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.     

Pristine and cobalt doped copper sulfide microsphere particles for seawater splitting

In this work, copper sulfide particles are synthesized with different Co doping concentrations such as 0, 1 and 5% at 80 °C by optimizing synthesis times from 1 to 3 h. Copper sulfide particles possess two structural phases of covellite CuS and digenite Cu₉S₅. The increase in synthesis time from 1 to 3 h increases the Cu₉S₅ phase growth and changes the morphology from flower to microsphere. The CuS synthesized with 0, 1 and 5% Co dopant concentrations demonstrate flower consisting of agglomerated nanosheets, microsphere and flower like microsphere. The elemental investigation substantiates Co ions presence in CuS microspheres. The A_1g (LO) mode intensity is decreased with increase in Co dopant concentration confirming Co incorporation into CuS microsphere. The CuS synthesized with 0, 1, 5% Co dopants exhibit 322 mV, 305 mV and 289 mV to attain 100 mA/cm² in 1 M KOH seawater. The CuS synthesized with 5% Co dopant demonstrates higher double layer capacitance (C_dl) of 173.9 mFcm^?2 and lower charge transfer resistance (R_ct) of 6.07 Ω with 78.84% retention after 10 h continuous stability than that of the other pristine (118.3 mFcm^?2, 13.72 Ω) and 1% Co doped CuS microsphere (165.7 mFcm^?2, 8.55 Ω) indicating more surface active site and rapid charge carrier transport, respectively.     

Synthesis of bristlegrass-like Co-doped Ni2P composites on Ni foam for overall seawater splitting

Seawater is the most abundant resource on earth, so developing cost-effective, highly durable corrosion resistance and efficient electrocatalysts are crucial to enhance seawater splitting. Herein, we prepared 3D bristlegrass-like Co-doped Ni₂P (Co-Ni₂P) composites supported on Ni foam (NF) through a facile solvothermal method combined and a subsequent phosphatization treatment. Benefiting from the unique structure, Co-Ni₂P shows excellent electrocatalytic activity as an electrode material for both the hydrogen evolution reaction (HER, low overpotential of 116 mV at 50 mA cm^?2) and oxygen evolution reaction (OER, low overpotential of 266 mV at 50 mA cm^?2). Moreover, the as-prepared Co-Ni₂P composites exhibit excellent stability and corrosion resistance in an alkaline medium. Density functional theory (DFT) calculations were employed to evaluate the H1 adsorption of Co-Ni₂P, and the results proved the high catalytic activity for the HER. This study provides new materials with a unique morphology for overall water splitting.     

Characterization of sea water ageing effects on mechanical properties of carbon/epoxy composites for tidal turbine blades

In recent years, many tidal turbine projects have been developed using composites blades. Tidal turbine blades are subject to ocean forces and sea water aggressions, and the reliability of these components is crucial to the profitability of ocean energy recovery systems. The majority of tidal turbine developers have preferred carbon/epoxy blades, so there is a need to understand how prolonged immersion in the ocean affects these composites. In this study the long term behaviour of different carbon/epoxy composites has been studied using accelerated ageing tests. A significant reduction of composite strengths has been observed after saturation of water in the material. For longer immersions only small further changes in these properties occur. No significant changes have been observed for moduli nor for composite toughness. The effect of sea water ageing on damage thresholds and kinetics has been studied and modelled. After saturation, the damage threshold is modified while kinetics of damage development remain the same.     

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.     

Electrochemical behavior of metallic materials used in seawater—interactions between glucose oxidase and passive layers

Six materials (stainless steel, nickel-base alloy, titanium, chromium, nickel and admiralty brass) are tested in chemical and biochemical synthetic seawaters. The biochemical seawater contains enzymes catalyzing oxidation of glucose (glucose oxidase), simulating the action of natural biofilms. The evolutions of free corrosion potential (Ecor) versus time, and of cathodic and anodic reactions are compared with those obtained in natural seawater. Then, electrochemical behavior is related to semi-conducting properties of passive films. When glucose oxidase is present, increase of Ecor versus time is only reported for materials presenting a n-type semi-conductor passive film, and whose cathodic reaction current is increased. On the contrary, when passive layers are p-type semi-conductors, cathodic and anodic reactions are increased, and lead to a global Ecor constant with time of immersion. It appears that interaction between bacteria, medium and materials includes evolution of semi-conducting properties of passive layers.     

Influence of Solution Composition on the Formation of Crystalline Scales

Scale formation is a difficulty encountered with water containing ions of sparingly soluble salts that can readily precipitate on heat transfer surfaces in evaporative concentration operations. Scale formation, hindering the heat transfer process, increases specific energy consumption and operating costs and causes frequent shut down of the evaporator for cleaning. The effects of changes in composition of the solution due to evaporation and CO₂ release on the formation of crystalline scales in seawater evaporators are studied. A model that predicts the CO₂ release is presented. The carbonate system in the salt solution on its whole flow path through the evaporator and the scaling (crystallization) tendency are described. Simulation results for different process configurations are shown and the differences are discussed, particularly with regard to the incrustation tendency.     

低合金耐海水腐蚀钢在模拟腐蚀环境下的耐蚀性能研究

以普碳钢为对比样,采用模拟海水全浸和间浸、盐雾、湿热等加速腐蚀实验并结合电化学测试技术研究了Cu-Cr-Mo系低合金耐海水腐蚀钢Q345C-NHY3的耐蚀性能.结果表明：在各种模拟环境条件下与碳钢相比Q345C-NHY3钢都具有较好的耐蚀性能.     

Modelling of marine immersion corrosion for copper-bearing steels

The non-linear phenomenological model previously proposed for the ‘general’ corrosion loss of mild and low alloy steels under fully aerated ‘at-sea’ near-surface immersion conditions is applied to provide a new interpretation of literature data for copper-bearing steels. The data is examined to extract the parameters required for the model as a function of average seawater temperature. On the basis of the expectation of consistency, the data is then used to calibrate the parameters. All are generally consistent with the parameters derived earlier for mild and low alloy steels. The calibrated parameters are used to predict a consolidated plot of expected corrosion loss-time-temperature for copper-bearing steels. This compares favourably with a similar plot derived earlier from observed data alone.