A high-performance electrocatalyst for oxygen reduction derived from copolymer-anchored polyoxometalates
Graphical Abstract
Abstract
The development and synthesis of cathode electrocatalysts with high activity and durable stability for metal-air batteries is an important challenge in the area of electrocatalysis. Herein, we introduce a novel in-situ nitriding and phosphating strategy for producing W3N4 and WP from phosphotungstic acid (HPW)-polyaniline-phytic acid-Fe3+ organic–inorganic hybrid material. The final material has a three-dimensional porous framework with W3N4-WP heterostructures embedded in the carbon matrix (W3N4-WP@NPC). As-made materials exhibit exceptional electrocatalytic performance for the oxygen reduction reaction (ORR), with a diffusion-limiting current density of 6.9 mA·cm−2 and a half-wave potential of 0.82 V. As a Zn-air primary cathode, the W3N4-WP@NPC assembled battery can provide a relatively high peak power density (194.2 mW·cm−2). As a Zn-air secondary air-cathode, it has great cycling stability over 500 h. This work provides a simple and efficient method for rationally designing high-performance air cathodes from copolymer-anchored polyoxometalates.
Keywords
Electronic Supplementary Material
References
Cao, W. Z.; Zhang, J. N.; Li, H. Batteries with high theoretical energy densities. Energy Storage Mater. 2020, 26, 46–55.
Zhuang, Z. C.; Li, Y. H.; Yu, R. H.; Xia, L. X.; Yang, J. R.; Lang, Z. Q.; Zhu, J. X.; Huang, J. Z.; Wang, J. O.; Wang, Y. et al. Reversely trapping atoms from a perovskite surface for high-performance and durable fuel cell cathodes. Nat. Catal. 2022, 5, 300–310.
Zhuang, Z. C.; Xia, L. X.; Huang, J. Z.; Zhu, P.; Li, Y.; Ye, C. L.; Xia, M. G.; Yu, R. H.; Lang, Z. Q.; Zhu, J. X. et al. Continuous modulation of electrocatalytic oxygen reduction activities of single-atom catalysts through p-n junction rectification. Angew. Chem., Int. Ed. 2023, 62, e202212335.
Zhuang, Z. C.; Li, Y.; Huang, J. Z.; Li, Z. L.; Zhao, K. N.; Zhao, Y. L.; Xu, L.; Zhou, L.; Moskaleva, L. V.; Mai, L. Q. Sisyphus effects in hydrogen electrochemistry on metal silicides enabled by silicene subunit edge. Sci. Bull. 2019, 64, 617–624
Li, W. H.; Yang, J. R.; Wang, D. S. Long-range interactions in diatomic catalysts boosting electrocatalysis. Angew. Chem. Int. Ed. 2022, 61, e202213318.
Han, A. L.; Sun, W. M.; Wan, X.; Cai, D. D.; Wang, X. J.; Li, F.; Shui, J. L.; Wang, D. S. Construction of Co4 atomic clusters to enable Fe-N4 motifs with highly active and durable oxygen reduction performance. Angew. Chem. Int. Ed. 2023, 62, e202213318.
Chen, Y. H.; Xu, J. J.; He, P.; Qiao, Y.; Guo, S. H.; Yang, H. J.; Zhou, H. S. Metal-air batteries: Progress and perspective. Sci. Bull. 2022, 67, 2449–2486.
Ma, R. G.; Lin, G. X.; Zhou, Y.; Liu, Q.; Zhang, T.; Shan, G. C.; Yang, M. H.; Wang, J. C. A review of oxygen reduction mechanisms for metal-free carbon-based electrocatalysts. npj Comput. Mater. 2019, 5, 78.
Wang, Y.; Zheng, M.; Li, Y. R.; Ye, C. L.; Chen, J.; Ye, J. Y.; Zhang, Q. H.; Li, J.; Zhou, Z. Y.; Fu, X. Z.; Wang, J.; Sun, S. G.; Wang, D. S. p–d orbital hybridization induced by a monodispersed Ga site on a Pt3Mn nanocatalyst boosts ethanol electrooxidation. Angew. Chem. Int. Ed. 2022, 61, e202115735.
Wang, Y.; Wu, J.; Tang, S. H.; Yang, J. Y.; Ye, C. L.; Chen, J.; Lei, Y. P.; Wang, D. S. Synergistic Fe-Se atom pairs as bifunctional oxygen electrocatalysts boost low-temperature rechargeable Zn-Air battery. Angew. Chem. Int. Ed. 2023, 62, e202219191.
Lin, Z. X.; Richardson, J. J.; Zhou, J. J.; Caruso, F. Direct synthesis of amorphous coordination polymers and metal-organic frameworks. Nat. Rev. Chem. 2023, 7, 273–286.
Zhao, W.; Li, P.; Han, K.; Cui, K. X.; Liu, C. R.; Tan, Q. W.; Qu, X. H. Low-temperature and high-voltage Zn-based liquid metal batteries based on multiple redox mechanism. J. Power Sources 2020, 463, 228233.
Paul, R. J.; Zhai, Q. F.; Roy, A. K.; Dai, L. M. Charge transfer of carbon nanomaterials for efficient metal-free electrocatalysis. Interdiscip. Mater. 2022, 1, 28–50.
Zhang, L.; Zhu, J. W.; Li, X.; Mu, S. C.; Verpoort, F.; Xue, J. M.; Kou, Z. K.; Wang, J. Nurturing the marriages of single atoms with atomic clusters and nanoparticles for better heterogeneous electrocatalysis. Interdiscip. Mater. 2022, 1, 51–87.
Leong, K. W.; Wang, Y. F.; Ni, M.; Pan, W. D.; Luo, S. J.; Leung, D. Y. C. Rechargeable Zn-air batteries: Recent trends and future perspectives. Renew. Sustain. Energy Rev. 2022, 154, 111771.
Wang, C.; Li, J.; Zhou, Z.; Pan, Y. Q.; Yu, Z. X.; Pei, Z. X.; Zhao, S. L.; Wei, L.; Chen, Y. Rechargeable zinc-air batteries with neutral electrolytes: Recent advances, challenges, and prospects. EnergyChem. 2021, 3, 100055.
Li, T.; Huang, M.; Bai, X.; Wang, Y. X. Metal-air batteries: A review on current status and future applications. Prog. Nat. Sci. Mater. Int. 2023, 33, 151–171.
Xiong, L. W.; Fu, Y. K.; Luo, Y. X.; Wei, Y. S.; Zhang, Z.; Wu, C. G.; Luo, S. C.; Wang, G.; Sawtell, D.; Xie, K. F. et al. Prospective applications of transition metal-based nanomaterials. J. Mater. Res. 2022, 37, 2109–2123.
Wang, X. Q.; Li, Z. J.; Qu, Y. T.; Yuan, T. W.; Wang, W. Y.; Wu, Y. E.; Li, Y. D. Review of metal catalysts for oxygen reduction reaction: From nanoscale engineering to atomic design. Chem. 2019, 5, 1486–1511.
Fan, J. T.; Chen, M.; Zhao, Z. L.; Zhang, Z.; Ye, S. Y.; Xu, S. Y.; Wang, H. J.; Li, H. Bridging the gap between highly active oxygen reduction reaction catalysts and effective catalyst layers for proton exchange membrane fuel cells. Nature Energy. 2021, 6, 475–486.
Chen, Y.; Qiao, Q. Y.; Gao, J. Z.; Li, H. X.; Bian, Z. F. Precious metal recovery. Joule. 2021, 5, 3097–3115.
Chen, Y.; Xu, M. J.; Wen, J. Y.; Wan, Y.; Zhao, Q. F.; Cao, X.; Ding, Y.; Wang, Z. L.; Li, H. X.; Bian, Z. F. Selective recovery of precious metals through photocatalysis. Nat. Sustain. 2021, 4, 618–626.
Zhang, L.; Shao, Q. S.; Zhang, J. J. An overview of non-noble metal electrocatalysts and their associated air cathodes for Mg-air batteries. Mater. Rep. Energy. 2021, 1, 100002.
Yang, Q. Y.; Liu, J. W.; Cai, W. T.; Liang, X.; Zhuang, Z. C.; Liao, T.; Zhang, F. X.; Hu, W. K.; Liu, P. X.; Fan, S. J. et al. Non-heme iron single-atom nanozymes as peroxidase mimics for tumor catalytic therapy. Nano Lett. 2023, 23, 8585–8592.
Kang, Q.; Zhuang, Z. C.; Liu, Y. J.; Liu, Z. H.; Li, Y.; Sun, B.; Pei, F.; Zhu, H.; Li, H. F.; Li, P. L. et al. Engineering the structural uniformity of gel polymer electrolytes via pattern-guided alignment for durable, safe solid-state lithium metal batteries. Adv. Mater. 2023, 35, 2303460.
Zhou, S.; Pei, W.; Zhao, Y. Y.; Yang, X. W.; Liu, N. S.; Zhao, J. J. Low-dimensional non-metal catalysts: Principles for regulating p-orbital-dominated reactivity. npj Comput. Mater. 2021, 7, 186.
Wang, H.; Li, J. M.; Li, K.; Lin, Y. P.; Chen, J. M.; Gao, L. J.; Nicolosi, V.; Xu, X.; Lee, J. M. Transition metal nitrides for electrochemical energy applications. Chem. Soc. Rev. 2021, 50, 1354–1390.
Zhang, G. X.; Jin, L.; Zhang, R. X.; Bai, Y.; Zhu, R. M.; Pang, H. Recent advances in the development of electronically and ionically conductive metal-organic frameworks. Coord. Chem. Rev. 2021, 439, 213915.
Chen, P. R.; Ye, J. S.; Wang, H.; Ouyang, L. Z.; Zhu, M. Recent progress of transition metal carbides/nitrides for electrocatalytic water splitting. J. Alloys Compd. 2021, 883, 160833.
Cao, X. J.; Wang, T. Z.; Jiao, L. F. Transition-metal (Fe, Co, and Ni)-based nanofiber electrocatalysts for water splitting. Adv. Fiber Mater. 2021, 3, 210–228.
Zhao, L.; Song, M.; Zhu, W. Y.; Zhuang, W. C.; Du, X. H.; Tian, L. MOF-derived hollow heterostructures for advanced electrocatalysis. Coord. Chem. Rev. 2021, 439, 213946.
Li, Y.; Wu, F.; Qian, J.; Zhang, M. H.; Yuan, Y. X.; Bai, Y.; Wu, C. Metal chalcogenides with heterostructures for high-performance rechargeable batteries. Small Sci. 2021, 1, 2100012.
Hao, J. C.; Zhu, H.; Zhuang, Z. C.; Zhao, Q.; Yu, R. H.; Hao, J. C.; Kang, Q.; Lu, S. L.; Wang, X. F.; Wu, J. S. et al. Competitive trapping of single atoms onto a metal carbide surface. ACS Nano. 2023, 17, 6955–6965.
Li, X. Y.; Zhuang, Z. C.; Chai, J.; Shao, R. W.; Wang, J. H.; Jiang, Z. L.; Zhu, S. W.; Gu, H. F.; Zhang, J.; Ma, Z. T. et al. Atomically strained metal sites for highly efficient and selective photooxidation. Nano Lett. 2023, 23, 2905–2914.
Meng, Z. H.; Zheng, S. H.; Luo, R.; Tang, H. B.; Wang, R.; Zhang, R. M.; Tian, T.; Tang, H. L. Transition metal nitrides for electrocatalytic application: Progress and rational design. Nanomaterials. 2022, 12, 2660.
Luo, Q.; Lu, C. C.; Liu, L. R.; Zhu, M. Y. A review on the synthesis of transition metal nitride nanostructures and their energy related applications. Green Energy Environ. 2023, 8, 406–437.
Li, H.; Fan, G.; Cao, L. Y.; Yang, Y.; Yan, X.; Dai, Y. P.; Zhang, G. J.; Wang, J. L. A comprehensive investigation on the design and off-design performance of supercritical carbon dioxide power system based on the small-scale lead-cooled fast reactor. J. Clean. Prod. 2020, 256, 120720.
Li, W.; Liu, J.; Zhao, D. Y. Mesoporous materials for energy conversion and storage devices. Nat. Rev. Mater. 2016, 1, 16023.
Zhang, W.; Feng, P.; Chen, J.; Sun, Z. M.; Zhao, B. X. Electrically conductive hydrogels for flexible energy storage systems. Prog. Polym. Sci. 2019, 88, 220–240.
Du, Y.; Chen, W. X.; Zhong, Z. Y.; Wang, S. Z.; Zhou, L. N.; Xiong, D. B.; Liu, Y. S.; Liu, Z. H.; Wang, K. Bifunctional oxygen electrocatalysts with WN@Ni nanostructures implanted on N-doped carbon nanorods for rechargeable Zn-air batteries. J. Alloys Compd. 2023, 960, 170789.
Du, Y.; Chen, W. X.; Zhou, L. N.; Hu, R.; Wang, S. Z.; Li, X. Q.; Xie, Y. L.; Yang, L.; Liu, Y. S.; Liu, Z. H. One-step, in situ formation of WN-W2C heterojunctions implanted on N doped carbon nanorods as efficient oxygen reduction catalyst for metal-air battery. Nano Res. 2023, 16, 8773–8781.
Liu, Y. S.; Li, Z. X.; Wang, S. Z.; Xuan, J. N.; Xiong, D. B.; Zhou, L. N.; Zhou, J. Q.; Wang, J.; Yang, Y. H.; Du, Y. Hierarchical porous yolk–shell Co-N-C nanocatalysts encaged in graphene nanopockets for high-performance Zn-air battery. Nano Res. 2023, 16, 8893–8901.
Li, S. J.; Tan, X. P.; Li, H.; Gao, Y.; Wang, Q.; Li, G. N.; Guo, M. Investigation on pore structure regulation of activated carbon derived from sargassum and its application in supercapacitor. Sci. Rep. 2022, 12, 10106.
Sun, X. P.; Wei, P.; He, Z. M.; Cheng, F. Y.; Tang, L.; Li, Q.; Han, J. T.; He, J. H. Novel transition-metal phosphides@N,P-codoped carbon electrocatalysts synthesized via a universal strategy for overall water splitting. J. Alloys Compd. 2023, 932, 167253.
Zhuang, Z. C.; Huang, J. Z.; Li, Y.; Zhou, L.; Mai, L. Q. The holy grail in platinum-free electrocatalytic hydrogen evolution: Molybdenum-based catalysts and recent advances. ChemElectroChem. 2019, 6, 3570–3589.
Zhuang, Z. C.; Li, Y.; Li, Y. H.; Huang, J. Z.; Wei, B.; Sun, R.; Ren, Y. J.; Ding, J.; Zhu, J. X.; Lang, Z. Q. et al. Atomically dispersed nonmagnetic electron traps improve oxygen reduction activity of perovskite oxides. Energy Environ. Sci. 2021, 14, 1016–1028.
Liu, Y. S.; Chen, Z. C.; Li, Z. X.; Zhao, N.; Xie, Y. L.; Du, Y.; Xuan, J, N.; Xiong, D. B.; Zhou, J. Q.; Cai, L. et al. CoNi nanoalloy-Co-N4 composite active sites embedded in hierarchical porous carbon as bi-functional catalysts for flexible Zn-air battery. Nano Energy. 2022, 99, 107325.
Liu, Z. H.; Du, Y.; Zhang, P. F.; Zhuang, Z. C.; Wang, D. S. Bringing catalytic order out of chaos with nitrogen-doped ordered mesoporous carbon. Matter. 2021, 4, 3161–3194.
Wang, Y.; Zheng, M.; Li, Y. R.; Chen, J.; Ye, C. L.; Li, S.; Wang, J.; Zhu, Y. F.; Sun, S. G.; Wang, D. S. Oxygen-bridged long-range dual sites boost ethanol electrooxidation by facilitating C–C bond vleavage. Nano Lett. 2023, 23, 8194–8202.
Wang, P.; Zhang, Z. C. Y.; Song, N.; An, X. G.; Liu, J.; Feng, J. K.; Xi, B. J.; Xiong, S. L. WP nanocrystals on N,P dual-doped carbon nanosheets with deeply analyzed catalytic mechanisms for lithium-sulfur batteries. CCS Chem. 2023, 5, 397–411.
Nkosi, F. P.; Raju, K.; Palaniyandy, N.; Reddy, M. V.; Billing, C.; Ozoemena, K. I. Insights into the synergistic roles of microwave and fluorination treatments towards enhancing the cycling stability of P2-type Na0.67[Mg0.28Mn0.72]O2 cathode material for sodium-ion batteries. J. Electrochem. Soc. 2017, 164, A3362–A3370.
Liu, D. M.; Yi, W. C.; Fu, Y. L.; Kong, Q. H.; Xi, G. C. In situ surface restraint-induced synthesis of transition-metal nitride ultrathin nanocrystals as ultrasensitive SERS substrate with ultrahigh durability. ACS Nano. 2022, 16, 13123–13133
Du, H. F.; Du, Z. Z.; Wang, T. F.; He, S.; Yang, K.; Wang, K.; Xie, L. H.; Ai, W.; Huang, W. Interface engineering of tungsten carbide/phosphide heterostructures anchored on N,P-codoped carbon for high-efficiency hydrogen evolution reaction. Sci. China Mater. 2022, 65, 967–973.
Yu, C.; Du, Y.; He, R. H.; Ma, Y.; Liu, Z. H.; Li, X. Y.; Luo, W.; Zhou, L.; Mai, L. Q. Hollow SiO x /C microspheres with semigraphitic carbon coating as the “lithium host” for dendrite-free lithium metal anodes. ACS Appl. Energy Mater. 2021, 4, 3905–3912.
Liu, Z. H.; Du, Y.; Yu, R. H.; Zheng, M. B.; Hu, R.; Wu, J. S.; Xia, Y. Y.; Zhuang, Z. C.; Wang, D. S. Tuning mass transport in electrocatalysis down to sub-5 nm through nanoscale grade separation. Angew. Chem., Int. Ed. 2023, 62, e202212653.
京公网安备11010802044758号