金属性Ni3N纳米粒子的制备与乙二醇电氧化性能★

doi:10.6023/A23050202

摘要/Abstract

利用小分子电催化氧化反应耦合水解制氢不仅有助于降低阳极反应过电位, 提高析氢反应(HER)效率, 而且产生高附加值的化学品, 是提升电催化水分解性能的有效策略. 其关键是开发具有高导电性和低氧化电位的非贵金属电催化剂. 以Ni(OH)₂纳米片为前驱物, 通过退火氮化工艺, 制备了具有低氧化电位和高导电性的金属相Ni₃N纳米颗粒(Ni₃N-NPs). 与Ni(OH)₂相比, Ni₃N-NPs具有较小的法拉第电阻, 更低的氧化电位(1.36 V时达到10 mA•cm^–2), 较小的Tafel斜率(29 mV•dec^–1), 表现出更好的乙二醇(EG)电催化氧化性能. 在1.36 V时, Ni₃N-NPs电催化氧化EG生成甲酸盐的法拉第效率高达91.16%. 通过X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)对反应前后Ni₃N-NPs结构进行详细表征发现, 在电催化 EG 氧化过程中, Ni₃N-NPs表面被氧化生成NiOOH, 同时EG在催化剂表面发生脱H氧化生成甲酸, H同步还原NiOOH并将其转化为Ni(OH)₂. 此外, Ni₃N-NPs对有机小分子电催化氧化具有良好的普适性.

关键词: 电催化, 电解水, 乙二醇, Ni(OH)₂, Ni₃N

Coupled small molecule electrocatalytic oxidation reaction can not only reduce anode overpotential, improve hydrogen evolution reaction (HER) efficiency, but also produce high value-added chemicals, which is an effective strategy to improve the performance of electrocatalytic water splitting. The development of non-noble metal based electrocatalysts with high conductivity and low oxidation potential is the key issue. Herein, Ni₃N nanoparticles (Ni₃N-NPs) with low oxidation potential and high conductivity were prepared by annealing and nitriding Ni(OH)₂ nanosheets precursors. Compared with Ni(OH)₂, Ni₃N-NPs has a smaller Faraday resistance, a lower oxidation potential, a smaller Tafel slope (29 mV•dec^–1), and exhibits the better electrocatalytic oxidation performance towards ethylene glycol (EG). At 1.36 V, the Faraday efficiency of electrocatalytic EG oxidation to formate reached 91.16%. The structure of Ni₃N-NPs before and after the electrocatalytic oxidation reaction was characterized in detail by X-ray diffractometer (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). It was found that in the electrocatalytic EG oxidation process, the surface of Ni₃N-NPs was oxidized into NiOOH, while EG underwent dehydrogenation and oxidation to form formic acid on the catalyst surface, and the NiOOH was synchronously reduced by H and converted into Ni(OH)₂. In addition, Ni₃N-NPs has good universality for electrocatalytic oxidation of small organic molecules.

Key words: electrocatalysis, water splitting, ethylene glycol, Ni(OH)₂, Ni₃N

引用此文

杨镇鸿, 干晓娟, 王书哲, 段君元, 翟天佑, 刘友文. 金属性Ni₃N纳米粒子的制备与乙二醇电氧化性能^★[J]. 化学学报, 2023, 81(11): 1471-1477.

Zhenhong Yang, Xiaojuan Gan, Shuzhe Wang, Junyuan Duan, Tianyou Zhai, Youwen Liu. Preparation of Metallic Ni₃N Nanoparticles and Its Electrooxidation Performance for Ethylene Glycol^★[J]. Acta Chimica Sinica, 2023, 81(11): 1471-1477.

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图/表 8

图1. Ni3N纳米颗粒的物相与结构表征. (a) XRD图谱; (b) Raman光谱; (c) TEM照片; (d) HRTEM照片

Figure 1. Phase and structure characterization of Ni3N nanoparticles (Ni3N-NPs). (a) XRD pattern; (b) Raman spectrum; (c) TEM and (d) HRTEM images

图2. Ni3N-NPs电催化乙二醇氧化性能. (a)有无EG的LSV曲线; (b) Ni3N-NPs和Ni(OH)2电催化EG氧化LSV曲线; (c) Tafel斜率; (d) 10 mA? cm–2下计时电位曲线; (e) Cdl值; (f)归一化后的LSV曲线

Figure 2. Electrocatalytic EG oxidation performance of Ni3N-NPs. (a) LSV curve with or without EG; (b) LSV curve of electrocatalytic EG oxidation for Ni3N-NPs and Ni(OH)2; (c) Tafel slopes; (d) chronopotential curve at 10 mA?cm–2; (e) Cdl values, and (f) normalized LSV curves

图3. 1.4 V下(a)有无乙二醇时Nyquist图; (b) Ni3N-NPs与Ni(OH)2的Nyquist图; 不同电位下Ni3N-NPs的(c) Nyquist图和(d) Bode图, Ni(OH)2的(e) Nyquist图和(f) Bode图; (g)电荷转移示意图(EDL代表双电层)以及等效电路图; (h) Rct与电位之间的关系; (i) Rp与电位之间的关系

Figure 3. (a) Nyquist diagram with or without EG; (b) Ni3N-NPs and Ni(OH)2 Nyquist diagram at 1.4 V; (c) Nyquist diagram and (d) Bode diagram of Ni3N-NPs; (e) Nyquist diagram and (f) Bode diagram of Ni(OH)2 under different potentials; (g) charge transfer diagram (EDL stands for double layer) and equivalent circuit diagram; (h) the relationships between Rct and potential; (i) the relationship between Rp and potential

图4. (a)不同电位下乙二醇氧化产物的核磁共振氢谱; (b)不同电位电催化EG氧化产甲酸盐的法拉第效率; (c)有无乙二醇的电解水的LSV曲线; (d)不同电流密度所需的电解槽电位

Figure 4. (a) 1H NMR spectra of EG oxidation products at different potentials; (b) Faraday efficiency of EG oxidation to formate at different potentials; (c) LSV curves of the electrolytic water splitting with or without EG; (d) cell voltage required by different current densities

图5. (a) Ni3N的电荷密度图; (b) Ni3N的态密度; (c) Ni3N的能带图; (d) Ni3N-NPs和Ni(OH)2在1 mol/L KOH中OER的LSV曲线

Figure 5. (a) Charge density diagram of Ni3N; (b) state density of Ni3N; (c) band diagram of Ni3N; (d) LSV curve of OER of Ni3N-NPs and Ni(OH)2 in 1 mol/L KOH

图6. 电催化氧化EG反应后Ni3N-NPs的(a) TEM和(b~d) HRTEM照片

Figure 6. (a) TEM and (b~d) HRTEM images of Ni3N-NPs after electrocatalytic EG oxidation reaction

图7. Ni3N-NPs电催化氧化EG过程机理图

Figure 7. Schematic diagram of Ni3N-NPs electrocatalytic oxidation reaction towards EG

图8. Ni3N-NPs电催化氧化(a)甲醇、(b)尿素和(c)苯甲醇的LSV曲线; (d)在1.4 V各种有机小分子氧化的电流密度对比

Figure 8. LSV curves of Ni3N-NPS electrocatalytic oxidation (a) methanol, (b) urea and (c) benzyl alcohol; (d) the current densities of electrocatalytic oxidation of various organic small molecule at 1.4 V

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金属性Ni₃N纳米粒子的制备与乙二醇电氧化性能^★

Preparation of Metallic Ni₃N Nanoparticles and Its Electrooxidation Performance for Ethylene Glycol^★

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