硫氧基团修饰以增强NiFe-S/NF电极在碱性海水OER稳定性

蔡家阳; 曲德智; 苏萍萍; 何雄

硫氧基团修饰以增强NiFe-S/NF电极在碱性海水OER稳定性

广西科技大学　生物与化学工程学院, 广西糖资源绿色加工重点实验室, 柳州545000

基金项目: 国家自然科学基金青年科学基金项目(2209028))；广西科技基地和人才专项(AD21075032)；广西高校中青年教师科研基础能力提升项目(2021 KY0359)；研究生教育创新计划项目(GKYC202236)

详细信息

通讯作者:
曲德智，博士，副教授，研究方向：功能高分子材料，电催化材料，　E-mail：qudezhi199166@outlook.com

中图分类号: TB333; TQ426.82
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- 文章访问数: 31
- HTML全文浏览量: 25
- 被引次数: 0
出版历程
- 收稿日期: 2024-08-12
- 修回日期: 2024-09-06
- 录用日期: 2024-09-15
- 网络出版日期: 2024-09-27

Sulfur-oxygen group modification to enhance NiFe-S/NF electrode OER stability in alkaline seawater

College of Biological and Chemical Engineering, Guangxi University of Science and Technology, Guangxi Key Laboratory of Green Processing of Sugar Resources, Liuzhou545000

Funds: National Natural Science Foundation of China Youth Science Fund Project (2209028)); Guangxi Science and Technology Base and Talent Special Project (AD21075032); Guangxi Universities and Colleges Young and Middle-aged Teachers' Scientific Research Basic Ability Enhancement Project (2021 KY0359); and Graduate Student Education Innovation Plan Project (GKYC202236)

摘要

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。
- OER /
- 海水电解 /
- 硫化物 /
- 重建 /
- 阴离子屏蔽
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.
- OER /
- seawater electrolysis /
- sulfide /
- reconstruction /
- anionic shielding

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图 1 NiFe/泡沫镍(NF)和NiFe-S/NF的(a)XRD图和(b)拉曼光谱图

Figure 1. (a) XRD, and (b) Raman spectrum of NiFe/nickel foam (NF) and NiFe-S/NF

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图 2 NiFe/NF的(a，b)SEM图，NiFe-S/NF的(c，d)SEM，(e)TEM图，(f)HRTEM图和(g-j)元素分布图

Figure 2. (a, b) SEM images of NiFe/NF, (c, d) SEM images, (e) TEM image, (f) HRTEM image, and (g-j) elemental distributions of NiFe-S/NF

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图 3 NiFe/NF和NiFe-S/NF的(a)N₂吸附/解吸等温线和(b)孔径曲线。

Figure 3. (a) N₂ adsorption/desorption isotherms and (b) pore size profiles of NiFe/NF and NiFe-S/NF

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图 4 NiFe/NF和NiFe-S/NF CV激活前后的(a)Ni 2p，(b)Fe 2p光谱，NiFe-S/NFCV激活前后的(c)S 2p和(d)O 1 s光谱

Figure 4. (a) Ni 2p, (b) Fe 2p spectra of NiFe/NF and NiFe-S/NF before and after CV activation, (c) S 2p and (d) O 1 s spectra before and after NiFe-S/NFCV activation

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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C_dl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) C_dl plot of all samples.

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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

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图 7 NiFe/NF和NiFe-S/NF在不同电位下的拉曼光谱图

Figure 7. Raman spectra of (a) NiFe/NF and (b) NiFe-S/NF at different potentials

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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 efficiency	References
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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