Chlorine redox chemistry is not rare in biology

Chlorine is abundant in cells and biomolecules, yet the biology of chlorine oxidation and reduction is poorly understood. Some bacteria encode the enzyme chlorite dismutase (Cld), which detoxifies chlorite (CIO2-) by converting it to chloride (Cl-) and molecular oxygen (O2). Cld is highly specific for chlorite and aside from low hydrogen peroxide activity has no known alternative substrate. Here, we reasoned that because chlorite is an intermediate oxidation state of chlorine, Cld can be used as a biomarker for oxidized chlorine species in microorganisms and microbial habitats. Cld was abundant in metagenomes from soils and freshwater to water treatment systems. About 5% of bacterial and archaeal genera contain an organism encoding Cld in its genome, and within some genera Cld is nearly conserved. Cld has been subjected to extensive horizontal gene transfer, suggesting selection by chlorite is episodic yet strong. Cld was also used as a biomarker to predict genes related to chlorine redox chemistry. Genes found to have a genetic association with Cld include known genes for responding to reactive chlorine species and uncharacterized genes for transporters, regulatory elements, and putative oxidoreductases that present targets for future research. Cld was repeatedly co-located in genomes with genes for enzymes that can inadvertently reduce perchlorate (CIO4-) or chlorate (CIO3-), confirming that in nature (per)chlorate reduction does not only occur in specialized anaerobic respiratory metabolisms. The presence of Cld in genomes of obligate aerobes without such enzymes suggested that chlorite, like hypochlorous acid (HOCl), might be formed by oxidative processes within natural habitats. In summary, the comparative genomics of Cld has provided an atlas for a deeper understanding of chlorine oxidation and reduction reactions that are an underrecognized feature of biology.

Common-Ion Effect Triggered Highly Sustained Seawater Electrolysis with Additional NaCl Production

Developing efficient seawater-electrolysis system for mass production of hydrogen is highly desirable due to the abundance of seawater. However, continuous electrolysis with seawater feeding boosts the concentration of sodium chloride in the electrolyzer, leading to severe electrode corrosion and chlorine evolution. Herein, the common-ion effect was utilized into the electrolyzer to depress the solubility of NaCl. Specifically, utilization of 6 M NaOH halved the solubility of NaCl in the electrolyte, affording efficient, durable, and sustained seawater electrolysis in NaCl-saturated electrolytes with triple production of H2, O2, and crystalline NaCl. Ternary NiCoFe phosphide was employed as a bifunctional anode and cathode in simulative and Ca/Mg-free seawater-electrolysis systems, which could stably work under 500 mA/cm2 for over 100 h. We attribute the high stability to the increased Na+ concentration, which reduces the concentration of dissolved Cl- in the electrolyte according to the common-ion effect, resulting in crystallization of NaCl, eliminated anode corrosion, and chlorine oxidation during continuous supplementation of Ca/Mg-free seawater to the electrolysis system.