In-situ investigation and modeling of electrochemical reactions with simultaneous oxygen and hydrogen microbubble evolutions in water electrolysis

The development of water electrolyzer is challenging as we approach theoretical limits arising from electrochemical reactions and micro-scale bubble dynamics. In this research, two-phase flow and bubble dynamics are in-situ studied in a special designed single-channel electrolyzer. The devices fabricated by a 3D printer provide a whole vision of the electrochemical reaction within the channel. In-situ observations of channel-scale hydrogen and oxygen micro-bubbles dynamics are conducted, and the whole process of hydrogen evolution reactions (HERs) and oxygen evolution reactions (OERs) are simultaneously studied. The results indicate that all bubbles generate at the interface between the proton exchange membrane and the electrode wire, and the operating conditions have a great impact on the micro bubble evolution process. The bubble detachment diameter is inversely proportional to the flow velocity, but is in direct proportion to the current density. Finally, a mathematic model has been developed, and shows a good agreement with experimental data. Those results could help to better understand the bubble evolution mechanism, in order to further understand the electrochemical reaction.     

Design and characterization of compact proton exchange membrane water electrolyzer for component evaluation test

In this study, we designed and developed a compact electrolyzer for the evaluation of components in proton exchange membrane (PEM) water electrolysis. First, this electrolyzer features a precise pressure-control system that controls the active electrode area and facilitates setting the desired clamping pressure. This mechanism makes it possible to optimize the electrolyzer performance. Second, it has two reference electrodes that are connected on the faces of the active electrode area of the anode and the cathode on the PEM. The polarizations at the anode and the cathode, the membrane resistivity, and the porous transport layer (PTL) overpotential were measured. The details of the design are described, and the electrochemical performance was measured. The optimized clamping pressure for this electrolyzer component was obtained as the specific value. A new measurement method was developed for estimating polarizations at the anode and the cathode, membrane resistance, and PTL overpotential using two reference electrodes.     

Ni/Fe electrodes prepared by electrodeposition method over different substrates for oxygen evolution reaction in alkaline medium

A series of Ni/Fe electrodes have been prepared by electrodeposition of metal salt precursors on different substrates. The surface morphology, chemical composition and electrochemical characteristics of these electrodes were studied by various physico-chemical techniques such as X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). The electrochemical properties of the electrodes were examined by steady-state polarization curves. First, the influence of features such as Ni/Fe composition and type of substrate for the oxygen evolution reaction (OER) were determined by electrochemical techniques in a conventional 3-electrodes cell. The overpotential for the OER is lower for the electrodes with the higher concentrations of Ni. The electrodes with a Ni/Fe composition of 75/25 wt.% electrodeposited on steel mesh and/or 75/25 and 50/50 wt.% on nickel foam result in the most active configurations for the OER. These electrodes were further tested as anodes for alkaline water electrolysis during at least 70 h. In order to understand their activity and stability, the used electrodes were also characterized by SEM and compared to the fresh electrodes. Among the compositions and substrates examined, the Ni50Fe50-Nf electrode exhibited the lowest overpotential (2.1 V) for the OER and the higher stability as anode in an alkaline water electrolysis cell.     

Brazilian fly ash based inorganic polymers production using different alkali activator solutions

Inorganic polymers are a relatively new class of inorganic binders of elevated mechanical strength and chemical resistance which can be produced from various industrial byproducts containing alumina and silica such as fly ash, slag and kaolin. In this work, fly ash from a Brazilian thermoelectric power station at Capivari de Baixo, Santa Catarina, was used to produce the inorganic cement. Different alkaline activator solutions were used in order to study their influence on the properties of the produced inorganic polymers. The results demonstrated that this fly ash is a viable starting material for the production of inorganic binders with compression strength higher than 40 MPa. It has been observed that the compression strength increased with increasing curing time of up to 28 days. Phase analysis by X-ray diffraction analysis revealed the formation of new zeolithic phases during the polymerization process. The polymerization process was also confirmed by modifications of the binding structure, as indicated by altered and new absorption bands observed by infrared spectroscopy. Furthermore, it has been found that physical properties, such as density and porosity, not only varied for different activator solutions, but also with curing time.     

高电流密度膜极距电解装置运行经验

介绍湖北兴瑞化工有限公司第1期15万t/a离子膜法烧碱装置运行情况.在高电流密度下通过严格控制各项工艺指标及规范操作,可确保该装置长期稳定运行.     

Initial pH influences microbial communities composition in dark fermentation of scotta permeate

This study addresses for the first time the influence of initial pH on the evolution of microbial consortia in dark fermentation of scotta permeate, using a high-throughput sequencing approach. Three fermentation phases could be detected: 1) a lag phase with no substantial differences in microbial composition at different initial pH values; 2) an exponential H₂ production phase, accompanied by a general increase of Clostridium genus components and higher incidence of Trichococcus genus at neutral and alkaline pH; 3) a final stationary phase, characterized by a general increase of Bifidobacterium and Lactobacillus genera in all reactors. The initial pH value influenced the relative abundance of Trichococcus at 16–48 h of incubation. The metabolic activity of this genus increased the amount of metabolic precursors of H₂ so that, when pH lowered to 5.4, clostridia in the reactors with initial alkaline pH become more active H₂-producers than those in the others.     

The stability of monochlorotriazinyl reactive dyes on cellulose films in aqueous alkaline solutions containing peroxide bleaching agents

The stability of seven reactive (one difluoromonochloropyrimidinyl and six monochlorotriazinyl) dyes on cellulose immersed in sodium peroxoborate (PB) solution (UK–TO solution) containing tetraacetylethylenediamine (TAED) was examined using cellulosic films at 60 °C. The extent of dye loss that occurred from the dyed cellulosic films which were immersed in the UK–TO solution without detergent correlated closely to the ratings obtained using the BS 1006 UK–TO wash test. The dye loss that occurred from the dyed cellophane films was attributed to three contributions, namely, alkaline hydrolysis of dye–fibre bonds, oxidative fading of the dye chromophore by peroxides and cellulose degradation accelerated by PB and TAED. The alkaline hydrolysis of the dye–fibre bond and the extent of cellulose degradation in the UK–TO solution were the main contributions to the dye loss; dye oxidation was a minor factor in the dye loss mechanism. The physical bonding of the dye molecules reinforced the covalent dye–fibre bond stability towards the UK–TO solution.     

High efficiency process for the production of pure oxygen based on solid oxide fuel cell–solid oxide electrolyzer technology

This paper presents a novel system for production of pure oxygen based on the integration of a solid oxide fuel cell (SOFC) and a solid oxide electrolyzer (SOEC). In the proposed arrangement, the SOFC provides electricity, heat and H₂O in vapour phase to the SOEC which carries out the inverse reactions of the SOFC, that is the separation of H₂O into H₂ (used as a fuel for the SOFC) and O₂ (representing the yield of the system). Simulations carried out in different operating conditions show that when the integrated SOFC–SOEC device runs at low current densities (less than 1000 A m⁻²), pure oxygen can be generated with an electric consumption comparable to mid-size cryogenic air separation units, and significantly lower than small scale systems based on the PSA technology.     

Towards recycling purpose: Converting PET plastic waste back to terephthalic acid using pH-responsive phase transfer catalyst

Converting polyethylene terephthalate (PET) wastes to its monomer and valuable chemicals via eco-friendly chemical method is still a challenge task. Previously, phase transfer catalysts used for alkaline hydrolysis were soluble in reaction media and hardly separated after reaction. Here, we reported several pH-responsive catalysts combined alkyl quaternary ammonium units with heteropolyacid anion for achieving stepwise product/catalyst separation and catalyst recycling. The properties of homogeneous/heterogeneous transfer behavior allow catalyst to be easily separated from reaction media by adjusting of pH value. Among them, [C₁₆H₃₃N(CH₃)₃]₃PW₁₂O₄₀ (abbreviated as [CTA]₃PW) exhibits the highest activity and the most suitable pH responsive values. Such a pH triggered switchable catalytic system not only shows good performance for depolymerization of pure PET, but also some real PET wastes such as coloured trays and PE/PET complex films could be completely degraded into terephthalic acid. Additionally, the reaction kinetics and activation energy of PET alkaline hydrolysis also studied with and without pH-responsive [CTA]₃PW.     

硫酸根对离子膜电解工艺影响及处理

离子膜电解工艺中,硫酸根的影响有:硫酸根易与钙离子结合,降低氯气纯度,降低电解槽电流效率。提出去除硫酸根的方法有:钡法,钙法,碳酸钡法,树脂吸附法,膜法,以及膜法+冷冻结晶法。