电沉积制备多孔Ni-Fe-Sn合金电极及其析氧性能
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摘要
采用直流电沉积法在铜箔表面合成了多孔结构的Ni-Fe-Sn合金,用扫描电子显微镜、X射线能谱仪和X射线衍射仪对合金的微观组织形貌和相态进行了表征,用电化学工作站测试了合金电极在碱性环境中的析氧性能。结果表明,Ni-Fe-Sn合金电极主要由Ni3Sn2和FeNi3相组成,电极表面形成了多孔结构。在30wt%KOH溶液中,Ni-Fe-Sn合金的析氧过电位仅为261 mV(电流密度10 mA/cm2),Tafel斜率为69.9 mV/dec。电极在10 mA/cm2电流密度下能稳定工作12 h以上,具有良好的电化学稳定性。
Oxygen evolution reaction(OER) is one of the core reactions in the field of electrochemistry and subjected to a lot of studies for many years. But it is still one of the most complicated electrochemical processes and of practical importance. Specifically, the development of efficient and low-cost nonprecious catalyst for the OER is still a key challenge for the renewable energy research community. In this study, electrodeposited porous nickel-iron-tin(Ni-Fe-Sn) alloy on Cu foil as an efficient OER electrocatalyst inalkaline medium was introduced. The obtained alloy was analyzed by scanning electron microscopy(SEM) with energy dispersive spectroscopy(EDS), X-ray diffraction(XRD), respectively. The OER electrocatalytic performance of Ni-Fe-Sn alloy was investigated by linear sweep voltammetry(LSV), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), and chronoamperometry(CP) in 30 wt% KOH solution. In addition, the Ni-Fe-Sn alloy was further tested as anodes for alkaline water electrolysis during at least 12 h with good stability. The results showed that the obtained Ni-Fe-Sn alloy was composed of Ni3 Sn2 and FeNi3 phases. The EDS result of Ni-Fe-Sn alloy showed the existence of three elements(Fe, Ni and Sn). SEM images displayed that the surface of the Ni-Fe-Sn alloy had porous structure, which provided more active sites for the OER. OER measurements demonstrated that the Ni-Fe-Sn alloy was highly effective for the OER with a low overpotential of 261 mV to reach 10 mA/cm2 and a small Tafel slope of 69.9 mV/dec. The excellent electrocatalytic activity, long-term stability and facile preparation method enabled Ni-Fe-Sn alloy to be a viable candidate for its widespread use in various water-splitting technologies. The better OER activity of Ni-Fe-Sn alloy in comparison to Ni-Fe alloy originated from higher electrochemical active surface area(ECSA) and the improved mass/electron transport capability due to synergetic effect between Ni, Fe and Sn.
Oxygen evolution reaction(OER) is one of the core reactions in the field of electrochemistry and subjected to a lot of studies for many years. But it is still one of the most complicated electrochemical processes and of practical importance. Specifically, the development of efficient and low-cost nonprecious catalyst for the OER is still a key challenge for the renewable energy research community. In this study, electrodeposited porous nickel-iron-tin(Ni-Fe-Sn) alloy on Cu foil as an efficient OER electrocatalyst inalkaline medium was introduced. The obtained alloy was analyzed by scanning electron microscopy(SEM) with energy dispersive spectroscopy(EDS), X-ray diffraction(XRD), respectively. The OER electrocatalytic performance of Ni-Fe-Sn alloy was investigated by linear sweep voltammetry(LSV), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), and chronoamperometry(CP) in 30 wt% KOH solution. In addition, the Ni-Fe-Sn alloy was further tested as anodes for alkaline water electrolysis during at least 12 h with good stability. The results showed that the obtained Ni-Fe-Sn alloy was composed of Ni3 Sn2 and FeNi3 phases. The EDS result of Ni-Fe-Sn alloy showed the existence of three elements(Fe, Ni and Sn). SEM images displayed that the surface of the Ni-Fe-Sn alloy had porous structure, which provided more active sites for the OER. OER measurements demonstrated that the Ni-Fe-Sn alloy was highly effective for the OER with a low overpotential of 261 mV to reach 10 mA/cm2 and a small Tafel slope of 69.9 mV/dec. The excellent electrocatalytic activity, long-term stability and facile preparation method enabled Ni-Fe-Sn alloy to be a viable candidate for its widespread use in various water-splitting technologies. The better OER activity of Ni-Fe-Sn alloy in comparison to Ni-Fe alloy originated from higher electrochemical active surface area(ECSA) and the improved mass/electron transport capability due to synergetic effect between Ni, Fe and Sn.
引文
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[16]武刚,李宁,戴长松,等.阳极电沉积Co-Ni混合氧化物在碱性介质中的电催化析氧性能[J].催化学报,2004,25(4):319-325.Wu G,Li N,Dai C S,et al.Anodically electrodeposited cobalt-nickel mixed oxide electrodes for oxygen evolution[J].Chinese Journal of Catalysis,2004,25(4):319-325.
[17]Guan C,Xiao W,Wu H J,et al.Hollow Mo-doped CoP nanoarrays for efficient overall water splitting[J].Nano Energy,2018,48:73-80.
[18]Fang L,Jiang Z Q,Xu H T,et al.Crystal-plane engineering of NiCo2O4 electrocatalysts towards efficient overall water splitting[J].Journal of Catalysis,2018,357:238-246.
[2]Jun C,Hongmei Y.Water electrolysis based on renewable energy for hydrogen production[J].Chinese Journal of Catalysis,2018,39:390-394.
[3]吴靓,郭小花,徐阳,等.镍基析氢电极在碱性溶液中析氢行为[J].中国有色金属学报,2018,28(2):309-318.Wu L,Guo X H,Xu Y,et al.Electrochemical performance of porous Ni-based electrodes for hydrogen evolution reaction in alkaline solution[J].The Chinese Journal of Nonferrous Metals,2018,28(2):309-318.
[4]冉敏,吴艺辉,何捍卫.铁元素对镍基Ni-S合金涂层电极析氢性能的影响[J].粉末冶金材料科学与工程,2018,23(1):63-69.Ran M,Wu Y H,He H W.Effect of Fe on hydrogen evolution performance of Ni-based Ni-S alloy coating electrode[J].Materials Science and Engineering of Powder Metallurgy,2018,23(1):63-69.
[5]Wu A P,Xie Y,Ma H,et al.Integrating the active OER and HERcomponents as the heterostructures for the efficient overall water splitting[J].Nano Energy,2018,44:353-363.
[6]庄林.结晶度调控硼酸镍电催化析氧性能[J].物理化学学报,2017,33(8):1501-1502.Zhuang L.Crystallinity modulates the electrocatalytic activity of nickel(II)borate for water oxidation[J].Acta Physico-Chimica Sinica,2017,33(8):1501-1502.
[7]何杨华,徐金铭,王发楠,等.Ni-Fe基析氧阳极材料的研究进展[J].化工进展,2016,35(7):2057-2062.He Y H,Xu J M,Wang F N,et al.Recent advances in Ni-Fe-based electrocatalysts for oxygen evolution reaction[J].Chemical Industry and Engineering Progress,2016,35(7):2057-2062.
[8]Harshad A B,Amol R J,Hern K.Facile synthesis of bicontinuous Ni3Fe alloy for efficient electrocatalytic oxygen evolution reaction[J].Journal of Alloys and Compounds,2017,726:875-884.
[9]Michele O,Alberto M,Giacomo A,et al.On the effect of Sn-doping in hemiatite anodes for oxygen evolution[J].Electrochimica Acta,2016,214:345-353.
[10]Mani V,Anantharaj S,Soumyaranjan M,et al.Iron hydroxyphosphate and Sn-incorporated inon hydroxyphosphate:efficient and stable electrocatalysts for oxygen evolution reaction[J].Catalysis Science&Technology,2017,7:5092-5104.
[11]严朝雄,王菊平,徐志花,等.pH值对电沉积NiFe合金形貌及析氢性能的影响[J].黄冈师范学院学报,2013,33(6):26-29.Yan Z X,Wang J P,Xu Z H,et al.Influence of pH on the microstructure and electrochemical hydrogen evolution of NiFe alloy[J].Journal of Huanggang Normal University,2013,33(6):26-29.
[12]Liang J Q,Wu Y H,Zhang H A,et al.One-step electrodeposition synthesis of a Ni-Fe-Sn electrode for hydrogen production in alkaline solution[J].Materials Letters,2018,227:124-127.
[13]黄红菱,于畅,黄华伟,等.生物质衍生炭负载金属催化剂的制备及析氧性能研究[J].新型炭材料,2017,32(6):557-563.Huang H L,Yu C,Huang H W,et al.Synthesis of biomass-derived carbon sheets decorated with metal nanoparticles and their catalytic performance in the oxygen evolution reaction[J].New Carbon Materials,2017,32(6):557-563.
[14]Chen Z J,Kang Q,Cao G X,et al.Study of cobalt boride-derived electrocatalysts for overall water splitting[J].International Journal of Hydrogen Energy,2018,43(12):6076-6087.
[15]Fan Q,Zhao Z H,Alam M K,et al.Trimetallic NiFeMo for overall electrochemical water splitting with a low cell voltage[J].ACSEnergy Letters,2018,3(3):546-554.
[16]武刚,李宁,戴长松,等.阳极电沉积Co-Ni混合氧化物在碱性介质中的电催化析氧性能[J].催化学报,2004,25(4):319-325.Wu G,Li N,Dai C S,et al.Anodically electrodeposited cobalt-nickel mixed oxide electrodes for oxygen evolution[J].Chinese Journal of Catalysis,2004,25(4):319-325.
[17]Guan C,Xiao W,Wu H J,et al.Hollow Mo-doped CoP nanoarrays for efficient overall water splitting[J].Nano Energy,2018,48:73-80.
[18]Fang L,Jiang Z Q,Xu H T,et al.Crystal-plane engineering of NiCo2O4 electrocatalysts towards efficient overall water splitting[J].Journal of Catalysis,2018,357:238-246.
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