NiMoN催化电极材料的制备及其电解海水制氢性能

doi:10.12422/j.issn.1006-396X.2023.02.001

摘要/Abstract

摘要：

以四水合钼酸铵为钼源、六水合硝酸镍为镍源，采用水热法在泡沫镍基底上制备前驱体NiMoO₄纳米棒阵列，然后通过热氮化法得到具有棒状阵列结构的NiMoN催化电极材料（简称NiMoN）。采用X射线衍射和扫描电子显微镜对NiMoN的物相结构和表面形貌进行表征；通过线性扫描伏安法、塔菲尔斜率、电化学阻抗谱等电化学测试手段，对NiMoN的半反应析氧（OER）、析氢（HER）以及全解水性能进行测试。结果表明，在碱性淡水和碱性模拟海水电解液中，NiMoN均显示了突出的OER活性，产生100.00 mA/cm²的电流密度分别需要293、340 mV的过电位；NiMoN?9具有较好的HER活性，在两种电解液中产生100.00 mA/cm²的电流密度分别需要361、400 mV的过电位；NiMoN?9具有良好的全解水性能，在两种电解液中产生100.00 mA/cm²的电流密度所需电压分别为2.016、2.032 V，且可稳定运行55 h以上。

关键词: 镍钼氮化物, 催化电极材料, 电解海水, 析氢反应, 析氧反应

Abstract:

The precursor NiMoO₄ nanorod arrays were prepared on nickel foam by a hydrothermal method using ammonium molydate tetrahydrate [(NH₄)₆Mo₇O₂₄·4H₂O] as the Mo source and nickel nitrate hexahydrate [Ni(NO₃)₂·6H₂O] as the Ni source, and subsequently were nitrogenized via a thermal treatment to obtain the NiMoN with rod?like array structure.The phase structure and surface morphology of the catalytic electrode material were characterized by X?ray diffraction (XRD) and scanning electron microscopy (SEM).Besides,the half?reaction oxygen evolution reaction (OER),hydrogen evolution reaction (HER),and overall water electrolysis performance of the material were evaluated by adopting various electrochemical characterizations,including linear scanning voltammetry (LSV),Tafel slope, and electrochemical impedance spectroscopy (EIS).The test results show that the NiMoN?9 catalytic electrode material has both high OER and HER activities.The OER overpotentials for this material to reach 100.00 mA/cm² are only 293 mV and 340 mV respectively in alkaline fresh water and alkaline simulated seawater,while the corresponding HER overpotentials are 361 mV and 400 mV.In addition,the NiMoN?9 material also exhibits good activities in both water electrolysis and seawater electrolysis with the cell voltages of 2.016 V and 2.032 V respectively to obtain 100.00 mA/cm² as well as robust stabilities over 55 h.

Key words: NiMoN, Catalytic electrode material, Seawater electrolysis, Hydrogen evolution reaction, Oxygen evolution reaction

中图分类号:

TQ151

刘梦珊, 孟超, 胡涵, 吴明铂. NiMoN催化电极材料的制备及其电解海水制氢性能[J]. 石油化工高等学校学报, 2023, 36(2): 1-9.

Mengshan Liu, Chao Meng, Han Hu, Mingbo Wu. Preparation of NiMoN Catalytic Electrode Material for Hydrogen Production via Seawater Electrolysis[J]. Journal of Petrochemical Universities, 2023, 36(2): 1-9.

图/表 11

图1 NiMoN的合成流程示意图

Fig.1 Schematic illustration of the synthesis of NiMoN

图2 NiMoN?X和Ni3N的XRD图谱

Fig.2 XRD patterns of NiMoN?X and Ni3N

图3 不同催化电极材料的SEM照片

Fig.3 SEM photos of different catalytic electrode materials

图4 NiMoN?9的TEM照片

Fig.4 TEM photos of NiMoN?9

图5 不同水热反应时间制备的NiMoN?X和对比样Ni3N在碱性淡水中的OER性能和电化学阻抗谱

Fig.5 OER performance and electrochemical impedance spectroscopy of NiMoN?X and contrast Ni3N prepared at different hydrothermal reaction time in alkaline fresh water

图6 NiMoN?9在碱性淡水和碱性模拟海水中的OER性能

Fig.6 OER performance of NiMoN?9 in alkaline fresh water and alkaline simulated seawater

图7 不同催化电极材料在碱性淡水中的HER性能

Fig.7 HER performance of different catalytic electrode materials in alkaline fresh water

图8 NiMoN?9在碱性淡水和碱性模拟海水中的HER性能和Tafel斜率曲线

Fig.8 HER performance and Tafel slope curves of NiMoN?9 in alkaline fresh water and alkaline simulated seawater

图9 全解水/海水性能测试示意图

Fig.9 Schematic diagram of total solution water/seawater performance test

图10 不同催化电极材料在碱性淡水和碱性模拟海水中的全解水性能曲线

Fig.10 Performance curves of different catalytic electrode materials for total hydrolysis of water in alkaline fresh water and alkaline simulated seawater

图11 NiMoN?9在碱性淡水和碱性模拟海水中的稳定性及SEM图像

Fig.11 The stability of NiMon?9 in alkaline fresh water and alkaline simulated seawater and SEM image

参考文献 33

1	Jain I P. Hydrogen the fuel for 21st century［J］.International Journal of Hydrogen Energy，2009，34（17）：7368⁃7378.
2	Sdanghi G，Maranzana G，Celzard A，et al.Review of the current technologies and performances of hydrogen compression for stationary and automotive applications［J］.Renewable and Sustainable Energy Reviews，2019，102：150⁃170.
3	Ismagilov F R，Vavilov V E，Miniyarov A H，et al.Super high⁃speed electric motor with amorphous magnetic circuit for the hydrogen fuel cell air supply system［J］.International Journal of Hydrogen Energy，2018，43（24）：11180⁃11189.
4	Dufour J，Serrano David P，Gálvez Jose L，et al.Hydrogen production from fossil fuels：Life cycle assessment of technologies with low greenhouse gas emissions［J］.Energy & Fuels，2011，25（5）：2194⁃2202.
5	Sanz O，Velasco I，Pérez⁃miqueo I，et al.Intensification of hydrogen production by methanol steam reforming［J］.International Journal of Hydrogen Energy，2016，41（10）：5250⁃5259.
6	Balat M.Possible methods for hydrogen production［J］.Energy Sources，Part A：Recovery，Utilization， and Environmental Effects，2008，31（1）：39⁃50.
7	韩桥，宋健，杨占旭.NiMoP/C复合材料的制备及其电化学析氢性能［J］.石油化工高等学校报，2022，35（1）：1⁃9.
	Han Q，Song J，Yang Z X.Preparation of NiMoP/C composite material and electrocatalytic hydrogen evolution performance［J］.Journal of Petrochemical Universities，2022，35（1）：1⁃9.
8	Sun Z X，Wang G J，Koh S W，et al.Solar⁃driven alkaline water electrolysis with multifunctional catalysts［J］.Advanced Functional Materials，2020，30（27）：2002138.
9	Gao F Y，Yu P C，Gao M R.Seawater electrolysis technologies for green hydrogen production：Challenges and opportunities［J］.Current Opinion in Chemical Engineering，2022，36：100827.
10	Angelakis A N，Valipour M，Choo K H，et al.Desalination：From ancient to present and future［J］.Water，2021，13（16）：2222.
11	Jiang S Q，Suo H L，Zhang T，et al.Recent advances in seawater electrolysis［J］.Catalyts，2022，12（2）：123.
12	Asghari E，Abdullah M I，Foroughi F，et al.Advances，opportunities，and challenges of hydrogen and oxygen production from seawater electrolysis：An electrocatalysis perspective［J］.Current Opinion in Electrochemistry，2022，31：100879.
13	Zhou Q，Liao L L，Zhou H Q，et al.Innovative strategies in design of transition metal⁃based catalysts for large⁃current⁃density alkaline water/seawater electrolysis［J］.Materials Today Physics，2022，26：100727.
14	Chen L W，Liang H W.Ir⁃based bifunctional electrocatalysts for overall water splitting［J］.Catalysis Science & Technology，2021，11（14）：4673⁃4689.
15	Wang H，Li J M，Li K，et al.Transition metal nitrides for electrochemical energy applications［J］.Chemical Society Reviews，2021，50（2）：1354⁃1390.
16	Meng Z H，Zheng S H，Luo R，et al.Transition metal nitrides for electrocatalytic application：Progress and rational design［J］.2022，12（15）：2660.
17	Sun K Y，Qiao F，Yang J，et al.Fluff spherical Co⁃Ni₃S₂/NF for enhanced hydrogen evolution［J］.International Journal of Hydrogen Energy，2022，47（65）：27986⁃27995.
18	Gao M，Chen L L，Zhang Z H，et al.Interface engineering of the Ni（OH）₂⁃Ni₃N nanoarray heterostructure for the alkaline hydrogen evolution reaction［J］.Journal of Materials Chemistry A，2018，6（3）：833⁃836.
19	Wang B R，Jiao S H，Wang Z S，et al.Rational design of NiFe LDH@Ni₃N nano/microsheet arrays as bifunctional electrocatalyst for overall water splitting［J］.Journal of Materials Chemistry A，2020，8（33）：17202⁃17211.
20	Wu T，Song E H，Zhang S N，et al.Engineering metallic heterostructure based on Ni₃N and 2M⁃MoS₂ for alkaline water electrolysis with industry⁃compatible current density and stability［J］.Advanced Materials，2022，34（9）：2108505.
21	Zang Y P，Niu S W，Wu Y S，et al.Tuning orbital orientation endows molybdenum disulfide with exceptional alkaline hydrogen evolution capability［J］.Nature Communications，2019，10（1）：1217.
22	Yao N，Li P，Zhou Z R，et al.Synergistically tuning water and hydrogen binding abilities over Co₄N by Cr doping for exceptional alkaline hydrogen evolution electrocatalysis［J］.Advanced Energy Materials，2019，9（41）：1902449.
23	Ning M H，Zhang F H，Wu L B，et al.Boosting efficient alkaline fresh water and seawater electrolysis via electrochemical reconstruction［J］.Energy & Environmental Science，2022，15（9）：3945⁃3957.
24	Yu L，Zhu Q，Song S W，et al.Non⁃noble metal⁃nitride based electrocatalysts for high⁃performance alkaline seawater electrolysis［J］.Nature Communications，2019，10（1）：5106.
25	Gao X R，Liu X M，Zang W J，et al. Synergizing in⁃grown Ni₃N/Ni heterostructured core and ultrathin Ni₃N surface shell enables self⁃adaptive surface reconfiguration and efficient oxygen evolution reaction［J］.Nano Energy，2020，78：105355.
26	Lee S Y，Kim I S，Cho H S，et al.Resolving potential⁃dependent degradation of electrodeposited Ni（OH）₂ catalysts in alkaline oxygen evolution reaction （OER）：In situ XANES studies［J］.Applied Catalysis B：Environmental，2021，284：119729.
27	Sun H，Sun J K，Song Y Y，et al.Nickel⁃cobalt hydrogen phosphate on nickel nitride supported on nickel foam for alkaline seawater electrolysis［J］.ACS Applied Materials & Interfaces，2022，14（19）：22061⁃22070.
28	Zhao Y Q，Jin B，Vasileff A，et al.Interfacial nickel nitride/sulfide as a bifunctional electrode for highly efficient overall water/seawater electrolysis［J］.Journal of Materials Chemistry A，2019，7（14）：8117⁃8121.
29	Wang C Z，Zhu M Z，Cao Z Y，et al.Heterogeneous bimetallic sulfides based seawater electrolysis towards stable industrial⁃level large current density［J］.Applied Catalysis B：Environmental，2021，291：120071.
30	Li R P，Li Y Q，Yang P X，et al.Synergistic interface engineering and structural optimization of non⁃noble metal telluride⁃nitride electrocatalysts for sustainably overall seawater electrolysis［J］.Applied Catalysis B：Environmental，2022，318：121834.
31	Wang Q，Zhao H Y，Li F M，et al.Mo⁃doped Ni₂P hollow nanostructures：Highly efficient and durable bifunctional electrocatalysts for alkaline water splitting［J］.Journal of Materials Chemistry A，2019，7（13）：7636⁃7643.
32	Ge R Y，Zhao J L，Huo J J，et al.Multi⁃interfacial Ni/Mo₂C ultrafine hybrids anchored on nitrogen⁃doped carbon nanosheets as a highly efficient electrocatalyst for water splitting［J］.Materials Today Nano，2022，20：100248.
33	Li M X，Zhu Y，Wang H Y，et al.Ni strongly coupled with Mo₂C encapsulated in nitrogen⁃doped carbon nanofibers as robust bifunctional catalyst for overall water splitting［J］.Energy & Environmental，2019，9（10）：1803185.

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