisted synthesis of small and well-defined Rh nanoparticles as efficient catalysts toward ammonia borane hydrolysis

Hydrogen evolution from ammonia borane (AB) hydrolysis is of great importance considering the ever-increasing demand for green and sustainable energy. However, the development of a facile and efficient strategy to construct high-performance catalysts remains a grand challenge. Herein, we report an amino-group and space-confinement assisted strategy to fabricate Rh nanoparticles (NPs) using amino-functionalized metal-organic-frameworks (UiO-66-NH₂) as a NP matrix (Rh/UiO-66-NH₂). Owing to the coordination effect of amino-group and space-confinement of UiO-66-NH₂, small and well-distributed Rh NPs with a diameter of 3.38 nm are successfully achieved, which can be served as efficient catalysts for AB hydrolysis at room temperature. The maximum turnover frequency of 876.7 min^?1 is obtained by using the Rh/UiO-66-NH₂ with an optimal Rh loading of 4.38 wt% and AB concentration of 0.2 M at 25 °C, outperforming most of the previously developed Rh-based catalysts. The catalyst is also stable in repetitive cycles for five times. The high performance of this catalyst must be ascribed to the structural properties of UiO-66-NH₂, which enable the formation of small and well-dispersed Rh NPs with abundant accessible active sites. This study provides a simple and efficient method to significantly enhance the catalytic performance of Rh for AB hydrolysis.     

One-step synthesis of Cu@FeNi core–shell nanoparticles: Highly active catalyst for hydrolytic dehydrogenation of ammonia borane

This paper investigates a facile and one-step synthesis of trimetallic magnetic Cu@FeNi core–shell nanoparticles, which are composed of crystalline Cu cores and amorphous FeNi shells, at room temperature under ambient atmosphere within 2 min. It is found that among the Cu@FeNi system, Cu_0.4@Fe_0.1Ni_0.5 shows the best synergistic performance for catalyzing the hydrolytic dehydrogenation of ammonia borane with the activation energy of 32.9 kJ/mol, being lower than most of the reported data, and the catalytic activity of Cu_0.4@Fe_0.1Ni_0.5 is much better than its monometallic, bimetallic and trimetallic counterparts whether in states of pure metals, alloys or physical mixtures. Further, the present catalyst has a good recycle stability with an easy magnetic separation method.     

Evaluation of hydrogen producing cultures using pretreated food waste

In order to enhance bio-hydrogen production from food waste, pretreatment methods are widely used. The influence of the initial pH and autoclaving were investigated in batch experiments. Fermentative studies showed that pure cultures like Clostridium beijerinckii could directly utilize raw food waste to produce hydrogen, while other cultures (Clostridium butyricum and Clostridium pasteurianum) could produce hydrogen only after pH adjustment. In this case, the optimal starting pH of the culture was found to be 7. Autoclaving could further enhance hydrogen yields due to increased hydrolysis of food waste. The maximum hydrogen yield was achieved by C. butyricum (38.9 mL-H₂/g-VS_added) after autoclaving food waste with pH adjustment at 7. In addition, the ratio acetic to butyric acid was decreased by autoclaving pretreatment, because butyrate metabolic pathway was favored in the fermentation process. However, suitable pH for bacteria growth and the low ammonia production could be achieved from autoclaving food waste.