| Citation: |
CAI Jiayang, QU Dezhi, SU Pingping, et al. Sulfur-oxygen group modification to enhance NiFe-S/NF electrode OER stability in alkaline seawater[J]. Acta Materiae Compositae Sinica.
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The development and utilisation of hydrogen energy is of great significance in alleviating the energy crisis. Hydrogen production from electrolytic water is a stable and sustainable technology.However, the actual potential for initiating the electrolytic water reaction is affected by the four-electron transfer in the anodic oxygen evolution reaction (OER), which is much larger than the theoretical decomposition potential of 1.23 V. Therefore, the development of a durable and active electrocatalyst for the reduction of the additional electrical energy consumption for water decomposition is essential. In particular, an electrocatalyst that can exhibit excellent catalytic performance in both seawater and freshwater. Because the earth has much more seawater than fresh water, it is an inexhaustible resource. However, the complex ion environment in seawater is the bottleneck of hydrogen production in seawater. The core difficulty lies in the chlorination evolution reaction (CER) triggered by high concentration Cl on the anode surface, which can easily cause the local PH drop and damage the electrode activity and stability. Therefore, improving the activity, selectivity and stability of the anode has become the primary task of seawater decomposition. Precious metals are ideal for high performance OER catalysts, but their scarcity limits large-scale applications. In recent years, transition metal sulfides have been regarded as one of the most promising OER electrocatalysts, whose advantages mainly lie in their higher electrical conductivity and chemical stability.
NiFe-S/NF was synthesised using a simple one-step hydrothermal method, which can be used for direct seawater electrolysis and exhibits excellent OER catalytic performance and high durability.
OER electrochemical performance tests were carried out at 1 M KOH, and it was found that NiFe-S/NF exhibited outstanding OER performance, requiring 237 mV to reach 100 mA/cm, with a Tafel slope of 34.2 mV/dec, an Rct value of 0.157 Ω and a Cdl value of 3.16 mF/cm, and possessed a fast electron transfer efficiency and reaction kinetics, high conductivity and maximum electrochemically active area. This is attributed to the oxidation of sulphides in NiFe-S/NF after CV activation to thioredoxin anions that can have a shielding effect on Cl and the production of a large number of high-valent metal ions (NiOOH and Fe). These sulfur-oxygen anions facilitate the OER process as well as improve the lifetime of the electrode. In addition, NiFe-S/NF easily reaches 100 mA/cm in alkaline fresh water (1 mol/L KOH + ultrapure water) and seawater (1 mol/L KOH + seawater) requiring 237 and 248 mV, respectively. compared to the rapid weakening of NiFe/NF in alkaline seawater, NiFe-S/NF in alkaline fresh water shows only a slight decrease (11 mV) and at the same time exhibits good stability in structure and performance (oxygen precipitation efficiency remains 92.1% after 100 h of electrolysis at 100 mA/cm). This result suggests the feasibility of a strategy to enhance the seawater electrolysis stability of the catalysts by utilising the sulphur-oxygen anions formed after the electrochemical reconstruction of sulphides.Conclusions: XRD, Raman and TEM results showed that the one-step hydrothermal synthesis of NiFe-S/NF catalysts was successful.SEM and BET assays revealed that the introduction of S could increase the specific surface area and pore size of NiFe-S/NF catalysts, and these features were favourable for providing more active sites, and at the same time were helpful for coping with the clogging of active sites by precipitates and microorganisms in seawater. The results by Raman and XPS showed that the surface reconstruction of sulphide occurs after CV activation, and the sulphur in the sulphide is oxidised to form sulphur-oxygen anions, which are subsequently adsorbed on the surface of the electrodes and have a modifying effect on the electrodes. These anions can, on the one hand, promote the generation of high-valent metal ions, thus accelerating the catalytic efficiency of OER; on the other hand, they can also have a shielding effect on Cl, avoiding the occurrence of CER and improving the service life of the electrode. This work provides a simple, economical and highly feasible idea for electrolysis of seawater for hydrogen production.
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