Fabrication of tungsten oxide photoanode by doctor blade technique and investigation on its photocatalytic operation mechanism

WO₃ is a potential material candidate for construction of photoanode for solar driven water splitting. In this work, μm-thick porous WO₃ photoanode is prepared by depositing a stable ink made of WO₃ nanoparticles and Aristoflex velvet polymer in water using the doctor blade technique, followed by a sintering in air. The nature of WO₃ nanoparticles, its loading mass on F-doped tin oxide electrode as well as sintering temperature are examined in order to optimize the photocatalytic activity of the resultant WO₃ photoanode. The operation of WO₃ photoanode is investigated by varying the light illumination direction and light incident intensity as well as changing the nature of the electrolyte. Dissolved tungsten in electrolyte is quantified by ICP-MS providing insights into the influences of electrolyte nature and operating conditions to the corrosion of WO₃. It is proposed that the H₂O₂ and OH^. radical generated as by-products of the photo-driven water oxidation on the photoanode surface are harmful species that accelerate the dissolution of WO₃.     

Effects of corrosion in liquid fluoride salt on the tensile strength of domestic SiC fibers

The relationship between the tensile strength of corroded domestic second-generation (2ed-gen) SiC fibers at various temperatures for 500 h in 46.5LiF-11.5NaF-42.0KF (mol. %) eutectic salt and the typical microstructure was studied. Weibull theory was used to analyze the critical defects that caused the tensile fracture, and the microstructure of fibers before and after corrosion was characterized. It is concluded that the decrease of tensile strength after corrosion at 800 °C is caused by the surface injury of fibers, which led to the shift of critical defects from the internal defects of virgin fibers to surface defects. Moreover, corrosion at higher temperature accelerates the corrosion process and dissolve the surface O-contained layer thoroughly. This shifts the critical defects back to the internal defects and will be helpful for the recovery of tensile strength of corroded fibers at the higher temperature.     

Hydrogenation process in multiphase alloys of Ti-Zr-Mn-V system on the example of Ti42.75Zr27Mn20.25V10 alloy

The influence of phase composition and microstructure of Ti_42.75Zr₂₇Mn_20.25V₁₀ alloy on its hydrogenation kinetic and phase composition of hydrogenated product was studied. It is established that the process of dissociation of hydrogen molecules begins on the surface of Laves phase crystallites. The dissolution of atomic hydrogen in the material volume leads to the formation of cracks in the intermetallic crystallites, which further appear as additional centers of dissociation of hydrogen molecules and noticeably accelerate the diffusion of hydrogen into the bulk material. It was shown that the Laves phase acts as a donor of atomic hydrogen for the BCC solid solution during hydrogenation of two-phase structure, initiating intensive hydrogenation of the BCC phase at room temperature.     

Additive manufacturing of bipolar plates for hydrogen production in proton exchange membrane water electrolysis cells

Water electrolysis is a process that can produce hydrogen in a clean way when renewable energy sources are used. This allows managing large renewable surpluses and transferring this energy to other sectors, such as industry or transport. Among the electrolytic technologies to produce hydrogen, proton exchange membrane (PEM) electrolysis is a promising alternative. One of the main components of PEM electrolysis cells are the bipolar plates, which are machined with a series of flow distribution channels, largely responsible for their performance and durability. In this work, AISI 316L stainless steel bipolar plates have been built by additive manufacturing (AM), using laser powder bed fusion (PBF-L) technology. These bipolar plates were subjected to ex-situ corrosion tests and assembled in an electrolysis cell to evaluate the polarization curve. Furthermore, the obtained results were compared with bipolar plates manufactured by conventional machining processes (MEC). The obtained experimental results are very similar for both manufacturing methods. This demonstrates the viability of the PBF-L technology to produce metal bipolar plates for PEM electrolyzers and opens the possibilities to design new and more complex flow distribution channels and to test these designs in initial phases before scaling them to larger surfaces.     

The effect of Na addition on the first hydrogen absorption kinetics of cast hypoeutectic Mg–La alloys

With superior properties of Mg such as high hydrogen storage capacity (7.6 wt% H/MgH₂), low price, and low density, Mg has been widely studied as a promising candidate for solid-state hydrogen storage systems. However, a harsh activation procedure, slow hydrogenation/dehydrogenation process, and a high temperature for dehydrogenation prevent the use of Mg-based metal hydrides for practical applications. For these reasons, Mg-based alloys for hydrogen storage systems are generally alloyed with other elements to improve hydrogen sorption properties. In this article, we have added Na to cast Mg–La alloys and achieved a significant improvement in hydrogen absorption kinetics during the first activation cycle. The role of Na in Mg–La has been discussed based on the findings from microstructural observations, crystallography, and first principles calculations based on density functional theory. From our results in this study, we have found that the Na doped surface of Mg–La alloy systems have a lower adsorption energy for H₂ compared to Na-free surfaces which facilitates adsorption and dissociation of hydrogen molecules leading to improvement of absorption kinetic. The effect of Na on the microstructure of these alloys, such as eutectic refinement and a density of twins is not highly correlated with absorption kinetics.     

Polyetherimide-LaNi5 composite films for hydrogen storage applications

This study investigates the preparation of polyetherimide (PEI) – LaNi₅ composites films for hydrogen storage. Prior to the polymer addition, LaNi₅ was ball-milled at different conditions (250, 350, and 450 RPM) and annealed at 500 °C for 1 h under vacuum. The composites were produced with BM-LaNi₅-350 (PEI/LaNi₅-350) and annealed BM-LaNi₅-350 (PEI/LaNi₅-350-TT). Membranes were successfully produced through solvent casting assisted by an ultrasonic bath. The particles dispersion and the film morphology did not change after hydrogenation cycles. In the H₂ sorption experiments at 43 °C and 20 bar, the films stored H₂ without incubation time; both samples reached a capacity of ~0.6 wt%. The H₂ sorption kinetics of PEI/LaNi₅-350 was comparable to that of BM-LaNi₅-350, whereas PEI/LaNi₅-350-TT presented significantly slower kinetics. LaNi₅ oxidation was hindered by PEI, showing that it can be explored to improve metal hydrides air resistance. The results demonstrated that PEI films filled with LaNi₅ are promising materials for hydrogen storage.     

A gradient boosting decision tree approach for insider trading identification: An empirical model evaluation of China stock market

Insider trading is a kind of criminal behavior in stock market by using nonpublic information. In recent years, it has become the major illegal activity in China’s stock market. In this study, a combination approach of GBDT (Gradient Boosting Decision Tree) and DE (Differential Evolution) is proposed to identify insider trading activities by using data of relevant indicators. First, insider trading samples occurred from year 2007 to 2017 and corresponding non-insider trading samples are collected. Next, the proposed method is trained by the GBDT, and initial parameters of the GBDT are optimized by the DE. Finally, out-of-samples are classified by the trained GBDT–DE model and its performances are evaluated. The experiment results show that our proposed method performed the best for insider trading identification under time window length of ninety days, indicating the relevant indicators under 90-days time window length are relatively more useful. Additionally, under all three time window lengths, relative importance result shows that several indicators are consistently crucial for insider trading identification. Furthermore, the proposed approach significantly outperforms other benchmark methods, demonstrating that it could be applied as an intelligent system to improve identification accuracy and efficiency for insider trading regulation in China stock market.     

Effect of Ni/tubular g-C3N4 on hydrogen storage properties of MgH2

Additive doping is one of the effective methods to overcome the shortcomings of MgH₂ on the aspect of relatively high operating temperatures and slow desorption kinetics. In this paper, hollow g-C₃N₄ (TCN) tubes with a diameter of 2 μm are synthesized through the hydrothermal and high-temperature pyrolysis methods, and then nickel is chemically reduced onto TCN to form Ni/TCN composite at 278 K. Ni/TCN is then introduced into the MgH₂/Mg system by means of hydriding combustion and ball milling. The MgH₂–Ni/TCN composite starts to release hydrogen at 535 K, which is 116 K lower than the as-milled MgH₂ (651 K). The MgH₂–Ni/TCN composite absorbs 5.24 wt% H₂ within 3500 s at 423 K, and takes up 3.56 wt% H₂ within 3500 s, even at a temperature as low as 373 K. The apparent activation energy (E_a) of the MgH₂ decreases from 161.1 to 82.6 kJ/mol by the addition of Ni/TCN. Moreover, the MgH₂–Ni/TCN sample shows excellent cycle stability, with a dehydrogenation capacity retention rate of 98.0% after 10 cycles. The carbon material enhances sorption kinetics by dispersing and stabilizating MgH₂. Otherwise, the phase transformation between Mg₂NiH₄ and Mg₂NiH_0.3 accelerates the re/dehydrogenation reaction of the composite.     

Comparative techno-economic assessment of a large-scale hydrogen transport via liquid transport media

A large-scale point to point hydrogen transport is one strategy for a prospective energy import scenario for certain countries. The case for a hydrogen transport from Australia to Japan has been addressed in several studies. However, most studies lack transparency and detailed insights into the made assumptions thus a fair evaluation of different transport pathways is challenging. To address this issue, we developed a model where a large-scale point to point hydrogen transport of liquid hydrogen is compared with the transport via liquid organic hydrogen carrier (LOHC), namely via methyl cyclohexane and hydrogenated dibenzyl toluene. We analyzed, where energy is required along the different pathways, where hydrogen losses do occur and how the costs are put together. Furthermore, the influence of hydrogen feed costs is also considered. For hydrogen production costs of 5 €₂₀₁₈/kg_H2 the total delivery costs are in the range of 6.40– 8.10 €₂₀₁₈/kg_H2.     

Damage evolution in polymer due to exposure to high-pressure hydrogen gas

The use of hydrogen as a fuel is increasing exponentially, and the most economical way to store and transport hydrogen for fuel use is as a high-pressure gas. Polymers are widely used for hydrogen distribution and storage systems because they are chemically inert towards hydrogen. However, when exposed to high-pressure hydrogen, some hydrogen diffuses through polymers and occupies the preexisting cavities inside the material. Upon depressurization, the hydrogen trapped inside polymer cavities can cause blistering or cracking by expanding these cavities. A continuum mechanics–based deformation model was deployed to predict the stress distribution and damage propagation while the polymer undergoes depressurization after high-pressure hydrogen exposure. The effects of cavity size, cavity location, and pressure inside the cavity on damage initiation and evolution inside the polymer were studied. The stress and damage evolution in the presence of multiple cavities was also studied, because interaction among cavities alters the damage and stress field. It was found that all these factors significantly change the stress state in the polymer, resulting in different paths for damage propagation. The effect of adding carbon black filler particles and plasticizer on the damage was also studied. It was found that damage tolerance of the polymer increases drastically with the addition of carbon black fillers, but decreases with the addition of the plasticizer.