弱磁性Co0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

doi:10.1016/S1872-2067(20)63632-4

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 235-243.DOI: 10.1016/S1872-2067(20)63632-4

• 论文 • 上一篇

弱磁性Co_0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

孙小惠^a^,^b, 努扎艾提·艾比布^a^,^b, 杜虹^a^,^b^,^*()

^a新疆师范大学化学化工学院, 新疆乌鲁木齐830054
^b能源储存与光催化矿物材料新疆重点实验室, 新疆乌鲁木齐830054

收稿日期:2020-03-26 接受日期:2020-05-01 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 杜虹
基金资助:
国家自然科学基金(21862022);新疆教育厅高校科研项目(XJEDU2020Y028)

Co_0.85Se magnetic nanoparticles supported on carbon nanotubes as catalyst for hydrogen evolution reaction

Xiaohui Sun^a^,^b, Nuzahat Habibul^a^,^b, Hong Du^a^,^b^,^*()

^aCollege of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi 830054, Xinjiang, China
^bXinjiang Key Laboratory of Energy Storage and Photocatalytic Mineral Materials, Urumqi 830054, Xinjiang, China

Received:2020-03-26 Accepted:2020-05-01 Online:2021-01-18 Published:2021-01-18
Contact: Hong Du
About author:^*Tel: +86-13369677607; E-mail: 175790509@qq.com
Supported by:
National Natural Science Foundation of China(21862022);Scientific Research Program of the Higher Education Institution of Xinjiang, China(XJEDU2020Y028)

摘要/Abstract

摘要：

氢气是一种环境友好可再生的清洁能源, 电解水无疑是一种很好的制氢方法. 然而, 电催化分解水析氢受到其缓慢的动力学过程、较低的催化性能和较差的稳定性的限制. 为了使整个过程更节能, 具有高电流密度和低的过电势的高效电催化剂被广泛研究. 非化学计量相硒化钴(Co_0.85Se)作为一种重要的金属硫属化合物具有优异的催化性能而广受关注. 但是低维的Co_0.85Se活性位点少, 分散性差, 电子传递能力低, 导致其电催化剂活性差. 多壁碳纳米管(MWCNTs)具有多种电性能, 包括金属导电性和电子存储能力等. 因此, MWCNTs的特殊结构和高导电性可以有效地促进电子从电催化剂向碳纳米管的转移, 实现高效电分解水制氢性能.
本文在不使用表面活性剂和模板的情况下, 通过一步水热溶剂热法合成弱磁性Co_0.85Se纳米片负载碳纳米管电催化剂. 采用磁滞回线研究Co_0.85Se和MWCNTs/Co_0.85Se的磁性能, 结果表明其有弱顺磁性, Co_0.85Se纳米片之间的空间距离增强导致粒子间偶极相互作用减弱, 从而使MWCNTs/Co_0.85Se纳米复合材料的矫顽力值增加到158 Oe. 随着微晶尺寸的减小和纳米颗粒间距的增大, MWCNTs/Co_0.85Se催化剂的比表面积增大, 有利于提高其电催化活性. 扫描电镜和透射电镜展示出Co_0.85Se纳米片分散性较差, 且团聚现象严重, 而MWCNTs/Co_0.85Se纳米复合催化剂显示Co_0.85Se纳米片均匀分散在MWCNTs表面, 且纳米片尺寸明显减小, 有利于Co_0.85Se纳米片暴露更多的活性位点. 线性扫描伏安曲线测量表明, 在酸性溶液中Co_0.85Se纳米片在电流密度为10 mA cm^-2时, 其过电势为319 mV (vs. RHE), 30 wt% MWCNTs/Co_0.85Se的过电势为266 mV (vs. RHE). Co_0.85Se和MWCNTs/Co_0.85Se的Tafel斜率分别为92.6和60.5 mV dec^-1. 此外, MWCNTs/Co_0.85Se的电流交换密度(j₀)为0.07 mA cm^-2. 较小的Tafel斜率和高的电流交换密度表明, MWCNTs/Co_0.85Se具有良好的反应动力学和快速的质子分离速率. 交流阻抗谱表明MWCNTs/Co_0.85Se比Co_0.85Se电阻更小, 电子传输速率更快. 电化学活性表面积与双电层在固液界面处的电容测量值成正比. 结果显示, 30 wt% MWCNTs/Co_0.85Se的双电层电容为0.22 mF cm^-2, 高于Co_0.85Se和15 wt%的rGO/Co_0.85Se(0.04 mF cm^-2, 0.17 mF cm^-2), 这表明较大的电化学活性表面积有利于析氢反应进行. 30 wt% MWCNTs/Co_0.85Se的循环稳定测试表明其具有较好的稳定性.
综上, 本文介绍了通过一步水热法合成具有弱磁性的Co_0.85Se和MWCNTs/Co_0.85Se电催化剂, 碳纳米管作为一种高导电性材料被引入Co_0.85Se纳米片中以减少Co_0.85Se的团聚, 使Co_0.85Se的活性位点增加, 进而提高电催化制氢性能.

关键词: 硒化钴, 纳米复合物, 磁性, 电催化剂, 析氢反应

Abstract:

Co_0.85Se magnetic nanoparticles supported on carbon nanotubes were prepared by a one-step hydrothermal method. The saturation magnetization and coercivity of the MWCNTs/Co_0.85Se nanocomposites increased due to a decrease in the Co_0.85Se nanoparticle size in the MWCNTs/Co_0.85Se nanocomposites and an increase in the distance between the Co_0.85Se nanoparticles, which increased the specific surface area, thereby benefiting the electrocatalytic performance of the catalyst. Moreover, the MWCNTs/Co_0.85Se nanocomposites exhibited an excellent hydrogen evolution reaction performance owing to the presence of MWCNTs, which enhanced the mass transport during the electrocatalytic reactions. Furthermore, in an acid solution, the 30 wt% MWCNTs/Co_0.85Se composite catalyst exhibited a current density of 10 mA cm^-2 at a small overpotential of 266 mV vs. RHE, a small Tafel slope of 60.5 mV dec^-1, and good stability for HER.

Key words: Co_0.85Se, Nanocomposites, Magnetic, Electrocatalysis, Hydrogen evolution reaction

孙小惠, 努扎艾提·艾比布, 杜虹. 弱磁性Co_0.85Se纳米片负载碳纳米管作为电催化析氢催化剂[J]. 催化学报, 2021, 42(1): 235-243.

Xiaohui Sun, Nuzahat Habibul, Hong Du. Co_0.85Se magnetic nanoparticles supported on carbon nanotubes as catalyst for hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2021, 42(1): 235-243.

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图/表 9

Fig. 1. Schematic illustration of the preparation of MWCNTs/Co0.85Se nanocomposite.

Fig. 2. XRD patterns (a) and Raman spectra (b) of Co0.85Se, MWCNTs and 30 wt% MWCNTs/Co0.85Se.

Fig. 3. High-resolution XPS spectra of Co 2p (a), Se 3d (b), and C 1s (c) for 30 wt% MWCNTs/Co0.85Se.

Fig. 4. SEM images of Co0.85Se (a) and 30 wt% MWCNTs/Co0.85Se (b).

Fig. 5. TEM and HRTEM images of Co0.85Se (a,b) and MWCNTs/Co0.85Se (c,d); (e) STEM and EDS mapping images of MWCNTs/Co0.85Se.

Fig. 6. Magnetic hysteresis loops of Co0.85Se (a) and MWCNTs/Co0.85Se (b) at 27 °C.

Fig. 7. Electrochemical measurements of the samples. LSV curves (a) and Tafel slopes (b) of Co0.85Se, 30 wt% MWCNTs/Co0.85Se nanocomposite, and commercial 20 wt% Pt/C catalyst.

Fig. 8. (a) Electrochemical impedance spectra of Co0.85Se and 30 wt% MWCNTs/Co0.85Se composite at -0.2 V vs. RHE; (b) CV curves of 30 wt% MWCNTs/Co0.85Se; (c) estimated double-layer capacitances (CDL) of Co0.85Se and 30 wt% MWCNTs/Co0.85Se composite.

Fig. 9. (a) Durability test of 30 wt% MWCNTs/Co0.85Se before and after 1500 cycles; (b) time dependence of current density of 30 wt% MWCNTs/Co0.85Se at a static potential of 30 mV (vs. RHE).

参考文献

[1]	Q. S. Zhong, W. Y. Xia, B. C. Liu, C. W. Xu, N. Li, Int. J. Hydrogen Energy, 2019, 44, 10182-10189.
[2]	B. Yu, F. Qi, X. Q. Wang, B. J. Zheng, W. Q. Hou, Y. Hu, J. Lin, W. L. Zhang, Y. R. Li, Y. F. Chen, Electrochim. Acta, 2017, 247, 468-474.
[3]	J. N. Xing, F. Lin, L. T. Huang, Y. C. Si, Y. J. Wang, L. F. Jiao, Chin. J. Catal., 2019, 40, 1352-1359.
[4]	Y. F. Jiang, C. Z. Yuan, X. Zhou, Y. N. Liu, Z. W. Zhao, S. J. Zhao, A. W. Xu, Electrochim. Acta, 2018, 292, 247-255.
[5]	R. C. Shen, J. Xie, Q. J. Xiang, X. B. Chen, J. Z. Jiang, X. Li, Chin. J. Catal., 2019, 40, 240-288.
[6]	C. Z. Yuan, Y. F. Jiang, Z. W. Zhao, S. J. Zhao, X. Zhou, T. Y. Cheang, A. W. Xu, ACS Sustainable Chem. Eng., 2018, 6, 11529-11535.
[7]	P. F. Cheng, T. Feng, Z. W. Liu, D. Y. Wu, J. Yang, Chin. J. Catal., 2019, 40, 1147-1152.
[8]	P. Y. Kuang, T. Tong, K. Fan, J. G. Yu, ACS Catal., 2017, 7, 6179-6187.
[9]	J. Q. Wang, Z. Liu, C. H. Zhan, K. X. Zhang, X. Y. Lai, J. C. Tu, Y. Cao, J. Mater. Sci. Technol., 2020, 39, 155-160.
[10]	X. W. Hu, Y. H. Yin, W. Liu, X. W. Zhang, H. X. Zhang, Chin. J. Catal., 2019, 40, 1085-1092.
[11]	J. W. Li, Q. N. Zhuang, P. M. Xu, D. W. Zhang, L. C. Wei, D. S. Yuan, Chin. J. Catal., 2018, 39, 1403-1410.
[12]	X. L. Li, W. M. Xue, R. Mo, S. Yang, H. X. Li, J. X. Zhong, Chin. J. Catal., 2019, 40, 1576-1584.
[13]	H. Yuan, Q. Z. Jiao, J. Liu, X. F. Liu, Y. J. Li, D. X. Shi, Q. Wu, Y. Zhao, H. S. Li, Carbon, 2017, 122, 381-388.
[14]	G. Ma, C. Li, F. Liu, M. K. Majeed, Z. Feng, Y. Cui, Y. Qian, Mater. Today Energy, 2018, 10, 241-248.
[15]	X. H. Sun, H. Du, ACS Sustainable Chem. Eng., 2019, 7, 16320-16328.
[16]	L. Zhang, C. Zhang, Nanoscale, 2014, 6, 1782-1789.
[17]	B. Pan, Y. Wu, J. N. Qin, C. Y. Wang, Catal. Today, 2019, 335, 208-213.
[18]	J. F. Zhao, J. M. Song, C. C. Liu, B. H. Liu, H. L. Niu, C. J. Mao, Z. P. Zhang, CrystEngComm, 2011, 13, 5681-5684.
[19]	J. M. Song, C. C. Liu, S. S. Zhang, H. L. Niu, C. J. Mao, S. Y. Zhang, Y. H. Shen, Sep. Purif. Technol., 2014, 124, 148-154.
[20]	M. L.Yuan, M. Wang, P. L. Lu, Y. Sun, S. Dizapir, J. X. Zhang, S. W. Li, G. J. Zhang, J. Colloid Interface Sci., 2019, 533, 503-512.
[21]	T. Liu, Q. Liu, A. M. Asiri, Y. Luo, X. Sun, Chem. Commun., 2015, 51, 16683-16686.
[22]	Q. Liu, J. Q. Tian, W. Cui, P. Jiang, N. Y. Cheng, A. M. Asiri, X. P. Sun, Angew. Chem. Int. Ed., 2014, 53, 6710-6714.
[23]	R. Bose, T. H. Kim, B. Koh, C. Y. Jung, S. C. Yi, ChemistrySelect, 2017, 2, 10661-10667.
[24]	P. Y. Kuang, B. C. Zhu, Y. L. Li, H. B. Liu, J. G. Yu, K. Fan, Nanoscale Horiz., 2018, 3, 317-326.
[25]	Z. D. Meng, L. Zhu, K. Ullah, S. Ye, W. C. Oh, Appl. Surf. Sci., 2013, 286, 261-268.
[26]	G. Eda, G. Fanchini, M. Chhowalla, Nat. Nanotechnol., 2008, 3, 270-274.
[27]	X. R. Chen, J. W. Han, X. H. Lv, Z. Z. Pan, C. Luo, S. W. Zhang, Q. W. Qiao, F. Y. Fei, Q. H. Yang, J. Mater. Chem. A, 2019, 7, 12691-12697.
[28]	X. Xie, L. Lin, R. Y. Liu, Y. F. Jiang, Q. Zhu, A. W. Xu, J. Mater. Chem. A, 2015, 3, 8055-8061.
[29]	C. C. Liu, J. M. Song, J. F. Zhao, H. J. Li, H. S. Qian, H. L. Niu, C. J. Mao, S. Y. Zhang, Y. H. Shen, Appl. Catal. B, 2012, 119-120, 139-145.
[30]	J. L. Liu, J. B. Jiang, D. Qian, R. R. Tan, S. J. Peng, Y. H. Yuan, D. M. Luo, Q. F. Wang, Y. C. Liu, RSC Adv., 2013, 3, 15457-15466.
[31]	Y. Y. Zhang, Y. F. Qiu, X. Y. Ji, Z. Ma, A. P. Hu, ChemSusChem, 2019, 12, 3792-3800.
[32]	S. M. Senthil Kumar, K. Selvakumar, R. Thangamuthu, Int. J. Hydrogen Energy, 2018, 9, 4773-4783.
[33]	Z. Wu, J. Li, Z. Zou, X. Wang, J. Solid State Electrochem., 2018, 22, 1785-1794.
[34]	Q. Jiang, G. Hu, Materials Lett., 2015, 153, 114-117.
[35]	H. Wang, X. Wang, D. Yang, B. Zheng, Y. Chen, J. Power Sources, 2018, 400, 232-241.
[36]	Z. B. Feng, E. P. Wang, S. Huang, J. M. Liu, Nanoscale, 2020, 12, 4426-4434.
[37]	B. Yu, F. Qi, Y. Chen, X. Wang, B. Zheng, W. L. Zhang, Y. R. Li, L. C. Zhang, ACS Appl. Mater. Interfaces, 2017, 9, 30703-30710.
[38]	X. Xie, Y. F. Jiang, C. Z. Yuan, N. Jiang, S. J. Zhao, L. Jia, A. W. Xu, J. Phys. Chem. C, 2017, 121, 24979-24986.
[39]	X. Yang, W .Wang , L. P. Wu , X. J. Li, T. J. Wang, S. J. Liao, Appl. Catal. A, 2016, 526, 45-52.
[40]	T. Meng, Y. N. Hao, J. Qin, M. Cao, ACS Sustainable Chem. Eng., 2019, 7, 4657-4665.
[41]	A. Kapoor, A. B. Dey, C. Garg, A. Bajpai, Nanotechnology, 2019, 30(38), 385706.
[42]	Z. K. Heiba, N. Y. Mostafa, M. B. Mohamed, H. Al-Harthi, Mater. Lett., 2013, 93, 115-117.
[43]	H. B. Gu, C. Ma, J. W. Gu, J. Guo, X. R. Yan, J. N. Huang, Q. Y. Zhang, Z. H. Guo, J. Mater. Chem. C, 2016, 4, 5890-5906.
[44]	Y. Pan, Y. Lin, Y. Liu, C. Liu, Appl. Surf. Sci., 2016, 366, 439-447.
[45]	P. Y. Kuang, M. He, H. Y. Zou, J. G. Yu, K. Fan, Appl. Catal. B, 2019, 254, 15-25.
[46]	Q. Liu, J. Shi, J. Hu, A. M. Asiri, Y. Luo, X. Sun, ACS Appl. Mater. Interfaces, 2015, 7, 3877-3881.
[47]	P. Y. Kuang, M. He, B. C. Zhu, J. G. Yu, K. Fan, M. Jaroniec, J. Catal., 2019, 375, 8-20.
[48]	D. Kong, H. Wang, Z. Lu, Y. Cui, J Am. Chem. Soc., 2014, 136, 4897-4900.
[49]	Y. P. Zhu, H. C. Chen, C. S. Hsu, T. S. Lin, C. J. Chang, S. C. Chang, L. D. Tsai, H. M. Chen, ACS Energy Lett., 2019, 4, 987-994.
[50]	Y. Pan, Y. Lin, Y. Liu, C. Liu, Catal. Sci. Technol., 2016, 6, 1611-1615.
[51]	Q. Liu, J. Tian, W. Cui, P. Jiang, N. Cheng, A. M. Asiri, X. Sun, Angew. Chem. Int. Ed., 2014, 53, 6710-6714.
[52]	L. C. Wei, J. X. Luo, L. J. Jiang, L. J. Qiu, J. M. Zhang, D. W. Zhang, P. M. Xu, D. S. Yuan, Int. J Hydrogen Energy, 2018, 43, 20704-20711.
[53]	M. B. Li, H. H. Zhou, W. J. Yang, L. Cheng, Z. Huang, N. S. Zhang, C. P. Fu, Y. F. Kuan, J. Mater. Chem. A, 2017, 5, 1014-1021.
[54]	M. Y. Zhang, A. P. Hu, Z. Liu, Y. L. Xu, B. B. Fan, Q. L. Tang, S. Y. Zhang, W. N. Deng, X. H. Chen, Electrochim. Acta, 2018, 285, 254-261.
[55]	H. H. Gu, Y. P. Huang, L. Z. Zuo, W. Fan, T. Liu, Inorg. Chem. Front., 2016, 3, 1280-1288.
[56]	Y. R. Zheng, M. R. Gao, Z. Y. Yu, Q. Gao, H. L. Gao, S. H. Yu, Chem. Sci., 2015, 6, 4594.

弱磁性Co_0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

Co_0.85Se magnetic nanoparticles supported on carbon nanotubes as catalyst for hydrogen evolution reaction

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弱磁性Co0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

Co0.85Se magnetic nanoparticles supported on carbon nanotubes as catalyst for hydrogen evolution reaction

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弱磁性Co_0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

Co_0.85Se magnetic nanoparticles supported on carbon nanotubes as catalyst for hydrogen evolution reaction