多级纳米喇叭花苯基膦酸钴在中性pH下高效电催化水氧化

引用本文: 刘美蓉, 林仰鹏, 王凯, 陈淑妹, 王飞, 周天华. 多级纳米喇叭花苯基膦酸钴在中性pH下高效电催化水氧化[J]. 催化学报, 2020, 41(10): 1654-1662. doi: S1872-2067(19)63513-8 shu

Citation: Mei-Rong Liu, Yang-Peng Lin, Kai Wang, Shumei Chen, Fei Wang, Tianhua Zhou. Hierarchical cobalt phenylphosphonate nanothorn flowers for enhanced electrocatalytic water oxidation at neutral pH[J]. Chinese Journal of Catalysis, 2020, 41(10): 1654-1662. doi: S1872-2067(19)63513-8 shu

多级纳米喇叭花苯基膦酸钴在中性pH下高效电催化水氧化

a 福州大学化学学院, 福建福州 350108;
b 中国科学院福建物质结构研究所, 结构化学国家重点实验室, 福建福州 350002;
c 四川师范大学化学与材料科学学院, 四川成都 610068
基金项目:
国家自然科学基金（51772291，21871050）.

摘要: 电催化水分解产氢是从根本上解决当前能源及环境等难题的最理想途径.然而，由于析氧反应（OER）是一个涉及多质子耦合电子转移的复杂过程，其动力学缓慢限制了水分解的效率，成为光电水分解的速控步骤，是相关应用发展的一大瓶颈，受到学术界与工业界的广泛关注.如何设计制备出性能高效、稳定性突出、价廉环保的水氧化催化剂，并揭示构-效关系及深入理解其催化机制成为该领域的重要课题.IrO₂和RuO₂等贵金属化合物被公认为当前最好的电催化析氧催化剂，但高成本及稀缺性严重限制了它们大规模应用.为此，开发高效低成本廉价过渡金属OER催化剂成为能源催化学科的研究热点与重点.
在已报道的过渡金属催化剂中，原位电沉积制备的磷酸钴（Co-Pi）被认为是迄今为止最有效的OER催化剂之一.尽管Co-Pi展现出诱人的性能，但无序的非晶态结构限制了对其结构进行精确描述，至今它的详细结构尚没有定论.由于其在结构方面的局限性，影响了进一步揭示水氧化催化剂构-效关系及深入理解水氧化机理.作为引入磷酸基构筑的晶态金属有机骨架材料，其柔性的多阴离子官能团可能带来更多可调控的结构因素，其丰富的可调控结构因素有助于从原子-分子水平上揭示水氧化催化剂构-效关系及加深理解其反应机理，使其有望成为一种最有希望的新型水氧化催化剂.近来，在研究水氧化功能的金属有机膦酸盐材料时，我们发现八面体钴的桥联方式以及钴与钴、钴与氧键长细微差别，却展现出不同水氧化活性.然而，迄今为止，关于水氧化功能的金属有机骨架材料特别膦酸盐骨架材料研究仍未见系统研究，并且目前报道的水氧化功能金属有机膦酸盐材料，主要是从晶体结构角度揭示其构-效关系以及理解其反应机理，此外，尚未见相关工作探讨形貌对OER催化性能影响.系统研究形貌自组装机制并进一步揭示它们对材料水氧化性能的影响无疑至关重要.
因此本文发展一种结构导向策略，通过水热法构建不同形貌的苯膦酸钴（CoP-X）OER催化剂，系统考察了它们的自组装机理及催化性能.研究发现，在不使用结构导向试剂时，合成的CoP-0为不规则的片状结构，而当引入分子量为40000的PVP结构导向试剂，能获得针状形貌的CoP-1.当分子量增加到58000，能进一步组装得到层状纳米喇叭花状的CoP-2.这可能是因为低分子量的PVP的官能团（N和O）与金属中心相互作用阻止纳米片的团聚.当PVP分子量进一步增加，导致羟基数量随着增加，材料表面的氢键相互作用从而加速材料生长.为了进一步研究羟基对形貌的影响，用乙二醇代替PVP并加入尿素和碳酸铵，则合成出均匀层状花形貌的CoP-3.我们推测可能是羟基的数量在调整形貌方面起着决定作用，而且尿素可以增加溶液碱度，促进多级结构的生长.电催化水氧化结果表明，在0.1M PBs溶液中（pH=7.0），纳米喇叭花状的CoP-2的OER活性最好，在1mA cm^-2处的过电势仅为393mV，Tafel斜率为81mV dec^-1.这为了发展新型金属有机膦酸盐水氧化催化剂提供了一个新思路.

关键词:

English

Hierarchical cobalt phenylphosphonate nanothorn flowers for enhanced electrocatalytic water oxidation at neutral pH

a College of Chemistry, Fuzhou University, Fuzhou 350108, Fujian, China;
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China;
c College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, Sichuan, China
Received Date: 25 February 2020
Revised Date: 29 March 2020
Fund Project:
This work was supported by the National Natural Science Foundation of China (51772291, 21871050).

Abstract: Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutral pH. Herein, we reported a facile hydrothermal synthesis of various nanostructured cobalt phenylphosphonates. It is found that the number of hydroxyl group of structure-directing reagent is crucial for the construction of 3D hierarchical structures including hierarchical nanosheet flower-like assemblies and nanothorn microsphere. These samples were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, infrared, and X-ray photoelectron spectroscopy techniques. They can act as highly efficient electrocatalysts for the oxygen evolution reaction at neutral pH. Among these, hierarchical cobalt phenylphosphonate nanothorn flowers present excellent performance, affording a current density of 1 mA cm^-2 required a small overpotential of 393 mV. This work offers a new clue to develop high-performance metal phosphonate/phosphate catalysts toward electrochemical water oxidation.

Key words:

1. [1] F. Raziq, L. Sun, Y. Wang, X. Zhang, M. Humayun, S. Ali, L. Bai, Y. Qu, H. Yu, L. Jing, Adv. Energy Mater., 2018, 8, 1701580.
2. [2] S. W. Boettcher, Nat. Catal., 2018, 1, 814-815.
3. [3] G. M. Whitesides, G. W. Crabtree, Science, 2007, 315, 796-798.
4. [4] G. Glenk, S. Reichelstein, Nat. Energy, 2019, 4, 216-222.
5. [5] J.-P. Zou, Y. Chen, S.-S. Liu, Q.-J. Xing, W.-H. Dong, X.-B. Luo, W.-L. Dai, X. Xiao, J.-M. Luo, J. Crittenden, Water Res., 2019, 150, 330-339.
6. [6] H. Huang, J. Lin, G. Zhu, Y. Weng, X. Wang, X. Fu, J. Long, Angew. Chem. Int. Ed., 2016, 55, 8314-8318.
7. [7] G. Cui, X. Yang, Y. Zhang, Y. Fan, P. Chen, H. Cui, Y. Liu, X. Shi, Q. Shang, B. Tang, Angew. Chem. Int. Ed., 2019, 58, 1340-1344.
8. [8] Y. Guo, P. Wang, J. Qian, Y. Ao, C. Wang, J. Hou, Appl. Catal. B, 2018, 234, 90-99.
9. [9] W. Liu, J. Shen, X. Yang, Q. Liu, H. Tang, Appl. Surf. Sci., 2018, 456, 369-378.
10. [10] T. Zhou, D. Wang, S. Chun-Kiat Goh, J. Hong, J. Han, J. Mao, R. Xu, Energy Environ. Sci., 2015, 8, 526-534.
11. [11] H. N. Nong, T. Reier, H.-S. Oh, M. Gliech, P. Paciok, T. H. T. Vu, D. Teschner, M. Heggen, V. Petkov, R. Schlögl, T. Jones, P. Strasser, Nat. Catal., 2018, 1, 841-851.
12. [12] M. R. Liu, Q. L. Hong, Q. H. Li, Y. Du, H. X. Zhang, S. Chen, T. Zhou, J. Zhang, Adv. Funct. Mater., 2018, 28, 1801136.
13. [13] Z. Wang, W. Xu, X. Chen, Y. Peng, Y. Song, C. Lv, H. Liu, J. Sun, D. Yuan, X. Li, X. Guo, D. Yang, L. Zhang, Adv. Funct. Mater., 2019, 29, 1902875.
14. [14] Z. Chen, Q. Huang, B. Huang, F. Zhang, C. Li, Chin. J. Catal., 2019, 40, 38-42.
15. [15] F. Li, H. Li, Y. Zhu, J. Du, Y. Wang, L. Sun, Chin. J. Catal., 2017, 38, 1812-1817.
16. [16] Y. Li, F.-M. Li, X.-Y. Meng, S.-N. Li, J.-H. Zeng, Y. Chen, ACS Catal., 2018, 8, 1913-1920.
17. [17] P. Cai, J. Huang, J. Chen, Z. Wen, Angew. Chem. Int. Ed., 2017, 56, 4858-4861.
18. [18] X.-T. Wang, T. Ouyang, L. Wang, J.-H. Zhong, T. Ma, Z.-Q. Liu, Angew. Chem. Int. Ed., 2019, 10.1002/anie.201907595.
19. [19] B.-Q. Li, C.-X. Zhao, S. Chen, J.-N. Liu, X. Chen, L. Song, Q. Zhang, Adv. Mater., 2019, 31, 1900592.
20. [20] Q. Qin, H. Jang, P. Li, B. Yuan, X. Liu, J. Cho, Adv. Energy Mater., 2019, 9, 1803312.
21. [21] J. Chang, Y. Xiao, M. Xiao, J. Ge, C. Liu, W. Xing, ACS Catal., 2015, 5, 6874-6878.
22. [22] S. She, Y. Zhu, Y. Chen, Q. Lu, W. Zhou, Z. Shao, Adv. Energy Mater., 2019, 9, 1900429.
23. [23] D. Chen, M. Qiao, Y.-R. Lu, L. Hao, D. Liu, C.-L. Dong, Y. Li, S. Wang, Angew. Chem. Int. Ed., 2018, 57, 8691-8696.
24. [24] L. Lv, Z. Yang, K. Chen, C. Wang, Y. Xiong, Adv. Energy Mater., 2019, 9, 1803358.
25. [25] D. Zhou, S. Wang, Y. Jia, X. Xiong, H. Yang, S. Liu, J. Tang, J. Zhang, D. Liu, L. Zheng, Y. Kuang, X. Sun, B. Liu, Angew. Chem. Int. Ed., 2019, 58, 736-740.
26. [26] T. Wang, G. Nam, Y. Jin, X. Wang, P. Ren, M.G. Kim, J. Liang, X. Wen, H. Jang, J. Han, Y. Huang, Q. Li, J. Cho, Adv. Mater., 2018, 30, 1800757.
27. [27] S. Yin, W. Tu, Y. Sheng, Y. Du, M. Kraft, A. Borgna, R. Xu, Adv. Mater., 2018, 30, 1705106.
28. [28] J. Zhang, J. Liu, L. Xi, Y. Yu, N. Chen, S. Sun, W. Wang, K. M. Lange, B. Zhang, J. Am. Chem. Soc., 2018, 140, 3876-3879.
29. [29] J. Li, W. Huang, M. Wang, S. Xi, J. Meng, K. Zhao, J. Jin, W. Xu, Z. Wang, X. Liu, Q. Chen, L. Xu, X. Liao, Y. Jiang, K. A. Owusu, B. Jiang, C. Chen, D. Fan, L. Zhou, L. Mai, ACS Energy Lett., 2019, 4, 285-292.
30. [30] X. Zhao, B. Pattengale, D. Fan, Z. Zou, Y. Zhao, J. Du, J. Huang, C. Xu, ACS Energy Lett., 2018, 3, 2520-2526.
31. [31] X.-L. Wang, L.-Z. Dong, M. Qiao, Y.-J. Tang, J. Liu, Y. Li, S.-L. Li, J.-X. Su, Y.-Q. Lan, Angew. Chem. Int. Ed., 2018, 57, 9660-9664.
32. [32] W. Zhou, D.-D. Huang, Y.-P. Wu, J. Zhao, T. Wu, J. Zhang, D.-S. Li, C. Sun, P. Feng, X. Bu, Angew. Chem. Int. Ed., 2019, 58, 4227-4231.
33. [33] W. Cheng, X. Zhao, H. Su, F. Tang, W. Che, H. Zhang, Q. Liu, Nat. Energy, 2019, 4, 115-122.
34. [34] J. Li, W. Huang, M. Wang, S. Xi, J. Meng, K. Zhao, J. Jin, W. Xu, Z. Wang, X. Liu, Q. Chen, L. Xu, X. Liao, Y. Jiang, K.A. Owusu, B. Jiang, C. Chen, D. Fan, L. Zhou, L. Mai, ACS Energy Lett., 2019, 4, 285-292.
35. [35] F. L. Li, Q. Shao, X. Huang, J. P. Lang, Angew. Chem. Int. Ed., 2018, 57, 1888-1892.
36. [36] X.-F. Lu, P.-Q. Liao, J.-W. Wang, J.-X. Wu, X.-W. Chen, C.-T. He, J.-P. Zhang, G.-R. Li, X.-M. Chen, J. Am. Chem. Soc., 2016, 138, 8336-8339.
37. [37] S. Zhao, Y. Wang, J. Dong, C.-T. He, H. Yin, P. An, K. Zhao, X. Zhang, C. Gao, L. Zhang, J. Lv, J. Wang, J. Zhang, A. M. Khattak, N. A. Khan, Z. Wei, J. Zhang, S. Liu, H. Zhao, Z. Tang, Nat. Energy, 2016, 1, 16184.
38. [38] M. Jiang, J. Chen, Y. Li, Chin. J. Catal., 2018, 39, 1017-1026.
39. [39] J. Lin, B. Ma, M. Chen, Y. Ding, Chin. J. Catal., 2018, 39, 463-471.
40. [40] N. Wang, H. Zheng, W. Zhang, R. Cao, Chin. J. Catal., 2018, 39, 228-244.
41. [41] X. Wang, Z.-F. Cai, D. Wang, L.-J. Wan, J. Am. Chem. Soc., 2019, 141, 7665-7669.
42. [42] J. Huang, Y. Sun, Y. Zhang, G. Zou, C. Yan, S. Cong, T. Lei, X. Dai, J. Guo, R. Lu, Y. Li, J. Xiong, Adv. Mater., 2018, 30, 1705045.
43. [43] P. Feng, X. Cheng, J. Li, X. Luo, ChemistrySelect, 2018, 3, 760-764.
44. [44] R. Guo, X. Lai, J. Huang, X. Du, Y. Yan, Y. Sun, G. Zou, J. Xiong, ChemElectroChem, 2018, 5, 3822-3834.
45. [45] M. W. Kanan, D. G. Nocera, Science, 2008, 321, 1072-1075.
46. [46] M. Risch, V. Khare, I. Zaharieva, L. Gerencser, P. Chernev, H. Dau, J. Am. Chem. Soc., 2009, 131, 6936-6937.
47. [47] M. W. Kanan, J. Yano, Y. Surendranath, M. Dincă, V. K. Yachandra, D. G. Nocera, J. Am. Chem. Soc., 2010, 132, 13692-13701.
48. [48] H. Kim, J. Park, I. Park, K. Jin, S. E. Jerng, S. H. Kim, K. T. Nam, K. Kang, Nat Commun, 2015, 6, 8253-8263.
49. [49] J. Park, H. Kim, K. Jin, B. J. Lee, Y.-S. Park, H. Kim, I. Park, K. D. Yang, H.-Y. Jeong, J. Kim, K. T. Hong, H. W. Jang, K. Kang, K. T. Nam, J. Am. Chem. Soc., 2014, 136, 4201-4211.
50. [50] Z. Zhao, H. Wu, H. He, X. Xu, Y. Jin, Adv. Funct. Mater., 2014, 24, 4698-4705.
51. [51] K. Jin, J. Park, J. Lee, K. D. Yang, G. K. Pradhan, U. Sim, D. Jeong, H. L. Jang, S. Park, D. Kim, N.-E. Sung, S. H. Kim, S. Han, K. T. Nam, J. Am. Chem. Soc., 2014, 136, 7435-7443.
52. [52] C. P. Plaisance, R. A. van Santen, J. Am. Chem. Soc., 2015, 137, 14660-14672.
53. [53] T. Zhou, Y. Du, D. Wang, S. Yin, W. Tu, Z. Chen, A. Borgna, R. Xu, ACS Catal., 2017, 7, 6000-6007.
54. [54] R. Zhang, P. A. Russo, A. G. Buzanich, T. Jeon, N. Pinna, Adv. Funct. Mater., 2017, 27, 1703158.
55. [55] J. Saha, D. Roy Chowdhury, P. Jash, A. Paul, Chem. Eur. J, 2017, 23, 12519-12526.
56. [56] W.-X. Lu, B. Wang, W.-J. Chen, J.-L. Xie, Z.-Q. Huang, W. Jin, J.-L. Song, ACS Sustainable Chem. Eng., 2019, 7, 3083-3091.
57. [57] T. O. Salami, X. Fan, P. Y. Zavalij, S. R. J. Oliver, Dalton Trans, 2006, 1574-1578.
58. [58] T.-H. Zhou, F.-Y. Yi, P.-X. Li, J.-G. Mao, Inorg. Chem., 2010, 49, 905-915.
59. [59] Z. Liu, R. Ma, M. Osada, K. Takada, T. Sasaki, J. Am. Chem. Soc., 2005, 127, 13869-13874.
60. [60] K. M. Koczkur, S. Mourdikoudis, L. Polavarapu, S. E. Skrabalak, Dalton Trans., 2015, 44, 17883-17905.
61. [61] X. W. Lou, L. A. Archer, Adv. Mater., 2008, 20, 1853-1858.
62. [62] J. S. Chen, J. Liu, S. Z. Qiao, R. Xu, X. W. Lou, Chem. Commun., 2011, 47, 10443-10445.
63. [63] H. Shi, H. Liang, F. Ming, Z. Wang, Angew. Chem. Int. Ed, 2017, 56, 573-577.
64. [64] L. Zhan, S. Wang, L.-X. Ding, Z. Li, H. Wang, J. Mater. Chem. A, 2015, 3, 19711-19717.
65. [65] J. Wang, C. F. Tan, T. Zhu, G. W. Ho, Angew. Chem. Int. Ed., 2016, 55, 10326-10330.

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沈阳化工大学材料科学与工程学院沈阳 110142

多级纳米喇叭花苯基膦酸钴在中性pH下高效电催化水氧化

English

Hierarchical cobalt phenylphosphonate nanothorn flowers for enhanced electrocatalytic water oxidation at neutral pH

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中国化学会秘书处

多级纳米喇叭花苯基膦酸钴在中性pH下高效电催化水氧化

English

Hierarchical cobalt phenylphosphonate nanothorn flowers for enhanced electrocatalytic water oxidation at neutral pH

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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