NiFeOOH-Co₉S₈-Intercalated Nanostructure Arrays for Energy-Efficient H₂ Production and Sulfion Oxidation at High Current Density

Abstract

Though electrocatalysts displaying efficacy for the hydrogen evolution reaction (HER) or sulfion oxidation reaction (SOR) individually are available in the literature, systems exhibiting proficiency toward the HER and SOR together are desirable to produce H2 in a robustly energy-efficient manner. Furthermore, simultaneous facile growth and intercalation of multiple nanocatalyst systems to achieve the above objective are synthetically challenging. Herewith, the reactivity preferences of Lewis acid (FeCl3) and salt [Co­(NO3)2] are utilized to longitudinally grow NiFeOOH-Co9S8-n intercalated nanostructure arrays of varied Fe:Co ratios on Nickel foam using a one-step procedure at low temperature (50 °C). The NiFeOOH-Co9S8-n exhibit bifunctionality and H2 production at a relatively high j value of 1000 mA/cm2 is realized at a low overall potential (SOR + HER) value of 0.84 V in NaOH (1.0 M)-Na2S (1.0 M). The efficiency of the electrode enabled the SOR j value to reach 1000 mA/cm2 at 0.72 V in 1.0 M Na2S solution in the absence of NaOH. The density functional theory analysis revealed that the oxide doping of the Co9S8 facilitated by the FeOOH-Co9S8 intercalation promoted the electrocatalytic activity. The nanocatalyst promotes highly energy-efficient and sustainable H2 production, where a j value of 100 mA/cm2 under the electrolyzer mode is realized at an unprecedented potential of 0.44 V (iR-uncorrected) and ultralow power consumption (11.8 kW h/kg H2), which is minimum among reported systems suggesting its viability toward commercial production of H2 in future.

Eggshell membrane-derived metal sulfide catalysts for seawater splitting

“…2b, the Raman spectrum of Co 9 S 8 /ESM-900 shows bands of 461, 506, and 664 cm −1 , which can be assigned to the E 2g , F 2g , and A 1g vibrational modes of Co 9 S 8 , respectively. 45,48,49 In contrast, the peak positions of Co 8 FeS 8 /ESM-900 are positively shifted, manifesting the changes in the electronic structures after Fe doping. The introduction of iron into the Co 9 S 8 lattice facilitates the charge transfer and increases its polarizability, leading to a blue shift in the Raman spectra.…”