自牺牲模板法制备氮掺杂碳化钼/碳析氢电催化剂

doi:10.11949/0438-1157.20200207

摘要/Abstract

摘要：

采用g-C₃N₄为自牺牲模板和氮源，葡萄糖为碳源，钼酸铵为钼源，制备具有二维纳米结构的氮掺杂碳化钼修饰碳纳米片(N-Mo₂C/C)，并评价其电催化析氢性能。利用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)、拉曼(Raman)等测试手段对N-Mo₂C/C的组成、形貌及结构进行分析。结果表明，氮掺杂的Mo₂C纳米颗粒均匀分散在二维碳纳米片上，粒径主要分布在3~5 nm。利用电化学工作站测试 N-Mo₂C/C的电催化析氢性能，在1 mol/L KOH溶液中，电流密度为10 mA/cm²时其对应的过电势为185 mV，Tafel斜率为69 mV/dec，经20 h循环可维持稳定的析氢电势。

关键词: 碳化钼, 纳米材料, 电化学, 催化剂, 析氢性能

Abstract:

Using g-C₃N₄as self-sacrificing template and nitrogen source, glucose as carbon source, and ammonium molybdate as molybdenum source, nitrogen-doped molybdenum carbide modified carbon nanosheets (N-Mo₂C/C) with two-dimensional nanostructures were prepared and evaluated its electrocatalytic hydrogen evolution performance. X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), Raman spectroscopy, etc. were employed to analyze the compositions, morphologies and microstructures of the as-prepared N-Mo₂C/C. The results show that ultrafine nitrogen-doped Mo₂C nanoparticles with a diameter of 3—5 nm can be uniformly distributed on the 2D carbon nanosheets. The electrocatalytic performances of N-Mo₂C/C for hydrogen evolution were tested by using an electrochemical workstation, which demonstrates that the N-Mo₂C/C only exhibits an overpotential of 185 mV at 10 mA/cm² in 1 mol/L KOH solution, and a stable hydrogen evolution potential could be maintained for 20 h in a long-term cycling test.

Key words: molybdenum carbide, nanomaterials, electrochemistry, catalyst, hydrogen evolution performance

中图分类号:

O 614.61

范小明, 陈希奎, 汪子涵, 曹帅, 程凤如, 杨则恒, 张卫新. 自牺牲模板法制备氮掺杂碳化钼/碳析氢电催化剂[J]. 化工学报, 2020, 71(6): 2840-2849.

Xiaoming FAN, Xikui CHEN, Zihan WANG, Shuai CAO, Fengru CHENG, Zeheng YANG, Weixin ZHANG. Self-sacrificing templated preparation of nitrogen-doped molybdenum carbide/carbon as hydrogen evolution electrocatalyst[J]. CIESC Journal, 2020, 71(6): 2840-2849.

图/表 9

图1 NMC的制备流程示意图

Fig.1 Schematic diagram of the preparation process of NMC

图2 NMC-700、NMC-800和NMC-900样品的XRD谱图(a)及拉曼谱图(b)

Fig.2 XRD patterns (a) and Raman spectra (b) of NMC-700, NMC-800 and NMC-900 samples

图3 NMC-700(a)、NMC-800(b)和NMC-900(c)的FESEM图；NMC-800的TEM图(d)；NMC-800的HRTEM图(e)和选区电子衍射图(f)；NMC-800TEM图(g)及相应的元素分布图(C，N和Mo元素)[(h)~(j)]

Fig.3 FESEM images of NMC-700 (a), NMC-800 (b) and NMC-900 (c); TEM image of NMC-800 (d) ; HRTEM image (e) and selected area electron diffraction pattern (f) of NMC-800; TEM image(g) and corresponding element mapping images of NMC-800 (C, N and Mo elements) [(h)~(j)]

图4 NMC-800样品的氮气吸附-脱附等温线(a)及对应的孔径分布曲线(b)

Fig.4 Nitrogen adsorption-desorption isotherm of NMC-800 (a), and corresponding pore size distribution curve (b)

图5 不同催化剂的C，N，Mo元素高分辨XPS谱图：NMC-700 (a)~(c)，NMC-800 (d)~(f)，NMC-900 (g)~(i)

Fig.5 High-resolution C, N, Mo XPS spectra of different catalysts: NMC-700 (a)—(c), NMC-800 (d)—(f), NMC-900 (g)—(i)

表1 高分辨XPS谱图中不同催化剂的各元素含量

Table 1 Contents of each element in different catalysts from high-resolution XPS spectra

催化剂

C/%

(atom)

Mo/%

(atom)

N/%

(atom)

O/%

(atom)

图6 CFP、NMC-700、NMC-800、NMC-900和商用Pt/C的极化曲线(a)和Tafel图(b)(电解液：1 mol/L KOH，扫描速率：10 mV/s)；NMC-800在1 mol/L KOH中的稳定性测试曲线(c)；NMC-800经过2000次循环前后的极化曲线(d)

Fig.6 Polarization curves (a) and Tafel plots of CFP, NMC-700, NMC-800, NMC-900 and commercial Pt/C (b) (scanning rate: 10 mV/s, electrolyte: 1 mol/L KOH); stability test curve of NMC-800 in 1 mol/L KOH (c); polarization curve of NMC-800 before and after 2000 cyclic voltammetry cycles (d)

表2 N-Mo2C/C催化剂的HER活性与文献报道结果比较

Table 2 Comparison of HER activity for N-Mo2C/C catalysts with the results in recently reported literatures

Electrocatalyst	j/ (mA/cm²)	η/(mV)	b/ (mV/dec )	Electrolyte solution	Ref.
NMC-800	10	185	69	1M KOH	this work
MoC/C	10	≈200	114	1M KOH	[30]
Mo₂C@N-C(S)	10	271	90	1M KOH	[31]
Mo₂C NWAs/CFP	10	≈168	72	1M KOH	[32]
Mo/Mo₂C@G-800	10	159	78	1M KOH	[33]
Mo₂C@NC	10	≈247	78	1M KOH	[17]

图7 NMC-700(a)、NMC-800(b)及NMC-900(c)在不同扫描速率下的CV曲线(1 mol/L KOH)；NMC-700，NMC-800及NMC-900电容电流与扫描速率的关系(d)

Fig.7 CV curves of NMC-700 (a), NMC-800 (b) and NMC-900 (c) at different scanning rates (1 mol/L KOH); relationship between capacitor current and scanning rate for NMC-700, NMC-800 and NMC-900 (d)

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