Completely eliminating the metal barrier cracks on Nafion for suppressing methanol crossover with anodic aluminum oxide substrates

Methanol crossover is one of the main challenges for direct methanol fuel cells (DMFCs). Depositing a metal barrier on Nafion can reduce the crossover but usually faces the metal cracking issues. This study presents a new composite membrane in which an anodic aluminum oxide (AAO) substrate is impregnated with a Nafion solution and then coated with a layer of Au. The AAO/Nafion/Au composite membrane shows an ideal metal crack-free surface. Higher and more stable voltage has been achieved for the cell with the membrane, indicating an effectively suppressed methanol-crossover. Results reveal that there is a tradeoff between suppressing the methanol crossover and increasing the ion transmission. By optimizing the membrane, it can not only suppress the methanol crossover but also enhance the output performance of DMFCs. The current density and power density of the cells can be enhanced by 59% and 52.85%, respectively, compared to the cell with a commercial Nafion 117. Overall, this work provides a new approach to designing crack-free membranes for DMFCs.     

Numerical study on laminar burning velocity of ammonia flame with methanol addition

The combustion characteristics of ammonia/methanol mixtures were investigated numerically in this study. Methanol has a dramatic promotive effect on the laminar burning velocity (LBV) of ammonia. Three mechanisms from literature and another four self-developed mechanisms constructed in this study were evaluated using the measured laminar burning velocities of ammonia/methanol mixtures from Wang et al. (Combust.Flame. 2021). Generally, none of the selected mechanisms can precisely predict the measured laminar burning velocities at all conditions. Aiming to develop a simplified and reliable mechanism for ammonia/methanol mixtures, the constructed mechanism utilized NUI Galway mechanism (Combust.Flame. 2016) as methanol sub-mechanism and the Otomo mechanism (Int. J. Hydrogen. Energy. 2018) as ammonia sub-mechanism was optimized and reduced. The reduced mechanism entitled ‘DNO-NH3’, can accurately reproduce the measured laminar burning velocities of ammonia/methanol mixtures under all conditions. A reaction path analysis of the ammonia/methanol mixtures based on the DNO-NH3 mechanism shows that methanol is not directly involved in ammonia oxidation, instead, the produced methyl radicals from methanol oxidization contribute to the dehydrogenation of ammonia. Besides, NO_x emission analysis demonstrates that 60% methanol addition results in the highest NO_x emissions. The most important reactions dominating the NO_x consumption and production are identified in this study.     

Progress and major BARRIERS of nanocatalyst development in direct methanol fuel cell: A review

Direct methanol fuel cells (DMFC), among the most suited and prospective alternatives for portable electronics, have lately been treated with nanotechnology. DMFCs may be able to remedy the energy security issue by having low operating temperatures, high conversion efficiencies, and minimal emission levels. Though, slow reaction kinetics are a significant restriction of DMFC, lowering efficiency and energy output. Nowadays, research is more focused on fundamental studies that are studying the factors that can improve the capacity and activity of catalysts. In DMFC, among the most widely explored catalysts are platinum and ruthenium which are enhanced in nature by the presence of supporting materials such as nanocarbons and metal oxides. As a result, this research sheds light on nanocatalyst development for DMFCs based on Platinum noble metal. To summarize, this research focuses on the structure of nanocatalysts, as well as support materials for nanocatalysts that can be 3D, 2D, 1D, or 0D. The support material described is made up of CNT, CNF, and CNW, which are the most extensively used because they improve the performance of catalysts in DMFCs. In addition, cost estimations for fuel cell technology are emphasized to show the technology's status and requirements. Finally, challenges to nanocatalyst development have been recognized, as well as future prospects, as recommendations for more innovative future research.     

Hydrogen carriers: Production,transmission, decomposition,and storage

Recognizing the potential role of liquid hydrogen carriers in overcoming the inherent limitations in transporting and storing gaseous and liquid hydrogen, a complete production and use scenario is postulated and analyzed for perspective one-way and two-way carriers. The carriers, methanol, ammonia and toluene/MCH (methylcyclohexane), are produced at commercially viable scales in a central location, transmitted by rail or pipelines for 2000 miles, and decomposed near city gates to generate fuel-cell quality hydrogen for distribution to refueling stations. In terms of the levelized cost of H₂ distributed to the stations, methanol is less expensive to produce ($1.22/kg-H₂) than MCH ($1.35/kg-H₂) or ammonia ($2.20/kg-H₂). Levelized train transmission cost is smaller for methanol ($0.63/kg-H₂) than ammonia ($1.29/kg-H₂) or toluene/MCH system ($2.07/kg-H₂). Levelized decomposition cost is smaller for ammonia ($0.30–1.06/kg-H₂) than MCH ($0.54–1.22/kg-H₂) or methanol ($0.43–1.12/kg-H₂). Over the complete range of demand investigated, 10–350 tpd-H₂, the levelized cost of H₂ distributed to stations is aligned as methanol « ammonia ~ MCH. With pipelines at much larger scale, 6000 tpd-H₂, the levelized cost decreases by ~1 $/kg-H₂ for ammonia and MCH and much less for methanol. Methanol is a particularly attractive low-risk carrier in the transition phase with lower than 50-tpd H₂ demand.     

Stripping and recycling of metal ions in aqueous nitric acid solutions: Experimental and molecular dynamics insights

Stripping of metal ions (i.e., Cs⁺ and Na⁺) in presence of ionophore such as dibenzo-18-crown-6, (DB18C6) from the ionic liquid phase to the aqueous nitric acid phase by molecular dynamics simulation is reported. The experimentally determined stripping percentages of Na⁺ (i.e., 43.4, 38.5, 34.4, and 31.9%) were found to be higher than the same for Cs⁺ (i.e., 32.6, 32.0, 31.3, and 30.2%). The nonbonded and the hydrogen bond energies between Na⁺ and water (i.e., −356.41 and −363.77 kcal/mol) were higher when compared with Cs⁺ (i.e., −212.43 and −221.04 kcal/mol). The spatial distribution functions further confirmed that the surfaces of Na⁺ were very closely distributed around the active sides of water whereas for Cs⁺, it was distributed very far from the water molecules. In the penultimate section, the effect of methanol to the aqueous phase was studied so as to enhance the extraction efficiency of the complex.     

甲醇转化制丙烯反应机理研究

以杂化轨道理论和关于含Si、Al元素催化剂酸中心的认识为理论依据和研究方法，从反应物与催化剂B酸中心相互作用为切入点，分析相互作用过程中甲醇与B酸中心分子结构变化，揭示甲醇制烯烃反应机理本质。研究结果表明甲醇转化制丙烯反应过程可分为3步：(1)B酸中心释放H+攻击甲醇分子中C-O键，C-O键断裂生成甲基碳正离子(CH+3)和H2O，CH+3中C原子外层有个空轨道，释放了H+后的B酸中心失去活性。(2)失活B酸中心从CH+3中获得H+，反应生成了一种新中间体H-form，H-form中C原子外层有1对孤对电子(e-)和1个空轨道，结构式为C↑↓〇H2；失活的B酸中心获得H+后恢复活性。第3步，有3个H-form结构的C原子，第1个C原子上的孤对e－占据第2个C原子上空轨道，第2个C原子上的孤对e－占据第1个C原子上空轨道，彼此共用2对e-，形成C=C键；第3个C原子上的空轨道与第1个C原子上C、H原子重叠轨道再次重叠，形成C、H和C三原子共用1对e－结构，结果是第1个C原子与第2个C原子形成C=C键，第1个C原子与第3个C原子形成C-C键，3个C原子形成C=C-C结构，即生成丙烯。     

Hydrogen production by oxidative steam reforming of methanol over anodic aluminum oxide-supported Cu-Zn catalyst

Oxidative steam reforming of methanol (OSRM), which is a convenient reaction for producing hydrogen, suffers from the hot spot formation problem when conventional particle catalysts are used. Recently, an anodic aluminum oxide (AAO)-supported Cu-Zn catalyst was proposed as an OSRM catalyst for its high thermal conductivity through the aluminum metal body. In this study, OSRM was conducted in a prototype reactor packed with the AAO plate catalyst strips. It was verified that the high thermal conductivity of the catalyst effectively suppresses the hot spot formation and makes the temperature profile smooth along the reactor. The start-up time of the reactor depended on the preheating temperature and was very short (less than 2 min) for preheating over 503 K. The methanol conversion and reactor temperature increased with increasing O₂/CH₃OH mole ratio, indicating that the mole ratio can be used as a control variable to operate the reactor at desired conditions. Further, a reactor model was developed and verified, and the simulation showed that for a given total reactor volume, an optimal reactor configuration could be achieved by shortening the reactor length while widening the cross-sectional area.     

便携式近红外甲醇检测仪与实验室仪器预测能力比较

目的探究联合研发便携式近红外检测仪检测白酒基酒中甲醇含量的可行性。方法分别用比色皿、液体探头取样检测白酒基酒中甲醇的含量,借助化学计量学方法建立白酒中甲醇含量的预测模型,并与实验室VECTOR33型近红外光谱仪所建模型的预测能力进行比较。结果校正集决定系数分别为:0.819、0.838、0.886,校正标准差分别为:16.13、15.78、14.60mg/L,验证集的决定系数分别为:0.814、0.820、0.844,预测标准差分别为:19.99、19.25、20.44 mg/L,平均相对误差分别为:8.94%、8.32%、9.34%。结论研发的便携式近红外检测仪与实验室仪器的检测结果具有较好的一致性,可以用来检测白酒基酒中甲醇含量。