无模板合成微米管状Co3O4基复合材料高效催化电解水析氧反应

doi:10.1016/S1872-2067(21)63902-5

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2275-2286.DOI: 10.1016/S1872-2067(21)63902-5

无模板合成微米管状Co₃O₄基复合材料高效催化电解水析氧反应

胡佳妮^a^,†, 张晓峰^a^,†, 肖娟^b, 李如春^a, 王毅^b, 宋树芹^a^,^*()

^a中山大学材料科学与工程学院, 广东省低碳化学与过程节能重点实验室, 聚合物复合材料及功能材料教育部重点实验室, 广东广州510275
^b中山大学化学工程与技术学院, 广东珠海519000

收稿日期:2021-02-05 接受日期:2021-02-05 出版日期:2021-12-18 发布日期:2021-09-10
通讯作者: 宋树芹
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(21975292);国家自然科学基金(21978331);国家自然科学基金(21905311);广东省基础与应用基础研究基金(2020A1515010343);广东省基础与应用基础研究基金(2021A1515010167);中央高校基本科研业务费专项资金(19lgpy136);中央高校基本科研业务费专项资金(19lgpy116);国家级大学生创新创业训练计划项目资金(202010558059)

Template-free synthesis of Co₃O₄ microtubes for enhanced oxygen evolution reaction

Jiani Hu^a^,†, Xiaofeng Zhang^a^,†, Juan Xiao^b, Ruchun Li^a, Yi Wang^b, Shuqin Song^a^,^*()

^aThe Key Lab of Low-carbon Chemistry & Energy Conservation of Guangdong Province, PCFM Lab, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, China
^bSchool of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519000, Guangdong, China

Received:2021-02-05 Accepted:2021-02-05 Online:2021-12-18 Published:2021-09-10
Contact: Shuqin Song
About author:* E-mail: stsssq@mail.sysu.edu.cn
First author contact:
^†Contributed equally.
Supported by:
National Natural Science Foundation of China(21975292);National Natural Science Foundation of China(21978331);National Natural Science Foundation of China(21905311);Guangdong Basic and Applied Basic Research Foundation(2020A1515010343);Guangdong Basic and Applied Basic Research Foundation(2021A1515010167);Fundamental Research Funds for Central Universities(19lgpy136);Fundamental Research Funds for Central Universities(19lgpy116);National Undergraduate Training Program for Innovation and Entrepreneurship(202010558059)

摘要/Abstract

摘要：

电解水制氢因具有清洁高效的优点而被认为是大规模生产氢能最有希望的技术之一. 然而, 电解水半反应之一的析氧反应(OER)需经历复杂且动力学缓慢的4电子转移过程. 加之热力学上的阻碍, OER实际需要的电位远大于1.23 V的理论值, 导致其能耗高, 限制了电解水的效率和商业化应用. 因此, 亟待开发高效的OER电催化剂.

管状结构具有较高的比表面积、充分暴露的活性位点和丰富的短路径扩散通道, 是一种理想的电催化结构. 同时, Co₃O₄基材料因其制备容易、成本低和OER电催化学活性较高等特点, 成为近年来电催化材料的研究热点. 此外, 非金属元素P的掺杂条件温和, 并且可以有效改变过渡金属电子结构. 因此, 本文通过合理设计管状的Co₃O₄基电催化剂并进行P掺杂, 尝试将形貌调控和元素改性的优势发挥到最大.

为了解析影响生成管状结构的因素, 本文通过控制变量法系统地研究了管状Ni/Co₃O₄的制备条件, 包括阳离子种类和含量、添加剂种类和含量、阴离子种类等对催化剂形貌和性能的影响. 表征结果表明, 初始的乙酸钴镍氢氧化物棱柱对反应环境较为敏感, 从而成为直接影响最终微米管状结构的关键因素. 此外, 对Ni/Co₃O₄微米管进行适量的P掺杂, 能提高材料的电子传输性能和优化材料的电子结构; 而且P的掺杂直接提高了样品中的M³⁺/M²⁺比例(M代表Co和Ni), 而M³⁺是M基电催化材料的活性位点, 这进一步增加了OER的活性位点进而提高其催化活性. 总之, 通过结构和成分的优化, 得到了OER催化性能显著提高的微米管状P-Ni/Co₃O₄, 其性能甚至超过了商业化RuO₂电催化剂.

关键词: 析氧反应, Co₃O₄, 微米管, P掺杂

Abstract:

To fully exploit the superiority of tubular structures, in this study, we systematically explore the optimal preparation conditions for Ni/Co₃O₄, including cation species and content, additive species and content, and anion species. Our results reveal that the formation of an initial cobalt nickel acetate hydroxide prism is the key factor and directly affects the final microtubular structure. Moreover, P is subsequently doped into the Ni/Co₃O₄ lattice to increase the M³⁺/M²⁺ molar ratio (M = Co and Ni), promote reaction kinetics, and optimize electronic structure. Consequently, the oxygen evolution reaction performance of P-doped tubular Ni/Co₃O₄ is significantly higher than that of undoped Ni/Co₃O₄ and the state-of-the-art RuO₂ electrocatalyst.

Key words: Oxygen evolution reaction, Co₃O₄, Microtube, P doping

胡佳妮, 张晓峰, 肖娟, 李如春, 王毅, 宋树芹. 无模板合成微米管状Co₃O₄基复合材料高效催化电解水析氧反应[J]. 催化学报, 2021, 42(12): 2275-2286.

Jiani Hu, Xiaofeng Zhang, Juan Xiao, Ruchun Li, Yi Wang, Shuqin Song. Template-free synthesis of Co₃O₄ microtubes for enhanced oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2021, 42(12): 2275-2286.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63902-5

https://www.cjcatal.com/CN/Y2021/V42/I12/2275

图/表 10

Fig. 1. (a) Schematic diagram of the fabrication process and architecture of precursors prepared via hydrothermal growth (I) using Co(Ac)2·4H2O, Ni(Ac)2·4H2O, 1,3-propanediol and absolute ethanol and precursors after pyrolysis at 400 °C in air (II); (b) XRD; (c) SEM; (d) TEM; (e) selected area electron diffraction pattern; (f) HRTEM; (g) STEM image; Co (h), Ni (i), and O (j) energy-dispersive X-ray spectroscopy mapping images of Ni-1/Co3O4-2-pro-9-Ac. Here, Ac and pro denote CH3COO- and 1,3-propanediol, respectively.

Fig. 2. XRD patterns and SEM images of Ni-1/Co3O4-2-eth-9-Ac (a,d), Ni-1/Co3O4-2-gly-9-Ac (b,e), and Ni-1/Co3O4-2-iso-9-Ac (c,f).

Fig. 3. (a) XRD patterns of Ni-1/Co3O4-2-pro-Y-Ac; SEM images of Ni-1/Co3O4-2-pro-0-Ac (b), Ni-1/Co3O4-2-pro-3-Ac (c), Ni-1/Co3O4-2-pro-6-Ac (d), Ni-1/Co3O4-2-pro-12-Ac (e), Ni-1/Co3O4-2-pro-15-Ac (f), and Ni-1/Co3O4-2-pro-50-Ac (g).

Fig. 4. XRD patterns (a-d) and SEM images (e-h) of Cu-1/Co3O4-2-pro-9-Ac (a,e), Fe-1/Co3O4-2-pro-9-Ac (b,f), Mn-1/Co3O4-2-pro-9-Ac (c,g), and Zn-1/Co3O4-2- pro-9-Ac (d,h).

Fig. 5. XRD patterns (a-c) and SEM images (d-f) of Ni-0/Co3O4-3-pro-9-Ac (a,d), Ni-2/Co3O4-1-pro-9-Ac (b,e), and Ni-3/Co3O4-0-pro-9-Ac (c,f).

Fig. 6. XRD pattern and SEM image of Ni-1/Co3O4-2-pro-9-NO.

Fig. 7. Polarization curves in 1 M KOH with iR correction (a,d,g,j,m), onset potentials and overpotentials at a current density of 10 mA cm-2 (b,e,h,k,n) and Tafel slopes (c,f,i,l,o) of Ni-1/Co3O4-2-N-9-Ac (a-c), Ni-1/Co3O4-2-pro-Y-Ac (d-f), M-1/Co3O4-2-pro-9-Ac (g-i), Ni-(3-X)/Co3O4-X-pro-9-Ac (j-l), and Ni-1/Co3O4-2-pro-9-A (m-o).

Fig. 8. (a) Schematic diagram of the fabrication process and P doping mechanism of Ni-1/Co3O4-2-pro-9-Ac; TEM image (b), selected area electron diffraction pattern (c), HRTEM image (d), STEM image (e), and Co (f), Ni (g), O (h) and P (i) energy-dispersive X-ray spectroscopy mapping images of P0.5-Ni-1/Co3O4-2-pro-9-Ac.

Fig. 9. Co 2p (a), Ni 2p (b), O 1s (c), and P 2p (d) XPS profiles of P0.5-Ni-1/Co3O4-2-pro-9-Ac and Ni-1/Co3O4-2-pro-9-Ac.

Fig. 10. (a) Polarization curves with iR correction; (b) Onset potential and overpotential at a current density of 10 mA cm-2; (c) Tafel slopes; (d) Nyquist plots at an applied potential of 1.52 V; (e) Cyclic voltammograms of P0.5-Ni-1/Co3O4-2-pro-9-Ac; (f) Electrochemical surface areas of Ni-1/Co3O4-2-pro-9-Ac, P0.5-Ni-1/Co3O4-2-pro-9-Ac, P3-Ni-1/Co3O4-2-pro-9-Ac, P5-Ni-1/Co3O4-2-pro-9-Ac in 1.0 M KOH.

参考文献

[1]	R. A. E Acredra, G. Gupta, M. Mamlouk, M. D. L. Balela, J. Alloys Compd., 2020, 836, 154919.
[2]	H. Du, W. Pu, C. Yang, Appl. Surf. Sci., 2020, 541, 148221.
[3]	Q. Yan, X. Li, Q. Zhao, G. Chen, J. Hazard Mater. 2012, 209-210, 385-391.
[4]	W. Liu, R. Liu, X. Zhang, Appl. Surf. Sci., 2020, 507, 145174.
[5]	P. Li, W. Chen, Chin. J. Catal., 2019, 40, 4-22.
[6]	M. K. Keshmarizi, A. F. Zonouz, F. Poursalehi, B. Mosallanejad, A. A. Daryakenari, J. Solid State Chem., 2020, 288, 121471.
[7]	Y. Y. Tan, Z. Y. Zhang, Z. Lei, W. Wu, W. B. Zhu, N. C. Cheng, S. C. Mu, J. Power Sources, 2020, 473, 228570.
[8]	B. Dong, J. Y. Xie, Z. Tong, J. Q. Chi, Y. N. Zhou, X. Ma, Z. Y. Lin, L. Wang, Y. M. Chai, Chin. J. Catal., 2020, 41, 1782-1789.
[9]	L. Sun, H. Li, L. Ren, C. Hu, Solid State Sci., 2009, 11, 109-112.
[10]	S. Jamil, M. R. S. A. Janjua, T. Ahmad, Solid State Sci., 2014, 36, 73-79.
[11]	J. Liu, C. Zhou, W. Yue, B. Yan, Y. Li, A. Huang, Chem. Phys. Lett., 2020, 756, 137817.
[12]	H. Du, W. Pu, C. Yang, Appl. Surf. Sci., 2020, 541, 148221.
[13]	I. Nikolov, R. Darkaoui, E. Zhecheva, R. Stoyanova, N. Dimitrov, T. Vitanov, J. Electroanal. Chem., 1997, 429, 157-168.
[14]	Y. C. Wang, T. Zhou, K. Jiang, P. M. Da, Z. Peng, J. Tang, B. A. Kong, W. B. Cai, Z. Q. Yang, G. F. Zheng, Adv. Energy Mater., 2014, 4, 1400696.
[15]	R. Subbaraman, D. Tripkovic, K. C. Chang, D. Strmcnik, A. P Paulikas, P. Hirunsit, M. Chan, J. Greeley, V. Stamenkovic, N. M. Markovic, Nat. Mater., 2012, 11, 550-557.
[16]	L. Li, Z. Hu, L. Tao, J. Xu, J. C. Yu, ACS Appl. Energy Mater., 2020, 3, 3071-3081.
[17]	J. Swaminathan, A. B. Puthirath, M. R. Sahoo, S. K. Nayak, G. Costin, R. Vajtai, T. Sharifi, P. M. Ajayan, ACS Appl. Mater. Interfaces, 2019, 11, 39706-39714.
[18]	Y. Qi, L. Zhang, L. Sun, G. Chen, Q. Luo, H. Xin, J. Peng, Y. Li, F. Ma, Nanoscale, 2020, 12, 1985-1993.
[19]	Q. Zhou, Z. Shen, C. Zhu, J. Li, Z. Ding, P. Wang, F. Pan, Z. Zhang, H. Ma, S. Wang, H. Zhang, Adv. Mater., 2018, 30, 1800140.
[20]	Z. Li, L. Lv, J. Wang, X. Ao, Y. Ruan, D. Zha, G. Hong, Q. Wu, Y. Lan, C. Wang, J. Jiang, M. Liu, Nano Energy, 2018, 47, 199-209.
[21]	X. Zhou, X. Liao, X. Pan, M. Yan, L. He, P. Wu, Y. Zhao, W. Luo, L. Mai, Nano Energy, 2021, 105748.
[22]	B. Qiu, L. Cai, Y. Wang, X. Guo, S. Ma, Y. Zhu, Y. H. Tsang, Z. Zheng, R. Zheng, Y. Chai, Small, 2019, 15, 1904507.
[23]	F. X. Ma, L. Yu, C. Y. Xu, X. W. Lou, Energy Environ. Sci., 2016, 9, 862-866.
[24]	J. W. Nai, Y. Tian, X. Guan, L. Guo, J. Am. Chem. Soc., 2013, 135, 16082-16091.
[25]	M. H. Oh, T. Yu, S. H. Yu, B. Lim, K. T. Ko, M. G. Willinger, D. H. Seo, B. H. Kim, M. G. Cho, J. H. Park, K. Kang, Y. E. Sung, N. Pinna, T. Hyeon, Science, 2013, 340, 964-968.
[26]	C. Xia, P. Li, A. N. Gandi, U. Schwingenschlögl, H. N. Alshareef, Chem. Mater., 2015, 27, 6482-6485.
[27]	Z. Kang, H. Guo, J. Wu, X. Sun, Z. Zhang, Q. Liao, S. Zhang, H. Si, P. Wu, L. Wang, Y. Zhang, Adv. Funct. Mater., 2019, 29, 1807031.
[28]	G. Zhang, H. Wang, J. Yang, Q. Zhao, L. Yang, H. Tang, C. Liu, H. Chen, Y. Lin, F. Pan, Inorg. Chem., 2018, 57, 2766-2772.
[29]	W. H. Lee, J. H. Moon, ACS Appl. Mater. Interfaces, 2014, 6, 13968-13976.
[30]	J. F. Marco, J. R. Gancedo, M. Gracia, J. L. Gautier, E. Rios, F. J. Berry, J. Solid State Chem., 2000, 153, 74-81.
[31]	R. Z. Chen, Y. Y. Tan, Z. Y. Zhang, Z. Lei, W. Wu, N. C. Cheng, S. C. Mu, ACS Sustain. Chem. Eng., 2020, 8, 9813-9821.
[32]	L. M. Tao, P. H. Guo, W. L. Zhu, T. L. Li, X. T. Zhou, Y. Q. Fu, C. L. Yu, H. B. Ji, Chin. J. Catal., 2020, 41, 1855-1863.
[33]	Y. Zhang, F. Ding, C. Deng, S. Zhen, X. Li, Y. Xue, Y. M. Yan, K. Sun, Catal. Commun., 2015, 67, 78-82.
[34]	Y. Liang, H. Wang, J. Zhou, Y. Li, J. Wang, T. Regier, H. J. Dai, J. Am. Chem. Soc., 2012, 134, 3517-3523.
[35]	H. Liu, X. Liu, Z. Mao, Z. Zhao, X. Peng, J. Luo, X. Sun, J. Power Sources, 2018, 400, 190-197.
[36]	Z. Liu, G. Wang, X. Zhu, Y. Wang, Y. Zou, S. Zang, S. Wang, Angew. Chem. Int. Ed., 2020, 59, 4736-4742.
[37]	L. S. Peng, S. S. A Shah, Z. D. Wei, Chin. J. Catal., 2018, 39, 1575-1593.
[38]	J. B. Gerken, S. E. Shaner, R. C. Massé, N. J. Porubsky, S. S. Stahl, Energy Environ. Sci., 2014, 7, 2376-2382.
[39]	L. Lu, B. Wang, S. Wang, Z. Shi, S. Yan, Z. Zou, Adv. Funct. Mater., 2017, 27, 1702447.
[40]	M. A. Mamun, X. Su, H. Zhang, H. Yin, P. Liu, H. Yang, D. Wang, Z. Tang, Y. Wang, H. Zhao, Small, 2016, 12, 2866-2871.
[41]	V. M. Jiménez, A. Fernández, J. P. Espinós, A. R. González-Elipe, J. Electron. Spectrosc. Relat. Phenom., 1995, 71, 61-71.
[42]	T. Choudhury, S. O. Saied, J. L. Sullivan, A. M. Abbot, J. Phy. D: Appl. Phys., 1989, 22, 1185-1195.
[43]	Y. Y. Tan, W. B. Zhu, Z. Y. Zhang, W. Wu, R. Z. Chen, S. C. Mu, H. F. Lv, N. C. Cheng, Nano Energy, 2021, 83, 105813.
[44]	H. Jang, W. Jin, G. Nam, Y. Yoo, J. S. Jeon, J. Park, M. G. Kim, J. Cho, Energy Environ. Sci., 2020, 13, 2167-2177.
[45]	Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, Chem. Soc. Rev., 2015, 44, 2060-2086.
[46]	H. F. Wang, C. Tang, Q. Zhang, Adv. Funct. Mater., 2018, 28, 1803329.
[47]	Z. Zheng, H. H. Wu, H. Liu, Q. Zhang, X. He, S. Yu, V. Petrova, J. Feng, R. Kostecki, P. Liu, D. L. Peng, M. Liu, M. S. Wang, ACS Nano, 2020, 14, 9545-9561.

无模板合成微米管状Co₃O₄基复合材料高效催化电解水析氧反应

Template-free synthesis of Co₃O₄ microtubes for enhanced oxygen evolution reaction

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