不对称配位磷酸钴铵增强电催化水氧化反应性能

doi:10.1016/S1872-2067(21)64035-4

摘要/Abstract

摘要：

钴基材料被认为是有望替代贵金属材料的电催化水氧化反应催化剂之一. 研究发现, 高活性的钴基催化剂常发生表面重构行为, 深入研究表面重构行为对于阐明真实的催化活性位点和指导合成高性能的电催化剂至关重要. 但是受到复杂的催化剂结构以及多种性能影响因素限制, 钴基材料的配位结构对表面重构和电催化水氧化性能影响仍不清晰. 基于此, 本文设计了具有配位对称结构和不对称结构的两种磷酸钴基材料用于电催化水氧化反应, 探索配位对称性对表面重构和水氧化性能的影响.

本文通过调控共沉淀反应中磷酸铵的用量, 合成了具有对称配位结构的磷酸钴材料和不对称配位结构的磷酸钴铵材料. 采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和物理吸附等技术表征了两种材料的物理性质. 通过线性扫描法, 循环伏安法和恒电位电解法等电化学方法测定两种材料的电催化水氧化活性和稳定性. 采用原位电化学阻抗图谱、拉曼光谱(Raman)和XPS图分析水氧化反应中的表面重构过程.

晶体结构图表明, 磷酸钴材料和磷酸钴铵材料均由六配位的CoO₆八面体组成. 其中, 磷酸钴结构中钴中心由四个水分子和两个磷酸基团或两个水分子和四个磷酸基团配位, 钴-氧键键长呈现对称性. 在层间引入铵根离子后, 钴中心由一个水分子和五个磷酸基团配位, 形成具有不对称结构单元的磷酸钴铵结构. SEM和TEM结果表明, 两种材料具有类似的片状形貌. XPS分析发现, 两种材料具有相同的元素价态. 因此, 两种材料成为探索配位对称性对水氧化反应影响的理想平台.

在0.1 mol/L磷酸缓冲溶液中, 不对称配位磷酸钴铵的本征催化活性明显高于对称配位的磷酸钴催化剂. 利用原位阻抗分析, Raman光谱和XPS图谱研究了催化剂表面的化学状态, 测试结果表明, 不对称配位的八面体钴中心有利于原位生成活性氧化钴物种从而提高水氧化性能. 理论计算进一步证明不对称配位的钴中心可以增强Co-O共价性, 促进Co离子和含氧中间体之间的电子转移, 加速水氧化过程中的表面重构. 综上, 本文深入分析了水氧化反应的表面重构行为, 并为开发高性能的水氧化反应催化剂提供了新思路.

关键词: 磷酸钴铵, 配位对称性, 表面重构, 电催化, 水氧化反应

Abstract:

Cobalt-based materials have been considered as promising candidates to electrocatalyze water oxidation. However, the structure-performance correlation remains largely elusive, due to the complex material structures and diverse performance-influencing factors in those Co-based catalysts. In this work, we designed two cobalt phosphates with distinct Co symmetry to explore the effect of coordination symmetry on electrocatalytic water oxidation. The two analogues have similar morphology, Co valence and 6-coordinated Co octahedron, but with different coordination symmetry. In contrast to symmetric Co₃(PO₄)₂·8H₂O, asymmetric NH₄CoPO₄·H₂O exhibited enhanced electrocatalytic water oxidation activity in a neutral aqueous solution. It is proven that, by experimental and theoretical studies, the asymmetric Co coordination sites can facilitate the surface reconstruction under anodic polarization to boost the electrocatalysis. Based on this contrastive platform with distinct symmetry differences, the preferred configuration in cobalt-oxygen octahedrons for water oxidation has been straightforwardly assigned.

Key words: Ammonium cobalt phosphate, Coordination symmetry, Surface reconstruction, Electrocatalysis, Oxygen evolution reaction

齐静, 陈明星, 张伟, 曹睿. 不对称配位磷酸钴铵增强电催化水氧化反应性能[J]. 催化学报, 2022, 43(7): 1955-1962.

Jing Qi, Mingxing Chen, Wei Zhang, Rui Cao. Ammonium cobalt phosphate with asymmetric coordination sites for enhanced electrocatalytic water oxidation[J]. Chinese Journal of Catalysis, 2022, 43(7): 1955-1962.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64035-4

https://www.cjcatal.com/CN/Y2022/V43/I7/1955

图/表 5

Fig. 1. The crystal structures of the NH4CoPO4·H2O (a,c) and Co3(PO4)2·8H2O (b,d) materials.

Fig. 2. (a) The XRD patterns of the Co-based materials synthesized with different amounts of ammonium phosphate. The black and red vertical lines are the standard XRD patterns of Co3(PO4)2·8H2O (65687-ICSD) and NH4CoPO4·H2O (280044-ICSD), respectively. The TEM and SEM images of the Co3(PO4)2·8H2O (b,d) and NH4CoPO4·H2O (c,e).

Fig. 3. LSV curves (a), Tafel plots (b), Bode phase plots (c,d) of NH4CoPO4·H2O and Co3(PO4)2·8H2O in 0.1 mol/L phosphate buffer solution (pH = 7).

Fig. 4. Raman and XPS spectra of NH4CoPO4·H2O (a,c) and Co3(PO4)2·8H2O (b,d) under different electrolysis time.

Fig. 5. DFT crystal models, computed DOS and PDOS of NH4CoPO4·H2O (a-c) and Co3(PO4)2·8H2O (d-f).

参考文献

[1]	M. D. Symes, L. Cronin, Nat. Chem., 2013, 5, 403-409.
[2]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[3]	J. Qi, W. Zhang, R. Cao, Adv. Energy Mater., 2018, 8, 1701620.
[4]	Z. Liang, C. Qu, W. Guo, R. Zou, Q. Xu, Adv. Mater., 2018, 30, 1702891.
[5]	M. T. M. Koper, J. Electroanal. Chem., 2011, 660, 254-260.
[6]	M. M. Najafpour, G. Renger, M. Hołyńska, A. N. Moghaddam, E.-M. Aro, R. Carpentier, H. Nishihara, J. J. Eaton-Rye, J.-R. Shen, S. I. Allakhverdiev, Chem. Rev., 2016, 116, 2886-2936.
[7]	Y. Yan, C. Liu, H. Jian, X. Cheng, T. Hu, D. Wang, L. Shang, G. Chen, P. Schaaf, X. Wang, E. Kan, T. Zhang, Adv. Funct. Mater., 2021, 31, 2009610.
[8]	M. Yu, E. Budiyanto, H. Tüysüz, Angew. Chem. Int. Ed., 2021, 61, e202103824.
[9]	R. Beltrán-Suito, V. Forstner, J. N. Hausmann, S. Mebs, J. Schmidt, I. Zaharieva, K. Laun, I. Zebger, H. Dau, P. W. Menezes, M. Driess, Chem. Sci., 2020, 11, 11834-11842.
[10]	C.-X. Zhao, B.-Q. Li, M. Zhao, J.-N. Liu, L.-D. Zhao, X. Chen, Q. Zhang, Energy Environ. Sci., 2020, 13, 1711-1716.
[11]	W. Feng, H. Chen, Q. Zhang, R. Gao, X. Zou, Chin. J. Catal., 2020, 41, 1692-1697.
[12]	D. K. Bediako, C. Costentin, E. C. Jones, D. G. Nocera, J.-M. Savéant, J. Am. Chem. Soc., 2013, 135, 10492-10502.
[13]	Y. Shao, X. Xiao, Y.-P. Zhu, T.-Y. Ma, Angew. Chem. Int. Ed., 2019, 58, 14599-14604.
[14]	P. W. Menezes, C. Panda, C. Walter, M. Schwarze, M. Driess, Adv. Funct. Mater., 2019, 29, 1808632.
[15]	F. Dionigi, Z. Zeng, I. Sinev, T. Merzdorf, S. Deshpande, M. B. Lopez, S. Kunze, I. Zegkinoglou, H. Sarodnik, D. Fan, A. Bergmann, J. Drnec, J. F. de Araujo, M. Gliech, D. Teschner, J. Zhu, W.-X. Li, J. Greeley, B. R. Cuenya, P. Strasser, Nat. Commun., 2020, 11, 2522.
[16]	P. Chen, Y. Tong, C. Wu, Y. Xie, Acc. Chem. Res., 2018, 51, 2857-2866.
[17]	C. Baeumer, J. Li, Q. Lu, A. Y.-L. Liang, L. Jin, H. P. Martins, T. Duchon, M. Gloss, S. M. Gericke, M. A. Wohlgemuth, M. Giesen, E. E. Penn, R. Dittmann, F. Gunkel, R. Waser, M. Bajdich, S. Nemsak, J. T. Mefford, W. C. Chueh, Nat. Mater., 2021, 20, 674-682.
[18]	C. Guo, Y. Shi, S. Lu, Y. Yu, B. Zhang, Chin. J. Catal., 2021, 42, 1287-1296.
[19]	E. Fabbri, M. Nachtegaal, T. Binninger, X. Cheng, B.-J. Kim, J. Durst, F. Bozza, T. Graule, R. Schäublin, L. Wiles, M. Pertoso, N. Danilovic, K. E. Ayers, T. J. Schmidt, Nat. Mater., 2017, 16, 925-931.
[20]	J. Song, C. Wei, Z.-F. Huang, C. Liu, L. Zeng, X. Wang, Z. J. Xu, Chem. Soc. Rev., 2020, 49, 2196-2214.
[21]	Z. Liu, G. Wang, X. Zhu, Y. Wang, Y. Zou, S. Zang, S. Wang, Angew. Chem. Int. Ed., 2020, 59, 4736-4742.
[22]	H. Wan, R. Ma, X. Liu, J. Pan, H. Wang, S. Liang, G. Qiu, T. Sasaki, ACS Energy Lett., 2018, 3, 1254-1260.
[23]	T. W. Kim, M. A. Woo, M. Regis, K.-S. Choi, J. Phys. Chem. Lett., 2014, 5, 2370-2374.
[24]	R. D. L. Smith, C. Pasquini, S. Loos, P. Chernev, K. Klingan, P. Kubella, M. R. Mohammadi, D. González-Flores, H. Dau, Energy Environ. Sci., 2018, 11, 2476-2485.
[25]	H. Kim, J. Park, I. Park, K. Jin, S. E. Jerng, S. H. Kim, K. T. Nam, K. Kang, Nat. Commun., 2015, 6, 8253.
[26]	J. Huang, J. Chen, T. Yao, J. He, S. Jiang, Z. Sun, Q. Liu, W. Cheng, F. Hu, Y. Jiang, Z. Pan, S. Wei, Angew. Chem. Int. Ed., 2015, 54, 8722-8727.
[27]	S. Sun, Y. Sun, Y. Zhou, S. Xi, X. Ren, B. Huang, H. Liao, L. P. Wang, Y. Du, Z. J. Xu, Angew. Chem. Int. Ed., 2019, 58, 6042-6047.
[28]	Z. Zhang, C. Liu, C. Feng, P. Gao, Y. Liu, F. Ren, Y. Zhu, C. Cao, W. Yan, R. Si, S. Zhou, J. Zeng, Nano Lett., 2019, 19, 8774-8779.
[29]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[30]	G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[31]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[32]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[33]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010, 132, 154104.
[34]	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.
[35]	W. Zheng, L. Y. S. Lee, ACS Energy Lett., 2021, 6, 2838-2843.
[36]	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.
[37]	S. Yang, S. Wan, F. Shang, D. Chen, W. Zhang, R. Cao, Chem. Commun., 2021, 57, 6165-6168.
[38]	C. C. L. McCrory, S. Jung, J. C. Peters, T. F. Jaramillo, J. Am. Chem. Soc., 2013, 135, 16977-16987.
[39]	Y. Surendranath, M. W. Kanan, D. G. Nocera, J. Am. Chem. Soc., 2010, 132, 16501-16509.
[40]	H. Liu, X. Gao, X. Yao, M. Chen, G. Zhou, J. Qi, X. Zhao, W. Wang, W. Zhang, R. Cao, Chem. Sci., 2019, 10, 191-197.
[41]	J. Qi, Y.-P. Lin, D. Chen, T. Zhou, W. Zhang, R. Cao, Angew. Chem. Int. Ed., 2020, 59, 8917-8921.
[42]	Z. Xiao, Y.-C. Huang, C.-L. Dong, C. Xie, Z. Liu, S. Du, W. Chen, D. Yan, L. Tao, Z. Shu, G. Zhang, H. Duan, Y. Wang, Y. Zou, R. Chen, S. Wang, J. Am. Chem. Soc., 2020, 142, 12087-12095.
[43]	R. L. Frost, Spectrochim. Acta, Part A, 2004, 60, 1439-1445.
[44]	Y. Li, W. Qiu, F. Qin, H. Fang, V. G. Hadjiev, D. Litvinov, J. Bao, J. Phys. Chem. C, 2016, 120, 4511-4516.
[45]	J. Yang, H. Liu, W. N. Martens, R. L. Frost, J. Phys. Chem. C, 2010, 114, 111-119.
[46]	Y. Duan, S. Sun, Y. Sun, S. Xi, X. Chi, Q. Zhang, X. Ren, J. Wang, S. J. H. Ong, Y. Du, L. Gu, A. Grimaud, Z. J. Xu, Adv. Mater., 2019, 31, 1807898.
[47]	W. T. Hong, K. A. Stoerzinger, Y.-L. Lee, L. Giordano, A. Grimaud, A. M. Johnson, J. Hwang, E. J. Crumlin, W. Yang, Y. Shao-Horn, Energy Environ. Sci., 2017, 10, 2190-2200.
[48]	Y. Zhou, S. Sun, J. Song, S. Xi, B. Chen, Y. Du, A. C. Fisher, F. Cheng, X. Wang, H. Zhang, Z. J. Xu, Adv. Mater., 2018, 30, 1802912.
[49]	T. Wu, X. Ren, Y. Sun, S. Sun, G. Xian, G. G. Scherer, A. C. Fisher, D. Mandler, J. W. Ager, A. Grimaud, J. Wang, C. Shen, H. Yang, J. Gracia, H.-J. Gao, Z. J. Xu, Nat. Commun., 2021, 12, 3634.
[50]	J. Wang, S.-J. Kim, J. Liu, Y. Gao, S. Choi, J. Han, H. Shin, S. Jo, J. Kim, F. Ciucci, H. Kim, Q. Li, W. Yang, X. Long, S. Yang, S.-P. Cho, K. H. Chae, M. G. Kim, H. Kim, J. Lim, Nat. Catal., 2021, 4, 212-222.
[51]	X.-T. Wang, T. Ouyang, L. Wang, J.-H. Zhong, T. Ma, Z.-Q. Liu, Angew. Chem. Int. Ed., 2019, 58, 13291-13296.
[52]	J. Liu, Q. Hu, Y. Wang, Z. Yang, X. Fan, L.-M. Liu, L. Guo, Proc. Natl. Acad. Sci. U. S. A., 2020, 117, 21906-21913.
[53]	X. Bu, C. Chiang, R. Wei, Z. Li, Y. Meng, C. Peng, Y. Lin, Y. Li, Y. Lin, K. S. Chan, J. C. Ho, ACS Appl. Mater. Interfaces, 2019, 11, 38633-38640.