Recent advances in electrocatalysts for seawater splitting in hydrogen evolution reaction

Electrocatalytic water splitting is an important method to produce green and renewable hydrogen (H₂). One of the hindrances for wide applications of electrocatalysis in H₂ production is the lack of freshwater resources. Comparatively, seawater splitting has become an effective approach for large-scale H₂ production due to its abundant reserves. However, the increased complexity of seawater content emerged more problems in electrocatalytic seawater splitting. Recently, various strategies have been reported on improving the performance of electrocatalysts applied in seawater. Herein, this review firstly analyzed the mechanisms and challenges of electrocatalytic seawater splitting to evolve H₂, and summarized the recent progress on H₂ production in electrocatalytic seawater splitting. Furthermore, suggestions for future work have been provided for guidance.     

A review of hydrogen production processes by photocatalytic water splitting – From atomistic catalysis design to optimal reactor engineering

‘Renewable energy is an essential part of our strategy of decarbonization, decentralization, as well as digitalization of energy.’ – Isabelle Kocher.Current climate, health and economic condition of our globe demands the use of renewable energy and the development of novel materials for the efficient generation, storage and transportation of renewable energy. Hydrogen has been recognised as one of the most prominent carriers and green energy source with challenging storage, enabling decarbonization. Photocatalytic H₂ (green hydrogen) production processes are targeting the intensification of separated solar energy harvesting, storage and electrolysis, conventionally yielding O₂/H₂. While catalysis is being investigated extensively, little is done on bridging the gap, related to reactor unit design, optimisation and scaling, be it that of material or of operation. Herein, metals, oxides, perovskites, nitrides, carbides, sulphides, phosphides, 2D structures and heterojunctions are compared in terms of parameters, allowing for efficiency, thermodynamics or kinetics structure–activity relationships, such as the solar-to-hydrogen (STH). Moreover, prominent pilot systems are presented summarily.     

Investigation of liquid water heterogeneities in large area proton exchange membrane fuel cells using a Darcy two-phase flow model in a multiphysics code

Proper management of the liquid water and heat produced in proton exchange membrane (PEM) fuel cells remains crucial to increase both its performance and durability. In this study, a two-phase flow and multicomponent model, called two-fluid model, is developed in the commercial COMSOL Multiphysics® software to investigate the liquid water heterogeneities in large area PEM fuel cells, considering the real flow fields in the bipolar plate. A macroscopic pseudo-3D multi-layers approach has been chosen and generalized Darcy's relation is used both in the membrane-electrode assembly (MEA) and in the channel. The model considers two-phase flow and gas convection and diffusion coupled with electrochemistry and water transport through the membrane. The numerical results are compared to one-fluid model results and liquid water measurements obtained by neutron imaging for several operating conditions. Finally, according to the good agreement between the two-fluid and experimentation results, the numerical water distribution is examined in each component of the cell, exhibiting very heterogeneous water thickness over the cell surface.     

The dynamic effect of Micro-MHD convection on bubble grown at a horizontal microelectrode

Relatively low efficiency is the biggest obstacle to the popularization of water electrolysis, which is a particularly feasible way to produce super-pure hydrogen. Imposing a magnetic field can increase the hydrogen production efficiency of water electrolysis. However, the enhancement's detailed mechanism still lacks an insightful understanding of the bubbles' micro vicinity. Our recent work aims to understand why the micro-magnetohydrodynamic (MHD) convection hinders single bubbles' detachment on the microelectrode. A water electrolysis experiment by microelectrode is performed under an electrode-normal magnetic field, and dynamic analysis of the single bubble growing on microelectrodes is performed. The variation of bubble diameter with time in the presence or absence of the magnetic field was measured, and the forces acting on the bubble were quantified. The result shows that the micro-MHD convection, induced by Lorentz force, can give rise to a downward hydrodynamic pressure force that will not appear in large-scale MHD convection. This force can be of the same magnitude as the surface tension, so it dramatically hinders bubbles' detachment. Besides, the Kelvin force provides a new potential way for further improving the efficiency of water electrolysis.     

Charge source and the charging mechanism of the contact electrification of polymer powder

The charge sources, as well as the charging mechanism of the contact electrification (CE) of polymers, are still debatable. Since CE is accompanied by destruction, it is considered that “hard contacting” via ball milling can induce covalent bond scission and produce naked-activated-charge sources. Regarding “soft contacting” via nano-scale sliding, which does not induce covalent bond scission, a frontier-electron, “f-electron,” of the naked-activated-charge source is crucial to electron transfer among the naked-activated-charge sources. Here, we configure naked-activated-charge-source models, naked-activated-mechano-anion, and naked-activated-mechano-cation, which are produced by mechanical energy induced heterogeneous covalent bond scission, as well as naked-activated-mechano-radicals that are produced by homogeneous covalent bond scission. Regarding “soft contacting” among naked-activated-charge sources in a vacuum, f-electron can be transferred from a donor to an acceptor if the energy level of the donor is higher than that of the acceptor. The net amount of the normalized transferred-f-electrons is obtained by adopting settings in which the average energy level of the naked-activated-charge sources (as the donors) is higher than that of the sources employed as acceptors. Thus, the surfaces comprising the donors and acceptors will exhibit positive and negative net surface charges, respectively. We conclude that net surface charges depend on the average energy level of naked-activated-charge sources. Further, we observe that the alignment of polyethylene (PE)-polyvinyl chloride (PVC)-polytetrafluoroethylene (PTFE) to the average energy level is identical to that of the triboelectric series.     

Designing independent water transport channels to improve water flooding in ultra-thin nanoporous film cathodes for PEMFCs

Utilization of 3D nanostructured Pt cathodes could obviously improve performances of proton exchange membrane fuel cells (PEMFCs) owing to the reduced tortuosity and the bi-continuous nanoporous structure. However, these cathodes usually suffer from the flooding problem ascribed to the ionomer-free and nanoscale pores which are more susceptible to water condensation. In this paper, ultra-thin nanoporous metal films (100 nm) were utilized to construct PEMFC cathodes and independent transport channels were designed separately for water and gas aiming at the flooding problem. Nanoporous gold (NPG) film was used as the model support for loading Pt nanoparticles owing to its controllable and stable structure. After optimizing the polytetrafluoroethylene (PTFE) content and carbon loading in the gas diffusion layer (GDL), plasma treatment under O₂ atmosphere was used to pattern the GDL with independent water transport channels. The obtained liquid permeation coefficients and oxygen gains demonstrated the obviously improved water and O₂ transport. By using a home-made optimized GDL and a nanoporous film cathode with pore size ～60 nm, the flooding problem could be facilely solved. With a Pt loading of ～16 μg cm^?2, this 3D nanostructured cathode exhibits a PEMFC performance of ～957 mW cm^?2 at 80 °C. The Pt power efficiency is about 4 times higher than that of the commercial Pt/C cathode (50 μg cm^?2, 756 mW cm^?2). Obviously, this study provides a simple but effective methodology to solve the water flooding problem in the ultra-thin nanoporous film cathodes which is applicable for other types of 3D nanostructured PEMFC cathodes.     

Numerical study of entropy generation in Darcy-Forchheimer (D-F) Bödewadt flow of CNTs

Three-dimensional Bödewadt flow (fluid rotates at a large enough distance from the stationary plate) of carbon nanomaterial is examined. Single walled and multi walled CNTs are dissolved in water and gasoline oil baseliquids. Darcy-Forchheimer porous medium is considered. Stationary disk is further stretched linearly in radial direction. Heat transfer effect is examined in presence of radiation and convection. Effect of viscous dissipation is accounted. Entropy generation rate is studied. By using adequate transformation (von Kármán relations), the flow field equations (PDEs) are transmitted into ODEs. Solutions to these ODEs are constructed via implementation of shooting method (bvp4c). In addition to Entropy generation rate, Bejan number, heat transfer rate (Nusselt number), skin friction and temperature of fluid are examined through involved physical parameters. Axial component of velocity intensifies with increment in nanoparticles volume fraction and ratio of stretching rate to angular velocity parameter while it decays with higher porosity parameter. Higher nanoparticles volume fraction and porosity parameter lead to decay in radial as well as tangential component of velocity. However it enhances with higher ratio of stretching rate to angular velocity parameter. Temperature of fluid directly varies with higher ratio of stretching rate to angular velocity parameter, radiation parameter, Eckert number, Biot number and nanoparticles volume fraction. Rate of Entropy generation is reduced with higher estimations of porosity parameter, nanoparticles volume fraction and radiation parameter. Skin friction coefficient decays with higher porosity parameter and ratio of stretching rate to angular velocity parameter. Intensification in porosity parameter, nanoparticles volume fraction and Biot number leads to higher Nusselt number. Prominent impact is shown by multiple-walled CNTs with gasoline oil basefluid than single-walled CNTs with water basefluid.     

Fault handling in large water networks with online dictionary learning

Fault detection and isolation in water distribution networks is an active topic due to the nonlinearities of flow propagation and recent increases in data availability due to sensor deployment. Here, we propose an efficient two-step data driven alternative: first, we perform sensor placement taking the network topology into account; second, we use incoming sensor data to build a network model through online dictionary learning. Online learning is fast and allows tackling large networks as it processes small batches of signals at a time. This brings the benefit of continuous integration of new data into the existing network model, either in the beginning for training or in production when new data samples are gathered. The proposed algorithms show good performance in our simulations on both small and large-scale networks.     

Seawater-softening process through formation of calcite ooids

Conventional water-softening processes usually involve the exchange of Na⁺ ions for Ca²⁺ and Mg²⁺ using commercial or synthesized ion exchangers. The differences in chemical compositions of the ooids can be attributed to the formation in different environments. In this paper, ooid grains form inside assembled semi-pilot softening unit through a continuous chemical process involving reaction between bicarbonate ions and added lime using natural seawater. Our sample of Mediterranean seawater has low Mg²⁺/Ca²⁺ ratio (1.98%) within the range chemically favorable for precipitation of low-Mg calcite ooids. Precipitation of calcite occurs around pure quartz sand grains which act as nucleation points (the bed required for sand vessel is 1.65 l). The shape of the sand grains controls the overall external morphology of the resulting ooids; they vary in size from 0.5 to 3.0 mm and have a high degree of polish due to surface abrasion caused by continuous agitation inside the softening system. Calcite ooid grains (1.53 kg) formed within the seawater-softening unit every 18 days have many of the ooid features formed in marine environments. Ooids grow to a significant size, at a rate of about 0.17 mm of one layer thickness per day inside the softening unit. The average weight percent of calcite precipitate is 35.48% after 18 days, at 10 °C, 60 l/min and pH 9.0. The pellets comprise mainly CaCO₃ and SiO₂ and some metal ions which may substitute for calcium ions in calcite are present only in trace amounts of the total composition.     

尿素装置液位仪表失真分析及处理

介绍了尿素装置中3起液位仪表失真案例,分析了故障现象和设备工况,确定失真原因,采取了相应的处理措施,解决了仪表故障。