Solidophobic Surface for Electrochemical Extraction of High-Valued Mg(OH)2 Coupled with H2 Production from Seawater.

A significant challenge in direct seawater electrolysis is the rapid deactivation of the cathode due to the large scaling of Mg(OH)2. Herein, we synthesized a Pt-coated highly disordered NiCu alloy (Pt-NiCu alloy) electrode with superior solidophobic behavior, enabling stable hydrogen generation (100 mA cm-2, >1000 h durability) and simultaneous production of Mg(OH)2 (>99.0% purity) in electrolyte enriched with Mg2+ and Ca2+. The unconventional solidophobic property primarily stems from the high surface energy of the NiCu alloy substrate, which facilitates the adsorption of surface water and thereby compels the bulk formation of Mg(OH)2 via homogeneous nucleation. The discovery of this solidophobic electrode will revolutionarily simplify the existing techniques for seawater electrolysis and increase the economic viability for seawater electrolysis.

The Critical Role of Additive Sulfate for Stable Alkaline Seawater Oxidation on Nickel-Based Electrodes.

Seawater electrolysis to produce hydrogen is a critical technology in marine energy projects; however, the severe anode corrosion caused by the highly concentrated chloride is a key issue should be addressed. In this work, we discover that the addition of sulfate in electrolyte can effectively retard the corrosion of chloride ions to the anode. We take nickel foam as the example and observe that the addition of sulfate can greatly improve the corrosion resistance, resulting in prolonged operating stability. Theoretical simulations and in situ experiments both demonstrate that sulfate anions can be preferentially adsorbed on anode surface to form a negative charge layer, which repulses the chloride ions away from the anode by electrostatic repulsion. The repulsive effect of the adsorbed sulfate is also applicable in highly-active catalyst (nickel iron layered double hydroxide) on nickel foam, which shows ca. 5 times stability of that in traditional electrolyte.

Ag Nanoparticle-Induced Surface Chloride Immobilization Strategy Enables Stable Seawater Electrolysis.

Although hydrogen gas (H2 ) storage might enable offshore renewable energy to be stored at scale, the commercialization of technology for H2 generation by seawater electrolysis depends upon the development of methods that avoid the severe corrosion of anodes by chloride (Cl- ) ions. Here, it is revealed that the stability of an anode used for seawater splitting can be increased by more than an order of magnitude by loading Ag nanoparticles on the catalyst surface. In experiments, an optimized NiFe-layered double hydroxide (LDH)@Ag electrode displays stable operation at 400 mA cm-2 in alkaline saline electrolyte and seawater for over 5000 and 2500 h, respectively. The impressive long-term durability is more than 20 times that of an unmodified NiFe-LDH anode. Meticulous characterization and simulation reveals that in the presence of an applied electric field, free Cl- ions react with oxidized Ag nanoparticles to form stable AgCl species, giving rise to the formation of a Cl- -free layer near the anode surface. Because of its simplicity and effectiveness, it is anticipated that the proposed strategy to immobilize chloride ions on the surface of an anode has the potential to become a crucial technology to control corrosion during large-scale electrolysis of seawater to produce hydrogen.

Progress in Anode Stability Improvement for Seawater Electrolysis to Produce Hydrogen.

Seawater electrolysis for hydrogen production is a sustainable and economical approach that can mitigate the energy crisis and global warming issues. Although various catalysts/electrodes with excellent activities have been developed for high-efficiency seawater electrolysis, their unsatisfactory durability, especially for anodes, severely impedes their industrial applications. In this review, attention is paid to the factors that affect the stability of anodes and the corresponding strategies for designing catalytic materials to prolong the anode's lifetime. In addition, two important aspects-electrolyte optimization and electrolyzer design-with respect to anode stability improvement are summarized. Furthermore, several methods for rapid stability assessment are proposed for the fast screening of both highly active and stable catalysts/electrodes. Finally, perspectives on future investigations aimed at improving the stability of seawater electrolysis systems are outlined.

Stable Seawater Electrolysis Over 10 000 H via Chemical Fixation of Sulfate on NiFeBa-LDH.

Although hydrogen production through seawater electrolysis combined with offshore renewable energy can significantly reduce the cost, the corrosive anions in seawater strictly limit the commercialization of direct seawater electrolysis technology. Here, it is discovered that electrolytic anode can be uniformly protected in a seawater environment by constructing NiFeBa-LDH catalyst assisted with additional SO4 2- in the electrolyte. In experiments, the NiFeBa-LDH achieves unprecedented stability over 10 000 h at 400 mA cm-2 in both alkaline saline electrolyte and alkaline seawater. Characterizations and simulations reveal that the atomically dispersed Ba2+ enables the chemical fixation of free SO4 2- on the surface, which generates a dense SO4 2- layer to repel Cl- along with the preferentially adsorbed SO4 2- in the presence of an applied electric field. In terms of the simplicity and effectiveness of catalyst design, it is confident that it can be a beacon for the commercialization of seawater electrolysis technology.

Concerning the stability of seawater electrolysis: a corrosion mechanism study of halide on Ni-based anode.

The corrosive anions (e.g., Cl-) have been recognized as the origins to cause severe corrosion of anode during seawater electrolysis, while in experiments it is found that natural seawater (~0.41 M Cl-) is usually more corrosive than simulated seawater (~0.5 M Cl-). Here we elucidate that besides Cl-, Br- in seawater is even more harmful to Ni-based anodes because of the inferior corrosion resistance and faster corrosion kinetics in bromide than in chloride. Experimental and simulated results reveal that Cl- corrodes locally to form narrow-deep pits while Br- etches extensively to generate shallow-wide pits, which can be attributed to the fast diffusion kinetics of Cl- and the lower reaction energy of Br- in the passivation layer. Additionally, for the Ni-based electrodes with catalysts (e.g., NiFe-LDH) loading on the surface, Br- causes extensive spalling of the catalyst layer, resulting in rapid performance degradation. This work clearly points out that, in addition to anti-Cl- corrosion, designing anti-Br- corrosion anodes is even more crucial for future application of seawater electrolysis.

Tafel Analysis Guided Optimization of ZnNP-O-C Catalysts for the Selective 2-Electron Oxygen Reduction Reaction in Neutral Media.

The lack of characterizations of the adsorption capability toward intermediates during reactions causes difficulties in determining the structural optimization principle of the catalysts for the 2-electron oxygen reduction reaction (2e- ORR). Here, a Tafel-θ method is proposed to evaluate the surface coverage (θ) of important intermediates (*OOH and *OH) on the material surface and further help optimize the catalyst. With the assistance of Tafel-θ analysis, a Zn nanoparticle incorporated oxygen-doped carbon (ZnNP-O-C) catalyst with high 2e- ORR performance (onset of ∼0.57 V and selectivity of >90.4%) in neutral media was achieved. Both the theoretical calculation and characterization results are consistent with the Tafel-θ deduction, revealing that an appropriate ratio of Zn nanoparticles and bridging O can optimize the *OOH adsorption/desorption strength of the adjacent carbon site. This study not only provides an advanced ZnNP-O-C catalyst for electrochemical H2O2 production but also proposes a fast and precise method for the comprehensive assessment of future catalysts.