Metal-Triazolate-Framework-Derived FeN4Cl1 Single-Atom Catalysts with Hierarchical Porosity for the Oxygen Reduction Reaction
Linyu Hu
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorChunlong Dai
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorLiwei Chen
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorYuhao Zhu
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorYuchen Hao
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorDr. Qinghua Zhang
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Science, Beijing, 100081 P. R. China
Search for more papers by this authorProf. Dr. Lin Gu
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Science, Beijing, 100081 P. R. China
Search for more papers by this authorProf. Dr. Xiao Feng
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorShuai Yuan
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorCorresponding Author
Dr. Lu Wang
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Bo Wang
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorLinyu Hu
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorChunlong Dai
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorLiwei Chen
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorYuhao Zhu
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorYuchen Hao
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorDr. Qinghua Zhang
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Science, Beijing, 100081 P. R. China
Search for more papers by this authorProf. Dr. Lin Gu
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Science, Beijing, 100081 P. R. China
Search for more papers by this authorProf. Dr. Xiao Feng
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorShuai Yuan
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorCorresponding Author
Dr. Lu Wang
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Bo Wang
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Advanced Technology Research Institute (Jinan), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 P. R. China
Search for more papers by this authorGraphical Abstract
A Zn/Fe-bimetallic metal-triazolate framework (MET) modified with 4,5-dichloroimidazole (dcIm) was used to prepare the Fe single-atom catalyst FeN4Cl1/NC. In the oxygen reduction reaction (ORR), the catalyst offers fast mass transfer and high catalytic activity because of abundant mesopores (pore:volume ratio 0.92), a high Fe loading (2.78 wt %), and defined FeN4Cl1 sites with a distinct electronic structure.
Abstract
The construction of single-atom catalysts (SACs) with high single atom densities, favorable electronic structures and fast mass transfer is highly desired. We have utilized metal-triazolate (MET) frameworks, a subclass of metal–organic frameworks (MOFs) with high N content, as precursors since they can enhance the density and regulate the electronic structure of single-atom sites, as well as generate abundant mesopores simultaneously. Fe single atoms dispersed in a hierarchically porous N-doped carbon matrix with high metal content (2.78 wt %) and a FeN4Cl1 configuration (FeN4Cl1/NC), as well as mesopores with a pore:volume ratio of 0.92, were obtained via the pyrolysis of a Zn/Fe-bimetallic MET modified with 4,5-dichloroimidazole. FeN4Cl1/NC exhibits excellent oxygen reduction reaction (ORR) activity in both alkaline and acidic electrolytes. Density functional theory calculations confirm that Cl can optimize the adsorption free energy of Fe sites to *OH, thereby promoting the ORR process. The catalyst demonstrates great potential in zinc-air batteries. This strategy selects, designs, and adjusts MOFs as precursors for high-performance SACs.
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References
- 1
- 1aX. Wen, Q. Zhang, J. Guan, Coord. Chem. Rev. 2020, 409, 213214;
- 1bY. Zhang, M. Luo, Y. Yang, Y. Li, S. Guo, ACS Energy Lett. 2019, 4, 1672–1680;
- 1cC.-X. Zhao, J.-N. Liu, J. Wang, D. Ren, B.-Q. Li, Q. Zhang, Chem. Soc. Rev. 2021, 50, 7745–7778.
- 2
- 2aA. Wang, J. Li, T. Zhang, Nat. Rev. Chem. 2018, 2, 65–81;
- 2bY. Chen, S. Ji, C. Chen, Q. Peng, D. Wang, Y. Li, Joule 2018, 2, 1242–1264;
- 2cW. Zhao, G. Li, Z. Tang, Nano Today 2019, 27, 178–197.
- 3
- 3aC.-X. Zhao, B.-Q. Li, J.-N. Liu, Q. Zhang, Angew. Chem. Int. Ed. 2021, 60, 4448–4463; Angew. Chem. 2021, 133, 4496–4512;
- 3bH. Shen, E. Gracia-Espino, J. Ma, K. Zang, J. Luo, L. Wang, S. Gao, X. Mamat, G. Hu, T. Wagberg, S. Guo, Angew. Chem. Int. Ed. 2017, 56, 13800–13804; Angew. Chem. 2017, 129, 13988–13992;
- 3cJ. Wang, H. Li, S. Liu, Y. Hu, J. Zhang, M. Xia, Y. Hou, J. Tse, J. Zhang, Y. Zhao, Angew. Chem. Int. Ed. 2021, 60, 181–185; Angew. Chem. 2021, 133, 183–187;
- 3dH. Shang, X. Zhou, J. Dong, A. Li, X. Zhao, Q. Liu, Y. Lin, J. Pei, Z. Li, Z. Jiang, D. Zhou, L. Zheng, Y. Wang, J. Zhou, Z. Yang, R. Cao, R. Sarangi, T. Sun, X. Yang, X. Zheng, W. Yan, Z. Zhuang, J. Li, W. Chen, D. Wang, J. Zhang, Y. Li, Nat. Commun. 2020, 11, 3049;
- 3eY. Chen, S. Ji, S. Zhao, W. Chen, J. Dong, W. C. Cheong, R. Shen, X. Wen, L. Zheng, A. I. Rykov, S. Cai, H. Tang, Z. Zhuang, C. Chen, Q. Peng, D. Wang, Y. Li, Nat. Commun. 2018, 9, 5422;
- 3fC. Tang, Y. Jiao, B. Shi, J.-N. Liu, Z. Xie, X. Chen, Q. Zhang, S.-Z. Qiao, Angew. Chem. Int. Ed. 2020, 59, 9171–9176; Angew. Chem. 2020, 132, 9256–9261.
- 4
- 4aV. Yarlagadda, M. K. Carpenter, T. E. Moylan, R. S. Kukreja, R. Koestner, W. Gu, L. Thompson, A. Kongkanand, ACS Energy Lett. 2018, 3, 618–621;
- 4bH. Zhou, T. Yang, Z. Kou, L. Shen, Y. Zhao, Z. Wang, X. Wang, Z. Yang, J. Du, J. Xu, M. Chen, L. Tian, W. Guo, Q. Wang, H. Lv, W. Chen, X. Hong, J. Luo, D. He, Y. Wu, Angew. Chem. Int. Ed. 2020, 59, 20465–20469; Angew. Chem. 2020, 132, 20645–20649.
- 5
- 5aA. Schoedel, M. Li, D. Li, M. O'Keeffe, O. M. Yaghi, Chem. Rev. 2016, 116, 12466–12535;
- 5bD. Li, H.-Q. Xu, L. Jiao, H.-L. Jiang, EnergyChem 2019, 1, 100005;
- 5cL. Wang, Y. Han, X. Feng, J. Zhou, P. Qi, B. Wang, Coord. Chem. Rev. 2016, 307, 361;
- 5dJ. Gao, Q. Huang, Y. Wu, Y.-Q. Lan, B. Chen, Adv. Energy Sustainability Res. 2021, 2, 2100033.
- 6
- 6aL. Hu, W. Li, L. Wang, B. Wang, EnergyChem 2021, 3, 100056;
- 6bC.-C. Hou, H.-F. Wang, C. Li, Q. Xu, Energy Environ. Sci. 2020, 13, 1658–1693;
- 6cG. Yilmaz, S. B. Peh, D. Zhao, G. W. Ho, Adv. Sci. 2019, 6, 1901129;
- 6dL. Jiao, H.-L. Jiang, Chem 2019, 5, 786–804.
- 7F. Gándara, F. J. Uribe-Romo, D. K. Britt, H. Furukawa, L. Lei, R. Cheng, X. Duan, M. O'Keeffe, O. M. Yaghi, Chem. Eur. J. 2012, 18, 10595–10601.
- 8
- 8aR. Zhao, Z. Liang, S. Gao, C. Yang, B. Zhu, J. Zhao, C. Qu, R. Zou, Q. Xu, Angew. Chem. Int. Ed. 2019, 58, 1975–1979; Angew. Chem. 2019, 131, 1997–2001;
- 8bS. Li, Y. Liu, X. Gao, J. Wang, J. Zhou, L. Wang, B. Wang, J. Mater. Chem. A 2020, 8, 10354–10362;
- 8cY.-i. Fujiwara, J.-S. M. Lee, M. Tsujimoto, K. Kongpatpanich, T. Pila, K.-i. Iimura, N. Tobori, S. Kitagawa, S. Horike, Chem. Mater. 2018, 30, 1830–1834;
- 8dY. Hu, C. Li, S. Xi, Z. Deng, X. Liu, A. K. Cheetham, J. Wang, Adv. Sci. 2021, 8, 2003212.
- 9T. Sun, S. Mitchell, J. Li, P. Lyu, X. Wu, J. Pérez-Ramírez, J. Lu, Adv. Mater. 2021, 33, 2003075.
- 10
- 10aL. Jiao, G. Wan, R. Zhang, H. Zhou, S.-H. Yu, H.-L. Jiang, Angew. Chem. Int. Ed. 2018, 57, 8525–8529; Angew. Chem. 2018, 130, 8661–8665;
- 10bC.-C. Hou, L. Zou, L. Sun, K. Zhang, Z. Liu, Y. Li, C. Li, R. Zou, J. Yu, Q. Xu, Angew. Chem. Int. Ed. 2020, 59, 7384–7389; Angew. Chem. 2020, 132, 7454–7459;
- 10cX. Gong, J. Zhu, J. Li, R. Gao, Q. Zhou, Z. Zhang, H. Dou, L. Zhao, X. Sui, J. Cai, Y. Zhang, B. Liu, Y. Hu, A. Yu, S.-h. Sun, Z. Wang, Z. Chen, Adv. Funct. Mater. 2021, 31, 2008085;
- 10dX. Ge, G. Su, W. Che, J. Yang, X. Zhou, Z. Wang, Y. Qu, T. Yao, W. Liu, Y. Wu, ACS Catal. 2020, 10, 10468–10475;
- 10eY. Lin, P. Liu, E. Velasco, G. Yao, Z. Tian, L. Zhang, L. Chen, Adv. Mater. 2019, 31, 1808193.
- 11X. Zhang, X. Han, Z. Jiang, J. Xu, L. Chen, Y. Xue, A. Nie, Z. Xie, Q. Kuang, L. Zheng, Nano Energy 2020, 71, 104547.
- 12Y. Han, Y. Wang, R. Xu, W. Chen, L. Zheng, A. Han, Y. Zhu, J. Zhang, H. Zhang, J. Luo, C. Chen, Q. Peng, D. Wang, Y. Li, Energy Environ. Sci. 2018, 11, 2348–2352.
