现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (5) : 183-188. DOI: 10.16606/j.cnki.issn0253-4320.2025.05.030

科研与开发

Ni-Mo-N异质结构设计及电催化析氢性能研究

王杰 ^* ,
张晓嵘

作者信息 +

Construction of Ni-Mo-N heterostructure and study on its performance in electrocatalytic hydrogen evolution

WANG Jie ^* ,
ZHANG Xiao-rong

Author information +

文章历史 +

Received		Published
2024-12-24		2025-05-20
Issue Date	Revised Date
2025-05-19	2024-12-24

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摘要

利用水热-氮化的方法,通过对氮化温度进行调控,成功开发并合成了Ni-Mo-N异质结构电催化剂。经过相关表征发现,当氮化温度达到500℃时,形成了由Ni₃N和Ni_0.2Mo_0.8N所构成纳米阵列结构。凭借丰富的界面以及快速的电子传输能力,该催化剂在碱性条件下展现出极为出色的析氢反应(HER)活性与稳定性。当电流密度达到10 mA/cm²时,其过电位仅仅只有61 mV。与Ni₃N相比,Ni₃N/Ni_0.2Mo_0.8N的本征活性显著提升。

Abstract

A Ni-Mo-N heterostructure electrocatalyst is fabricated by using a hydrothermal-nitridation method and regulating the nitridation temperature.A series of characterization show that the nano-array structure composed of Ni₃N/Ni_0.2Mo_0.8N heterostructure is formed under a nitridation temperature of 500℃.By virtue of the rich interfaces and fast electron transport ability,Ni₃N/Ni_0.2Mo_0.8N catalyst exhibits superior hydrogen evolution reaction (HER) activity and stability under alkaline conditions.The overpotential of Ni₃N/Ni_0.2Mo_0.8N catalyst is 61 mV only at a current density of 10 mA·cm^-2.The intrinsic activity of Ni₃N/Ni_0.2Mo_0.8N is significantly higher than that of Ni₃N.

Graphical abstract

关键词

异质结构 / 过渡金属氮化物 / 氢产品 / 电解水

Key words

heterostructure / transition metal nitrides / hydrogen product / electrocatalytic water splitting

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氢能作为一种高效、清洁且可持续的能源载体受到广泛地关注^[1-2]。电解水制氢是一种极具潜力的绿色制氢技术,而开发高效、稳定且低成本的电催化剂是推动该技术大规模应用的关键^[3-4]。由于特殊的电子结构排布和类贵金属特性,过渡金属氮化物(TMNs)在电催化析氢反应(HER)领域应用广泛^[5-7]。镍基过渡金属氮化物更是在众多研究中崭露头角,成为HER研究的热点材料之一。然而,其电催化性能的进一步提升面临着诸多挑战,如活性位点有限、电子传输效率有待提高以及对反应中间体的吸脱附性能仍需优化等。

为了克服这些局限,学者们不断探索创新策略,其中,掺杂、缺陷工程以及界面工程等方法被广泛研究^[8-11]。在这些策略里,界面工程构建的异质结构脱颖而出。其一,由于不同组分功函数存在差异,所以会引发界面电荷极化现象,能够改变催化剂表面的电荷分布状态,使得反应中间体在催化剂表面的吸脱附行为得到优化^[12-14];其二,异质结构具备在界面产生新活性位点的能力,同时可以诱导电子重新分布,提升催化剂整体的导电性,最终实现催化性能的显著提升^[15-16]。如基于界面效应,Ni₃N-V₂O₃异质结构具有较好的碱性HER活性。表征和理论计算证实,引入V₂O₃所产生的限域效应和界面耦合效应能够极大地增加催化位点,调节界面处的电荷分布,提升材料的HER性能^[10]。

基于此,笔者以碳布(CC)作为支撑材料,利用水热-氮化方案原位合成Ni-Mo-N电极材料。通过XRD、SEM、TEM、XPS对材料结构、形貌等进行分析。采用电化学性能测试技术对材料的电催化HER进行评价。

1 实验部分

1.1 材料与试剂

四水合钼酸铵、聚乙烯吡咯烷酮(K30),国药集团化学试剂有限公司生产;乙酸镍、尿素,阿拉丁试剂(上海)有限公司生产;碳布,上海河森电气有限公司生产。

1.2 Ni-Mo-N异质结构的合成

NiMoO的合成:将1 mmol的乙酸镍、0.1 mmol的四水合钼酸铵、5 mmol的尿素以及0.2 g聚乙烯吡咯烷酮放置在30 mL去离子水中进行分散。随即把所得的混合溶液转移至容积为45 mL的反应釜中,并放入1片面积为2×4 cm²的碳布,在140℃持续反应6 h。反应完毕后,用水和乙醇对碳布进行冲洗,最后经干燥得到NiMoO/CC。

NiMoN-400的合成:前驱体NiMoO/CC在氨气气氛下400℃氮化2 h,待自然冷却后即可得到。

Ni₃N/Ni_0.2Mo_0.8N的合成:前驱体NiMoO/CC在氨气气氛下500℃氮化2 h,待自然冷却后即可得到。

Ni/Mo₅N₆的合成:前驱体NiMoO/CC在氨气气氛下600℃氮化2 h,待自然冷却后即可得到。

作为对比,合成了Ni₃N。与NiMoN-400的合成方法类似,除了前驱体合成中不加四水合钼酸铵。

1.3 电催化HER性能测试

电化学测试采用三电极体系并在CHI760E电化学工作站上完成。碳棒为对电极,Hg/HgO电极为参比电极,原位合成的材料为工作电极,电解液为1 mol/L KOH溶液。所有电位转化为可逆氢电位:

E R H E = E H g / H g O + 0.059 1 × p H + 0.098

双电层电容(C_dl)在0.1~0.2 V(vs RHE)并以不同扫速(10、20、40、60、80、100 mV/s)进行CV测试。取0.15 V(vs RHE)电流密度(Δj=j_anode-j_cathode)的一半(Δj/2)为纵坐标,扫速为横坐标,线性作图的斜率即为C_dl。电化学阻抗测试(EIS)在恒电位的条件下进行测试,振幅为5 mV,频率为100 kHz~0.01 Hz。

2 结果与分析

2.1 形貌与结构表征

2.1.1 XRD分析

用水热法在碳布基底上原位生长NiMoO前驱体,接着将所获得的前驱体置于氨气气氛中,在高温条件下进行退火处理,最终得到Ni-Mo-N异质结构。Ni₃N和Ni-Mo-N异质结构的XRD图谱如图1所示。

由图1(a)中可以看到,氮化温度为400℃时,Ni(OH)₂被完全氮化为Ni₃N。从图1(b)中可以看出,氮化温度为400℃时合成的样品中没有呈现出明显的Ni₃N及Mo基物种的衍射峰,意味着在低温条件下合成的双金属化合物的结晶性相对较差。随着氮化温度逐渐升高,Ni-Mo-N样品的衍射峰强度越来越明显。当温度达到500℃时,位于41.9、44.5°处的衍射峰分别与Ni₃N的(002)晶面及(111)晶面相互匹配。此外,在36.4°的位置上还出现1个新的特征峰,对应着Ni_0.2Mo_0.8N(PDF#29-0931)六方晶系的(100)晶面。表明氮化温度为500℃时所制备的Ni-Mo-N呈现为Ni₃N与 Ni_0.2Mo_0.8N的混合相形态。

从图1(c)中可以看出,当氮化温度达到600℃时,所制备的Ni-Mo-N材料在44.5、51.8°处出现新的衍射峰,分别对应于Ni的(111)晶面和(200)晶面。表明在氮化进程中前驱体NiMoO里的NiO在较低温度氮化时首先转化为Ni₃N,而随着温度进一步升高至600℃,在氨气的作用下,Ni₃N又被还原成了金属Ni,此变化规律与文献[17]中的报道相吻合。与此同时,该Ni-Mo-N材料在36.7、49.7°和66.0°位置还出现了Mo₅N₆(PDF#51-1326)的特征衍射峰。由此说明,在氮化温度为600℃条件下合成的Ni-Mo-N样品是由Ni和Mo₅N₆混合组成。

2.1.2 SEM分析

所有合成氮化物的SEM图如图2所示。由图2(a)中可以看出,Ni₃N呈现出纳米片阵列的形貌特征,其中各个纳米片均由众多颗粒聚集形成。添加Mo源后,前驱体NiMoO在氮化过程中形成较小的纳米片结构。由图2(b)和图2(c)可知,NiMoN-400和Ni₃N/Ni_0.2Mo_0.8N的形貌没有太大差异,均为纳米片结构。由图2(d)中可以看出,氮化温度进一步提升到600℃时,Ni/Mo₅N₆结构中的纳米片基本完全塌陷,并且产生大量粒径不一致的颗粒,说明高温氮化处理对纳米片的形成是不利的。

2.1.3 TEM用EDX分析

Ni₃N/Ni_0.2Mo_0.8N的TEM图、HRTEM图、选区电子衍射图和EDX元素分布图如图3所示。由图3(a)中可以看出,Ni₃N/Ni_0.2Mo_0.8N所呈现的纳米片状结构是由众多颗粒组装而成。由图3(b)中可以清楚地观测到晶格间距分别为0.244 nm和0.214 nm,分别与Ni_0.2Mo_0.8N的(100)晶面以及Ni₃N的(002)晶面相匹配。在Ni_0.2Mo_0.8N的(100)晶面与Ni₃N的(002)晶面明显观察到相界面的存在。从图3(c)中可以看出,所呈现出的衍射环分别和Ni_0.2Mo_0.8N的(110)、(101)、(100)晶面及Ni₃N的(002)晶面一一对应。从图3(d)~(g)中可以看出,Mo、Ni和N元素在整个纳米结构中均匀分布。结果证实Ni₃N/Ni_0.2Mo_0.8N异质结构已被成功合成。

2.1.4 XPS分析

利用XPS对Ni₃N/Ni_0.2Mo_0.8N异质结构的元素组成与价态进行研究,结果如图4所示。从图4(a)中可以看出,Ni₃N/Ni_0.2Mo_0.8N异质结构中Mo、Ni和N元素同时存在,这与图3(d)~(g)的EDX图所测得的元素结果相符。从图4(b)中可以看出,位于853.37 eV和870.68 eV处的峰分别归属于Ni-N中Ni⁺的Ni 2p_3/2和Ni 2

p 1 / 2 18

,而位于855.99 eV和861.70 eV处的2个峰则分别对应于Ni—O的Ni²⁺以及卫星峰^[6]。与Ni₃N样品相比,Ni₃N/Ni_0.2Mo_0.8N中Ni 2p_3/2和Ni 2p_1/2结合能峰发生了约0.15 eV的偏移,证明了在异质界面之间发生了电子转移^[14]。这种相互作用能够促使界面处的电荷重新分布,进而提升电催化反应性能^[19]。从图4(c)中可以看出,Mo 3d谱经拟合处理后得到6个峰,结合能为229.51 eV和232.79 eV处的特征峰归属于Mo³⁺,结合能在230.29/233.49 eV和232.31/235.57 eV处的2组双峰则分别对应于Mo⁴⁺和Mo⁶⁺。其中,Mo³⁺源自Ni_0.2Mo_0.8N中的Mo-N,据报道,其可作为析氢反应(HER)的活性位点^[20-21]。Mo⁴⁺和Mo⁶⁺则是由于Mo物种表面不可避免的氧化所产生。从图4(d)中可以看出,由于N 1s和Mo 3p存在部分重叠,在N 1s图谱中在395.47、397.62、399.26 eV处分别出现3个峰,分别对应于Mo 3p^[22]、Ni₃N/Ni_0.2Mo_0.8N异质结构中的Ni—N或Mo—N键及NH₃中的N—H^[23]。

2.2 Ni-Mo-N异质结构催化HER性能

碳布上原位合成的氮化物作为工作电极,Hg/HgO电极和石墨电极分别作为参比电极和对电极,在1 mol/L KOH电解液中研究其电催化析氢性能,如图5所示。从图5(a)中可以看出,相同电流密度下,Ni₃N的过电位最大。在电流密度10 mA/cm²时对应的过电位高达260 mV,表明Ni₃N展示出最差的碱性HER活性。在引入Mo源之后,Ni-Mo-N样品的析氢反应(HER)性能获得极大地提升。随着氮化温度的变化,在500℃合成的Ni₃N/Ni_0.2Mo_0.8N异质结构展现出了最为优异的HER活性,并且在电流密度大于20 mA/cm²时,其过电位显著低于其他样品。不同样品在10 mA/cm²时的过电位如表1所示。从表1中可以看出,在电流密度为10 mA/cm²时,Ni₃N/Ni_0.2Mo_0.8N仅需61 mV的过电位,明显好于Ni₃N(260 mV)、NiMoN-400(71 mV)、Ni/Mo₅N₆(137 mV)。

借助Tafel曲线评价了Ni-Mo-N材料的HER动力学过程^[24]。Tafel曲线斜率越低,则动力学反应进程越快。由图5(b)中可以看出,Ni₃N/Ni_0.2Mo_0.8N的Tafel斜率最小,为104.8 mV/dec,这意味着其在HER过程中遵循Volmer-Heyrovsky反应机制,且反应速率受电化学脱附所控制^[25-26]。此外,Ni₃N/Ni_0.2Mo_0.8N的Tafel斜率比Ni₃N更小,表明Ni₃N/Ni_0.2Mo_0.8N的HER动力学过程最为迅速。为进一步阐释Ni₃N/Ni_0.2Mo_0.8N催化剂HER性能得以提升的内在机理,运用EIS对催化剂的电子转移特性进行了分析^[8]。由图5(c)中可以看出,Ni₃N和Ni₃N/Ni_0.2Mo_0.8N的EIS曲线均呈现出典型的半圆形态。显而易见,Ni_0.2Mo_0.8N的圆弧直径最小,表明Ni₃N/Ni_0.2Mo_0.8N具有快速的电荷转移能力以及电催化动力学特性^[27]。

另外,借助对双层电容(C_dl)的计算,明确了电化学活性表面积(ECSA)。Ni₃N和Ni₃N/Ni_0.2Mo_0.8N不同扫速下的CV曲线和双电层电容曲线如图6所示。

从6(c)中可以看出,Ni₃N/Ni_0.2Mo_0.8N的C_dl值达到34.4 mV/dec。相比之下,Ni₃N的C_dl值仅为11.7 mV/dec,意味着Ni₃N/Ni_0.2Mo_0.8N异质结构的表面能够提供更多的活性位点。为了进一步揭示催化剂固有活性,将电流密度按照ECSA值进行归一化处理,如图7(a)所示。从图7(a)中可以看出,Ni₃N/Ni_0.2Mo_0.8N的归一化HER活性显著优于Ni₃N,说明Ni₃N/Ni_0.2Mo_0.8N异质结构具有较大的本征催化活性。最后,借助计时电位法在10 mA/cm²的条件下对Ni₃N/Ni_0.2Mo_0.8N的HER稳定性展开了评价,结果如图7(b)所示。从图7(b)中可以看出,Ni₃N/Ni_0.2Mo_0.8N在持续运行32 h后,电位仅仅出现了小幅的增加,说明Ni₃N/Ni_0.2Mo_0.8N具备十分优异的碱性HER稳定性。

在完成稳定性测试之后,测试了Ni₃N/Ni_0.2Mo_0.8N电极的XRD和TEM,结果如图8所示。从图8中可以看出,Ni₃N/Ni_0.2Mo_0.8N的组分以及形貌和最初相比并没有太大的差异,不过其结晶程度有一定程度的降低。以上电化学性能及表征结果共同表明,Ni₃N/Ni_0.2Mo_0.8N异质结构在碱性电解液中拥有优异的HER活性与稳定性。

3 结论

借助界面效应利用水热-氮化的方法设计了一种Ni-Mo-N异质结构电催化剂并研究其电催化HER性能。通过调控氮化温度,氧化物前驱体在500℃时可以合成Ni₃N和Ni_0.2Mo_0.8N的异质结构纳米阵列。该催化剂表现出优异的碱性HER活性和稳定性。在10 mA/cm²时过电位仅需61 mV。相比Ni₃N,Ni-Mo-N展示出优异的本征催化活性和较快的动力学过程。该催化剂优异的性能可以归因于异质结构提高较多的活性位点和较快的电子传输能力。

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