Sulfur-oxygen group modification to enhance NiFe-S/NF electrode OER stability in alkaline seawater
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摘要: 直接电解海水是一种更绿色、可持续性更高的氢能生产源途径。然而海水电解需要面临海水中有害离子的毒害,特别是海水中高浓度Cl−引发的析氯反应(CER),会对阳极析氧反应(OER)产生干扰。因此采用有效的Cl−屏蔽策略来提高催化剂的OER性能和长期电解寿命,是大范围开发海水制氢关键所在。本文采用一步水热硫化法在泡沫镍(NF)基底上成功制备可用于海水电解的NiFe-S/NF电催化剂。值得注意的是,NiFe-S/NF在碱性淡水(1 mol/L KOH +超纯水)和海水(1 mol/L KOH +海水)中分别需要237和248 mV便可轻松达到100 mA/cm2,并具有超过100 h的海水电解耐久度(100 mA/cm2)。这得益于硫化物中的硫在OER过程中氧化为硫氧阴离子,这些阴离子会吸附在电极表面,一方面加速电催化剂的OER过程,另一方面通过静电斥力形成Cl−排斥层,从而提升催化剂性能和寿命。本研究为高效、经济开发海水制氢提供了可行性较高的策略。Abstract: Direct electrolysis of seawater is a greener and more sustainable route to a source of hydrogen energy production. However, seawater electrolysis needs to face the toxicity of harmful ions in seawater, especially the interference of chlorine evolution reaction (CER) with anode oxygen evolution reaction (OER) triggered by high concentration of Cl− in seawater. Therefore the adoption of effective Cl− shielding strategies to improve the OER performance and long-term electrolysis lifetime of the catalysts is crucial for the wide-scale development of seawater hydrogen production. In this work, NiFe-S/NF electrocatalyst for seawater electrolysis was successfully prepared on nickel foam (NF) substrates via one-step hydrothermal vulcanisation. Notably, NiFe-S/NF easily reaches 100 mA/cm2 in alkaline freshwater (1 mol/L KOH + ultrapure water) and seawater (1 mol/L KOH + Seawater) requiring 237 and 248 mV, respectively, and has a seawater electrolysis endurance of more than 100 h (100 mA/cm2). This is attributed to the oxidation of sulphur in sulphide to sulphur-oxygen anions during the OER process, which are adsorbed on the surface of the electrode, accelerating the OER process of the electrocatalyst on the one hand, and forming a Cl− shielding layer through electrostatic repulsion on the other hand, thus enhancing the performance and lifetime of the catalyst. This study provides a highly feasible strategy for the efficient and economic development of seawater hydrogen production.
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Key words:
- OER /
- seawater electrolysis /
- sulfide /
- reconstruction /
- anionic shielding
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图 5 NF,NiFe/NF和NiFe-S/NF样品的(a)LSV极化曲线图,(b)10 mA/cm2、100 mA/cm2下的过电位性能图,(c)Tafel斜率图,(d)EIS图,(e)NiFe-S/NF在不同扫速下的CV图和(f)所有样品的Cdl图。
Figure 5. (a) LSV polarization curves, (b) overpotential at 10 and 100 mA/cm2, (c) Tafel slope, (d) electrochemical impedance test of NF, NiFe/NF and NiFe-S/NF, (e) CV curves of NiFe-S/NF at different scan rates, and (f) Cdl plot of all samples.
图 6 NiFe/NF和NiFe-S/NF在碱性淡水/海水中的(a)LSV极化曲线,(b)法拉第析氧效率,(c)稳定性测试图,(d)性能与稳定性结果图,NiFe-S/NF海水稳定性测试后的(e)SEM图和(f)XRD图
Figure 6. (a) LSV polarization curves, (b) Faraday oxygen precipitation efficiency, (c) stability test plots, (d) performance versus stability results plots for NiFe/NF and NiFe-S/NF in alkaline freshwater/seawater, (e) SEM and (f) XRD of NiFe-S/NF after seawate stability test
表 1 NiFe-S/NF与最近报道的催化剂对海水OER催化性能比较
Table 1. Comparison of NiFe-S/NF and recently reported catalysts for seawater OER performance
Catalyst electrolyte overpotential stability oxygen evolution
efficiencyReferences NiFe-S/NF 1 mol/L KOH + Seawater 248 mV at 100 mA/cm2 100 h at 100 mA/cm2 92.1% This work S-NiFe-Pi/NFF 1 mol/L KOH + Seawater 450 mV at 100 mA/cm2 100 h at 500 mA/cm2 86.6% [33] MnOx/NiFe-LDH/NF 1 mol/L KOH + Seawater 276 mV at 100 mA/cm2 70 h at 50 mA/cm2 About 90% [36] CoPx@FeOOH 1 mol/L KOH + Seawater 283 mV at 100 mA/cm2 80 h at 500 mA/cm2 92.3% [37] NiFeCo-LDH 1 mol/L KOH + Seawater 304 mV at 100 mA/cm2 80 h at 100 mA/cm2 94% [38] Fe-Ni(OH)2/Ni3S2 @NF 1 mol/L KOH + 0.5 mol/L NaCl 320 mV at 10 mA/cm2 27 h at 100 mA/cm2 Slight decline [39] BZ-NiFe-LDH/CC 1 mol/L KOH Seawater 300 mV at 100 mA/cm2 100 h at 0.5 A/cm2 72% [40] (NiFeCoV)S2 1 mol/L KOH + Seawater 299 mV at 100 mA/cm2 50 h at 100 mA/cm2 Slight decline [10] Fe-Co-S/Cu2O/Cu 1 mol/L KOH + Seawater 440 mV at 200 mA/cm2 70 h at 100 mA/cm2 70% [41] Notes: S-NiFe-Pi/NFF is S-modified NiFe-phosphate hierarchical hollow microspheres; NFF is NiFe foam; MnOx/NiFe-LDH/NF is the ultrathin MnOx film-covered NiFe-layered double-hydroxide nanosheet array; NF is nickel foam; BZ is benzoate intercalation; CC is carbon cloth; -0.05 M is 0.05 mmol/L thiourea. -
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