双金属氮化物NiMoN析氢催化剂制备及其电解海水析氢性能的研究

doi:10.6023/A22070309

摘要/Abstract

电解水制氢是最具潜力的绿氢制备技术, 而高效析氢反应(HER)催化剂的开发对其大规模推广意义重大. 选用氯化镍和钼酸铵为镍源和钼源, 通过原位生长法获得NiMo双金属催化剂前驱体, 再以二腈二胺为氮源, 高温氮化-程序升温法制备了一系列NiMo_xN@NC催化剂(x代表钼酸铵和氯化镍的物质的量比), 并对催化剂进行了结构、形貌以及金属价态表征. 分别在1 mol/L KOH碱液以及模拟海水中分析了析氢(HER)性能. 结果表明, 碱液中NiMo_xN@NC催化剂均具有良好的电荷转移速率(R_ct<1 Ω), 具有较好的内在催化活性(Tafel斜率103~168 mV/dec). 其中, NiMo_0.75N@NC催化剂具有最高的极限电流(–178 mA/cm²), 最小的过电势η₁₀=0.164 V, η₁₀₀=0.448 V), 最高的内在催化活性, Tafel斜率只有103 mV/dec, 且具有较好的稳定性. 在海水中, 在10 mA/cm²和40 mA/cm²的负载电流下, NiMo_0.75N@NC催化剂依旧表现出了较好的稳定性.

关键词: 氢能源, 过渡双金属氮化物催化剂, NiMoN@NC催化剂, 海水制氢, 析氢反应(HER)过程

Hydrogen production by water electrolysis was supposed to be the most potential green hydrogen production technology. The development of high-efficiency hydrogen evolution reaction (HER) catalyst is of great significance for its large-scale promotion. In this study, nickel chloride and ammonium molybdate were used as nickel and molybdenum sources respectively to obtain the precursor of NiMo bimetallic catalyst by in-situ growth method. The dinitrile diamine was used as nitrogen source and a series of NiMo_xN@NC (x represents the molar ratio of ammonium molybdate and nickel chloride) catalysts were prepared by high temperature nitridation temperature programmed method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The HER performance of as prepared catalysts was tested in 1 mol/L KOH solution and simulated seawater respectively. Results showed that all NiMo_xN@NC catalysts have presented a relatively high conductivity (R_ct<1 Ω) and intrinsic catalytic activity (Tafel slope of 103~168 mV/dec). Among them, the NiMo_0.75N@NC catalyst posessed the highest limiting current density (–178 mA/cm²) and the lowest overpotential η at certain current densities of 10 mA/cm² and 100 mA/cm² (η₁₀=0.164 V, η₁₀₀=0.448 V). Furthermore, the NiMo_0.75N@NC catalyst has also presented a relatively high stability in KOH solution and seawater.

Key words: hydrogen energy source, transition bimetallic nitride catalyst, NiMoN@NC catalyst, hydrogen production by seawater, hydrogen evolution reaction (HER) process

引用此文

蒋博龙, 崔艳艳, 史顺杰, 姜楠, 谭伟强. 双金属氮化物NiMoN析氢催化剂制备及其电解海水析氢性能的研究[J]. 化学学报, 2022, 80(10): 1394-1400.

Bolong Jiang, Yanyan Cui, Shunjie Shi, Nan Jiang, Weiqiang Tan. Preparation of Highly Active Transition Bimetallic Nitride NiMoN Hydrogen Evolution Reaction (HER) Catalyst and Its Performance Study in Seawater Electrolysis[J]. Acta Chimica Sinica, 2022, 80(10): 1394-1400.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 8

图1. NiMoxN@NC催化剂XRD谱图

Figure 1. XRD results of as prepared NiMoxN@NC catalysts

图2. NiMo0.25N@NC (a, b)和NiMo0.75N@NC (c, d)催化剂SEM图

Figure 2. SEM results of NiMo0.25N@NC (a, b) and NiMo0.75N@NC (c, d)

图3. NiMo0.75N@NC催化剂TEM图

Figure 3. TEM results of NiMo0.75N@NC catalyst

图4. NiMo0.75N@NC催化剂的XPS谱图. (a) Ni 2p; (b) Mo 3d; (c) N 1s; (d) C 1s

Figure 4. XPS results of NiMo0.75N@NC: (a) Ni 2p; (b) Mo 3d; (c) N 1s; (d) C 1s

图5. 在1 mol/L KOH溶液中NiMoxN@NC催化剂的线性伏安(LSV) (a)、奈奎斯特阻抗(EIS) (b)和Tafel斜率(c); NiMo0.75N@NC催化剂在不同负载电流密度下稳定性(d); NiMo0.75N@NC催化剂在不同扫描速率下的循环伏安曲线(e)和电容Cdl (f)

Figure 5. Electrochemical test of NiMoxN@NC catalyst in 1 mol/L KOH: (a) LSV, (b) EIS, (c) Tafel slope; (d) stability test of NiMo0.75N@NC catalyst under different current densities; (e) CV curves of NiMo0.75N@NC catalyst under different scanning rates and (f) Cdl results according to CV curves

催化剂名称	η₁₀/V	η₄₀/V	η₁₀₀/V
NiMo_0.25N@NC	0.326	0.463	0.590
NiMo_0.50N@NC	0.336	0.457	0.566
NiMo_0.75N@NC	0.164	0.304	0.448
NiMo_1.00N@NC	0.343	0.459	0.571

表1. NiMoxN@NC催化剂在10、40以及100 mA/cm2所对应的过电势

Table 1. Potential of NiMoxN@NC catalysts under different current densities (10, 40 and 100 mA/cm2)

图6. NiMo0.75N@NC催化剂的模拟海水制氢测试结果: (a)线性伏安(LSV); (b) Tafel斜率测试; (c) 奈奎斯特阻抗测试(EIS)和(d)不同负载电流密度下的稳定性

Figure 6. Electrochemical test of NiMo0.75N@NC catalyst for hydrogen evolution in simulated seawater: (a) LSV; (b) Tafel; (c) EIS and (d) stability test under different currrent densities

成分	在盐中的百分比/%	浓度/(g•L^‒1)
NaCl	77.76	27.2
MgCl₂	10.88	3.80
MgSO₄	4.38	1.70
CaSO₄	3.60	1.20
K₂SO₄	2.47	0.90
CaCO₃	0.35	0.10

表2. 模拟海水的配制成分表

Table 2. Main components of simulated seawater

参考文献 30

[1]	Zhang, Z.-H.; Jiang, F.-J.; Wu, K.-K.; Shen, P. Acta Chim. Sinica 2022, 80, 56. (in Chinese) doi: 10.6023/A21090440
	(张竹涵, 蒋峰景, 吴珂科, 申鹏, 化学学报, 2022, 80, 56.) doi: 10.6023/A21090440
[2]	Anantharaj, S.; Kundu, S.; Noda, S. J. Mater. Chem. A 2020, 8, 4174. doi: 10.1039/C9TA14037A
[3]	Wu, Y.; Wei, W.; Yu, R.; Xia, L.; Hong, X.; Zhu, J.; Li, J.; Lv, L.; Chen, W.; Zhao, Y.; Zhou, L.; Mai, L. Adv. Funct. Mater. 2022, 32, 2110910. doi: 10.1002/adfm.202110910
[4]	Mitchell, D. S. Int. J. Hydrogen Energ. 2022, 19, 10441.
[5]	Lv, X.; Yin, S. Appl. Surf. Sci. 2021, 537, 147834. doi: 10.1016/j.apsusc.2020.147834
[6]	Krishna, H. R. European Journal of Biotechnology and Bioscience 2013, 1, 84.
[7]	d’Amore-Domenech, R.; Leo, T. J. ACS Sustain. Chem. Eng. 2019, 7, 8006. doi: 10.1021/acssuschemeng.8b06779
[8]	Zhu, J.; Li, S.; Zhuang, Z.; Gao, S.; Hong, X.; Pan, X.; Yu, R.; Zhou, L.; Moskaleva, L. V.; Mai, L. Energy Environ. Mater. 2022, 5, 231. doi: 10.1002/eem2.12155
[9]	Silava, Y. S. K. D.; Middleton, P. H.; Kolhe, M. L. Renew. Energ. 2020, 149, 760. doi: 10.1016/j.renene.2019.12.087
[10]	Barco-Burgos, J.; Eicker, U.; Saldna-Robles, N.; Saldana-Robles, A. L.; Alcantar-Camarena, V. Fuel 2020, 15, 117910.
[11]	Lovell, E. C.; Lu, X. Y.; Zhang, Q. R.; Scott, J.; Amal, R. Chem. Commun. 2020, 56, 1709. doi: 10.1039/C9CC07486D
[12]	Zhang, W.; Han, N.; Luo, J. Small 2022, 18, 2103561. doi: 10.1002/smll.202103561
[13]	Zhao, Y.; Zhang, J.; Xie, Y. Nano Lett. 2021, 21, 823. doi: 10.1021/acs.nanolett.0c04569
[14]	Peng, X.; Li, C. H.; Zhang, X. M.; Li, S.; Huo, K. F.; Chu, P. K. Sustain. Energ. Fuels 2019, 3, 366. doi: 10.1039/C8SE00525G
[15]	Zeng, Q.-L.; Liu, X.-C.; Liu, C.; Qi, X.-P. Acta Materiae Compositae Sinica 2021, 38, 3764. (in Chinese)
	(曾庆乐, 刘小超, 刘超, 漆小鹏, 复合材料学报, 2021, 38, 3764.)
[16]	Zhang, Y. G.; Li, P. J.; Zhang, X. G.; Fa, W. J.; Ge, S. X. J. Alloy. Compd. 2018, 732, 248. doi: 10.1016/j.jallcom.2017.10.194
[17]	Yao, S.-W.; Li, H.; Zhang, W.-G.; Wang, H.-Z.; Ben, Y.-H. Acta Materiae Compositae Sinica 2006, 23, 77. (in Chinese)
	(姚素薇, 李贺, 张卫国, 王宏智, 贲宇恒, 复合材料学报, 2006, 23, 77.)
[18]	Qian, G.; Chen, J.; Yu, T.; Luo, L.; Yin, S. Nan-Micro Lett. 2021, 13, 77.
[19]	Chen, W. F.; Sasaki, K.; Ma, C. Angew. Chem. Int. Ed. 2012, 51, 6131. doi: 10.1002/anie.201200699
[20]	Jin, H. Y.; Liu, X.; Vasileff, A.; Jiao, Y.; Zhao, Y.; Zheng, Y.; Qiao, S. ACS Nano 2018, 12, 12761. doi: 10.1021/acsnano.8b07841
[21]	Miao, J.; Lang, Z. L.; Zhang, X. Y.; Kong, W. G.; Peng, O. W.; Yang, Y.; Wang, S. P.; Cheng, J. J.; He, T. C.; Amini, A.; Wu, Q. Y.; Zheng, Z. P.; Tang, Z. K.; Cheng, C. Adv. Funct. Mater. 2019, 29, 1805893.
[22]	Liu, Z.; Liu, D. Y.; Zhao, L. Y.; Tian, J.; Yang, J.; Feng, L. J. Mater. Chem. A 2020, 9, 7750. doi: 10.1039/D1TA01014J
[23]	Carmo, M.; Frit, D. L.; Mergel, J.; Stolten, D. Int. J. Hydrogen Energ. 2013, 38, 4901. doi: 10.1016/j.ijhydene.2013.01.151
[24]	Song, F.; Li, W.; Yang, J.; Han, G.; Liao, P.; Sun, Y. Nat. Commun. 2018, 9, 4531. doi: 10.1038/s41467-018-06728-7
[25]	Gong, Y.; Wang, L.; Xiong, H.; Shao, M. F.; Xu, L. D.; Xie, A.; Zhuang, S. X.; Tang, Y.; Yang, X. J.; Chen, Y. M.; Wan, P. Y. J. Mater. Chem. A 2019, 7, 13671. doi: 10.1039/c9ta03473k
[26]	Ma, B.; Liu, Y.; Li, J.; Lin, K.; Liu, W.; Zhan, H. Int. J. Hydrogen Energ. 2016, 47, 22009.
[27]	Wei, C.; Huang, Y.; Yan, J.; Chen, X.; Zhang, X. Ceram. Int. 2016, 42, 15694. doi: 10.1016/j.ceramint.2016.07.026
[28]	Yan, J.; Fan, Z.; Sun, W.; Ning, G. Q.; Wei, T.; Zhang, Q.; Zhang, R. F.; Zhi, L. J.; Wei, F. Adv. Funct. Mater. 2012, 22, 2632. doi: 10.1002/adfm.201102839
[29]	Yu, L.; Zhu, Q.; Song, S.; McElhenny, B.; Wang, D. Z.; Wu, C. Z.; Qin, Z. J.; Bao, J. M.; Yu, Y.; Chen, S.; Ren, Z. F. Nat. Commun. 2019, 10, 5106. doi: 10.1038/s41467-019-13092-7
[30]	Zhang, R.; Xu, L.; Wu, Z.; Wang, L.; Zhang, L.; Tang, Y.; Xu, L.; Xie, A.; Chen, Y.; Zhang, H.; Wan, P. Chem. Eng. J. 2022, 436, 134931. doi: 10.1016/j.cej.2022.134931