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.

The Recent Progresses of Electrodes and Electrolysers for Seawater Electrolysis.

The utilization of renewable energy for hydrogen production presents a promising pathway towards achieving carbon neutrality in energy consumption. Water electrolysis, utilizing pure water, has proven to be a robust technology for clean hydrogen production. Recently, seawater electrolysis has emerged as an attractive alternative due to the limitations of deep-sea regions imposed by the transmission capacity of long-distance undersea cables. However, seawater electrolysis faces several challenges, including the slow kinetics of the oxygen evolution reaction (OER), the competing chlorine evolution reaction (CER) processes, electrode degradation caused by chloride ions, and the formation of precipitates on the cathode. The electrode and catalyst materials are corroded by the Cl- under long-term operations. Numerous efforts have been made to address these issues arising from impurities in the seawater. This review focuses on recent progress in developing high-performance electrodes and electrolyser designs for efficient seawater electrolysis. Its aim is to provide a systematic and insightful introduction and discussion on seawater electrolysers and electrodes with the hope of promoting the utilization of offshore renewable energy sources through seawater electrolysis.

PEM Electrochemical Hydrogen Compression with Sputtered Pt Catalysts.

This work presents research on thin magnetron-sputtered platinum (Pt) films deposited over commercial gas diffusion electrodes and applied to convert and pressurize hydrogen in an electrochemical hydrogen pump. The electrodes were integrated into a membrane electrode assembly with a proton conductive membrane. Their electrocatalytic efficiency toward hydrogen oxidation and hydrogen evolution reactions was studied in a self-made laboratory test cell by means of steady-state polarization curves and cell voltage measurements (U/j and U/pdiff characteristics). The achieved current density at a cell voltage of 0.5 V, the atmospheric pressure of the input hydrogen, and a temperature of 60 °C was more than 1.3 A cm-2. The registered increase in the cell voltage with the increasing pressure was only 0.05 mV bar-1. Comparative data with commercial E-TEK electrodes reveal the superior catalyst performance and essential cost reduction of the electrochemical hydrogen conversion on the sputtered Pt films.

Gram-positive bacteria covered bioanode in a membrane-electrode assembly for use in bioelectrochemical systems.

A novel strain of Gram-positive bacteria Paenibacillus profundus YoMME was recognized by sequencing of 16S rRNA gene and after that tested for exoelectrogenicity for the first time. It was found that at an applied potential of -0.195 V (vs. SHE) the bacteria are capable of generating electricity and forming electroactive biofilms for 3-4 days. A tendency for the decrease in double-layer capacitance and the increase in the charge transfer resistance during the maturation of the biofilm was established. The formed bioanodes were used as a part of a membrane-electrode assembly (MEA) together with a selected cathode (E-Tek) and a separator (Zirfon). The applicability of MEA with the bioanode was tested by operating a newly designed bioelectrochemical system in a microbial fuel cell (MFC) or microbial electrolysis cell (MEC) mode. A current density of 200 mA m-2 was generated by the MFC after the improvement of the cathodic reaction through facilitated air access. The Coulombic efficiency in different MFC runs ranged from 5.2 to 7.4%. It was also determined that 0.65 V applied cell voltage is appropriate for the operation of the cell in the electrolysis mode, during which a current density of 2-3 Am-2 was reached. This, along with the evolved gas on the cathode, shows that as an anodic biocatalyst P. profundus YoMME assists the electrolysis processes at a significantly lower voltage than the theoretical one (1.23 V) for water decomposition. The hydrogen production rate varied between 0.5 and 0.7 m3/m3d and the cathodic hydrogen recovery ranged from 49.5 to 61.5 %. The estimated energy efficiency based on the electricity input exceeds 100 %, which indicates that additional energy is being gained from the biotic oxidation of the available organics.

The glyoxylate pathway contributes to enhanced extracellular electron transfer in yeast-based biofuel cell.

This study provides a new insight into our understanding of yeast response to starvation conditions (sole acetate as carbon source) and applied polarization and offers important information about the role of the glyoxylate cycle in the carbohydrate synthesis and extracellular charge transfer processes in biofuel cells. The biosynthetic capabilities of yeast C. melibiosica 2491 and the up/down-regulation of the glyoxylate cycle are evaluated by modifying the cellular metabolism by feedback inhibition or carbohydrate presence and establishing the malate dehydrogenase activity and carbohydrate content together with the electric charge passed through bioelectrochemical system. 10mM malate leads to a decrease of the produced quantity of electricity with ca. 55%. At the same time, 24-times lower intracellular malate dehydrogenase activity is established. At polarization conditions the glyoxylate pathway is up-regulated and huge amount of malate is intra-converted into oxaloacetate. The yeasts are able to synthesize carbohydrates from acetate and a part of them is used for the electricity generation. It is recognized that the enhanced charge transfer in acetate fed yeast-based biofuel cell is implemented by secreted endogenous mediator and changes in the cellular surface redox activity depending on the addition of carbohydrate in the medium.

Hampering of the Stability of Gold Electrodes by Ferri-/Ferrocyanide Redox Couple Electrolytes during Electrochemical Impedance Spectroscopy.

In the past decades, numerous measurements have applied electrochemical impedance spectroscopy (EIS) in an electrode-electrolyte system consisting of gold electrodes and the redox couple potassium ferrocyanide/potassium ferricyanide (HCF). Yet these measurements are often hampered by false positive and negative results. Electrochemical impedance signals often display a nonlinear drift in electrolyte systems containing the HCF redox couple, which can mask the accuracy of the analysis. Thus, this Article aims to elucidate the stability and reliability of this particular electrode-electrolyte system. Here, different gold electrode cleaning treatments were compared with respect to adsorption and roughness of the surface of gold electrodes. They show substantial nonlinear long-term drifts of the charge-transfer resistance RD. In particular, the use of HCF-containing electrolytes causes adsorption and corrosion on the gold electrode surface, resulting in a nonlinear impedance behavior that depends on the incubation period as well as on electrolyte composition. Consequently, it is strongly recommended not to use HCF containing electrolytes in combination with gold electrodes.