AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Non-bonding modulations between single atomic cerium and monodispersed selenium sites towards efficient oxygen reduction

Leilei Yin1, Shuai Zhang1, Mingzi Sun2, Siyuan Wang1, Bolong Huang2,3 ( ), Yaping Du1( )
Tianjin Key Lab for Rare Earth Materials and Applications, Center for Rare Earth and Inorganic Functional Materials, Haihe Laboratory of Sustainable Chemical Transformations, Smart Sensing Interdisciplinary Science Center, School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin 300350, China
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon 999077, Hong Kong, China
Research Centre for Carbon-Strategic Catalysis, The Hong Kong Polytechnic University, Hung Hom, Kowloon 999077, Hong Kong, China
Show Author Information

Graphical Abstract

The interplay of neighboring active sites in dual atomic catalysts (DACs) still requires in-depth experimental and theoretical investigations. This work reports the developments of heteronuclear diatomic electrocatalyst Ce-Se diatomic catalysts (Ce-Se DAs/NC) prepared by a two-step pyrolysis, which delivers efficient oxygen reduction reaction (ORR) performances with a half-wave potential of 0.886 V, enabling the improved higher peak power density and specific capacity than commercial Pt/C.

Abstract

Currently, dual atomic catalysts (DACs) with neighboring active sites for oxygen reduction reaction (ORR) still meet lots of challenges in the synthesis, especially the construction of atomic pairs of elements from different blocks of the periodic table. Herein, a “rare earth (Ce)-metalloid (Se)” non-bonding heteronuclear diatomic electrocatalyst has been constructed for ORR by rational coordination and carbon support defect engineering. Encouraging, the optimized Ce-Se diatomic catalysts (Ce-Se DAs/NC) displayed a half-wave potential of 0.886 V vs. reversible hydrogen electrode (RHE) and excellent stability, which surpass those of separate Ce or Se single atoms and most single/dual atomic catalysts ever reported. In addition, a primary zinc-air battery constructed using Ce-Se DAs/NC delivers a higher peak power density (209.2 mW·cm−2) and specific capacity (786.4 mAh·gZn−1) than state-of-the-art noble metal catalysts Pt/C. Theoretical calculations reveal that the Ce-Se DAs/NC has improved the electroactivity of the Ce-N4 region due to the electron transfer towards the nearby Se specific activity (SA) sites. Meanwhile, the more electron-rich Se sites promote the adsorptions of key intermediates, which results in the optimal performances of ORR on Ce-Se DAs/NC. This work provides new perspectives on electronic structure modulations via non-bonded long-range coordination micro-environment engineering in DACs for efficient electrocatalysis.

Keywords

catalystrare earthoxygen reduction reaction (ORR)metalloidnon-bonding modulation

Electronic Supplementary Material

Download File(s)
12274_2024_6416_MOESM1_ESM.pdf (3.4 MB)

References

[1]

Huang, Y. C.; Guo, Z. J.; Liu, H.; Zhang, S. Q.; Wang, P. S.; Lu, J.; Tong, Y. X. Heterojunction architecture of N-doped WO3 nanobundles with Ce2S3 nanodots hybridized on a carbon textile enables a highly efficient flexible photocatalyst. Adv. Funct. Mater. 2019, 29, 1903490.
Crossref Google Scholar
[2]

Wang, Y. X.; Chen, D. M.; Zhang, J. N.; Balogun, M. S.; Wang, P. S.; Tong, Y. X.; Huang, Y. C. Charge relays via dual carbon-actions on nanostructured BiVO4 for high performance photoelectrochemical water splitting. Adv. Funct. Mater. 2022, 32, 2112738.
Crossref Google Scholar
[3]
Zhu, Z. X.; Luo, L.; He, Y. X.; Mushtaq, M.; Li, J. Q.; Yang, H.; Khanam, Z.; Qu, J.; Wang, Z. M.; Balogun, M. S. High-performance alkaline freshwater and seawater hydrogen catalysis by sword-head structured Mo2N-Ni3Mo3N tunable interstitial compound electrocatalysts. Adv. Funct. Mater., in press, https://doi.org/10.1002/adfm.202306061.
[4]

Zhang, S. L.; Zhai, D.; Sun, T. T.; Han, A. J.; Zhai, Y. L.; Cheong, W. C.; Liu, Y.; Su, C. L.; Wang, D. S.; Li, Y. D. In situ embedding Co9S8 into nitrogen and sulfur codoped hollow porous carbon as a bifunctional electrocatalyst for oxygen reduction and hydrogen evolution reactions. Appl. Catal. B Environ. 2019, 254, 186–193.
Crossref Google Scholar
[5]

Fu, J.; Cano, Z. P.; Park, M. G.; Yu, A. P.; Fowler, M.; Chen, Z. W. Electrically rechargeable zinc-air batteries: Progress, challenges, and perspectives. Adv. Mater. 2017, 29, 1604685.
Crossref Google Scholar
[6]

Fu, J.; Liang, R. L.; Liu, G. H.; Yu, A. P.; Bai, Z. Y.; Yang, L.; Chen, Z. W. Recent progress in electrically rechargeable zinc-air batteries. Adv. Mater. 2019, 31, 1805230.
Crossref Google Scholar
[7]

Liu, J. N.; Zhao, C. X.; Wang, J.; Ren, D.; Li, B. Q.; Zhang, Q. A brief history of zinc-air batteries: 140 years of epic adventures. Energy Environ. Sci. 2022, 15, 4542–4553.
Crossref Google Scholar
[8]

Zhu, X. F.; Hu, C. G.; Amal, R.; Dai, L. M.; Lu, X. Y. Heteroatom-doped carbon catalysts for zinc-air batteries: Progress, mechanism, and opportunities. Energy Environ. Sci. 2020, 13, 4536–4563.
Crossref Google Scholar
[9]

Huang, H. J.; Yu, D. S.; Hu, F.; Huang, S. C.; Song, J. N.; Chen, H. Y.; Li, L. L.; Peng, S. J. Clusters induced electron redistribution to tune oxygen reduction activity of transition metal single-atom for metal-air batteries. Angew. Chem., Int. Ed. 2022, 61, e202116068.
Crossref Google Scholar
[10]

Shao, M. H.; Chang, Q. W.; Dodelet, J. P.; Chenitz, R. Recent advances in electrocatalysts for oxygen reduction reaction. Chem. Rev. 2016, 116, 3594–3657.
Crossref Google Scholar
[11]

Zhao, C. X.; Liu, J. N.; Wang, J.; Ren, D.; Li, B. Q.; Zhang, Q. Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts. Chem. Soc. Rev. 2021, 50, 7745–7778.
Crossref Google Scholar
[12]

Shang, H. S.; Jiang, Z. L.; Zhou, D. N.; Pei, J. J.; Wang, Y.; Dong, J. C.; Zheng, X. S.; Zhang, J. T.; Chen, W. X. Engineering a metal-organic framework derived Mn-N4-C x S y atomic interface for highly efficient oxygen reduction reaction. Chem. Sci. 2020, 11, 5994–5999.
Crossref Google Scholar
[13]

Shang, H. S.; Liu, D. Atomic design of carbon-based dual-metal site catalysts for energy applications. Nano Res. 2023, 16, 6477–6506.
Crossref Google Scholar
[14]

Shang, H. S.; Sun, W. M.; Sui, R.; Pei, J. J.; Zheng, L. R.; Dong, J. C.; Jiang, Z. L.; Zhou, D. N.; Zhuang, Z. B.; Chen, W. X. et al. Engineering isolated Mn-N2C2 atomic interface sites for efficient bifunctional oxygen reduction and evolution reaction. Nano Lett. 2020, 20, 5443–5450.
Crossref Google Scholar
[15]

Shang, H. S.; Zhou, X. Y.; Dong, J. C.; Li, A.; Zhao, X.; Liu, Q. H.; Lin, Y.; Pei, J. J.; Li, Z.; Jiang, Z. L. et al. Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity. Nat. Commun. 2020, 11, 3049.
Crossref Google Scholar
[16]

Zhang, W. Y.; Chao, Y. G.; Zhang, W. S.; Zhou, J. H.; Lv, F.; Wang, K.; Lin, F. X.; Luo, H.; Li, J.; Tong, M. P. et al. Emerging dual-atomic-site catalysts for efficient energy catalysis. Adv. Mater. 2021, 33, 2102576.
Crossref Google Scholar
[17]

Zhang, H. W.; Jin, X. D.; Lee, J. M.; Wang, X. Tailoring of active sites from single to dual atom sites for highly efficient electrocatalysis. ACS Nano 2022, 16, 17572–17592.
Crossref Google Scholar
[18]

Li, W. H.; Yang, J. R.; Wang, D. S. Long-range interactions in diatomic catalysts boosting electrocatalysis. Angew. Chem., Int. Ed. 2022, 61, e202213318.
Crossref Google Scholar
[19]
Sun, J. K.; Pan, Y. W.; Xu, M. Q.; Sun, L.; Zhang, S. L.; Deng, W. Q.; Zhai, D. Heteroatom doping regulates the catalytic performance of single-atom catalyst supported on graphene for ORR. Nano Res., in press, https://doi.org/10.1007/s12274-023-5898-1.
[20]

Fu, J. H.; Dong, J. H.; Si, R.; Sun, K. J.; Zhang, J. Y.; Li, M. R.; Yu, N. N.; Zhang, B. S.; Humphrey, M. G.; Fu, Q. et al. Synergistic effects for enhanced catalysis in a dual single-atom catalyst. ACS Catal. 2021, 11, 1952–1961.
Crossref Google Scholar
[21]

Yu, D. S.; Ma, Y. C.; Hu, F.; Lin, C. C.; Li, L. L.; Chen, H. Y.; Han, X. P.; Peng, S. J. Dual-sites coordination engineering of single atom catalysts for flexible metal-air batteries. Adv. Energy Mater. 2021, 11, 2101242.
Crossref Google Scholar
[22]

Sui, R.; Zhang, X. J.; Wang, X. D.; Wang, X. Y.; Pei, J. J.; Zhang, Y. F.; Liu, X. R.; Chen, W. X.; Zhu, W.; Zhuang, Z. B. Silver based single atom catalyst with heteroatom coordination environment as high performance oxygen reduction reaction catalyst. Nano Res. 2022, 15, 7968–7975
Google Scholar
[23]

Wang, J.; Zhao, C. X.; Liu, J. N.; Song, Y. W.; Huang, J. Q.; Li, B. Q. Dual-atom catalysts for oxygen electrocatalysis. Nano Energy 2022, 104, 107927.
Crossref Google Scholar
[24]

Zhang, S. L.; Hou, M. C.; Zhai, Y. L.; Liu, H. J.; Zhai, D.; Zhu, Y. Q.; Ma, L.; Wei, B.; Huang, J. Dual-active-sites single-atom catalysts for advanced applications. Small 2023, 19, 2302739.
Crossref Google Scholar
[25]

Greeley, J.; Jaramillo, T. F.; Bonde, J.; Chorkendorff, I.; Nørskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 2006, 5, 909–913.
Crossref Google Scholar
[26]

Zhang, J. C.; Yang, H. B.; Liu, B. Coordination engineering of single-atom catalysts for the oxygen reduction reaction: A review. Adv. Energy Mater. 2021, 11, 2002473.
Crossref Google Scholar
[27]

Zhao, C. X.; Li, B. Q.; Liu, J. N.; Zhang, Q. Intrinsic electrocatalytic activity regulation of M-N-C single-atom catalysts for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2021, 60, 4448–4463.
Crossref Google Scholar
[28]

Teng, Z. Y.; Zhang, Q. T.; Yang, H. B.; Kato, K.; Yang, W. J.; Lu, Y. R.; Liu, S. X.; Wang, C. Y.; Yamakata, A.; Su, C. L. et al. Atomically dispersed antimony on carbon nitride for the artificial photosynthesis of hydrogen peroxide. Nat. Catal. 2021, 4, 374–384.
Crossref Google Scholar
[29]

Wang, X.; Zhu, Y.; Li, H.; Lee, J. M.; Tang, Y. W.; Fu, G. T. Rare-earth single-atom catalysts: A new frontier in photo/electrocatalysis. Small Methods 2022, 6, 2200413.
Crossref Google Scholar
[30]

Sun, M. Z.; Wong, H. H.; Wu, T.; Dougherty, A. W.; Huang, B. L. Stepping out of transition metals: Activating the dual atomic catalyst through main group elements. Adv. Energy Mater. 2021, 11, 2101404.
Crossref Google Scholar
[31]

Sun, K. A.; Yu, K.; Fang, J. J.; Zhuang, Z. W.; Tan, X.; Wu, Y.; Zeng, L. Y.; Zhuang, Z. B.; Pan, Y.; Chen, C. Nature-inspired design of molybdenum-selenium dual-single-atom electrocatalysts for CO2 reduction. Adv. Mater. 2022, 34, 2206478.
Crossref Google Scholar
[32]

Wang, Y.; Wu, J.; Tang, S. H.; Yang, J. R.; 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. 2023, 135, e202219191.
Crossref Google Scholar
[33]

Yin, L. L.; Zhang, S.; Sun, M. Z.; Wang, S. Y.; Huang, B. L.; Du, Y. P. Heteroatom-driven coordination fields altering single cerium atom sites for efficient oxygen reduction reaction. Adv. Mater. 2023, 35, 2302485.
Crossref Google Scholar
[34]

Wang, X.; Wang, J. W.; Wang, P.; Li, L. C.; Zhang, X. Y.; Sun, D. M.; Li, Y. F.; Tang, Y. W.; Wang, Y.; Fu, G. T. Engineering 3d-2p-4f gradient orbital coupling to enhance electrocatalytic oxygen reduction. Adv. Mater. 2022, 34, 2206540.
Crossref Google Scholar
[35]

Wang, X.; Tang, Y. W.; Lee, J. M.; Fu, G. T. Recent advances in rare-earth-based materials for electrocatalysis. Chem Catal. 2022, 2, 967–1008.
Crossref Google Scholar
[36]

Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. I. J.; Refson, K.; Payne, M. C. First principles methods using CASTEP. Z. Kristallogr. Cryst. Mater. 2005, 220, 567–570.
Crossref Google Scholar
[37]

Hasnip, P. J.; Pickard, C. J. Electronic energy minimisation with ultrasoft pseudopotentials. Comput. Phys. Commun. 2006, 174, 24–29.
Crossref Google Scholar
[38]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
[39]

Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B, 1992, 46, 6671–6687.
Crossref Google Scholar
[40]

Head, J. D.; Zerner, M. C. A Broyden–Fletcher–Goldfarb–Shanno optimization procedure for molecular geometries. Chem. Phys. Lett. 1985, 122, 264–270.
Crossref Google Scholar
[41]

McNellis, E. R.; Meyer, J.; Reuter, K. Azobenzene at coinage metal surfaces: Role of dispersive van der Waals interactions. Phys. Rev. B 2009, 80, 205414.
Crossref Google Scholar
[42]

Grimme, S.; Hansen, A.; Brandenburg, J. G.; Bannwarth, C. Dispersion-corrected mean-field electronic structure methods. Chem. Rev. 2016, 116, 5105–5154.
Crossref Google Scholar
[43]

Zhu, M. Z.; Zhao, C.; Liu, X. K.; Wang, X. L.; Zhou, F. Y.; Wang, J.; Hu, Y. M.; Zhao, Y. F.; Yao, T.; Yang, L. M. et al. Single atomic cerium sites with a high coordination number for efficient oxygen reduction in proton-exchange membrane fuel cells. ACS Catal. 2021, 11, 3923–3929.
Crossref Google Scholar
[44]

Hu, H.; Wang, J. J.; Cui, B. F.; Zheng, X. R.; Lin, J. G.; Deng, Y. D.; Han, X. P. Atomically dispersed selenium sites on nitrogen-doped carbon for efficient electrocatalytic oxygen reduction. Angew. Chem., Int. Ed. 2022, 61, e202114441.
Crossref Google Scholar
[45]

He, Y. T.; Yang, X. X.; Li, Y. S.; Liu, L. T.; Guo, S. W.; Shu, C. Y.; Liu, F.; Liu, Y. N.; Tan, Q.; Wu, G. Atomically dispersed Fe-Co dual metal sites as bifunctional oxygen electrocatalysts for rechargeable and flexible Zn-air batteries. ACS Catal. 2022, 12, 1216–1227.
Crossref Google Scholar
[46]

Peng, L. S.; Yang, J.; Yang, Y. Q.; Qian, F. R.; Wang, Q.; Sun-Waterhouse, D.; Shang, L.; Zhang, T. R.; Waterhouse, G. I. N. Mesopore-rich Fe-N-C catalyst with FeN4-O-NC single-atom sites delivers remarkable oxygen reduction reaction performance in alkaline media. Adv. Mater. 2022, 34, 2202544.
Crossref Google Scholar
[47]

Tang, X. N.; Wei, Y. H.; Zhai, W. J.; Wu, Y. G.; Hu, T.; Yuan, K.; Chen, Y. W. Carbon nanocage with maximum utilization of atomically dispersed iron as efficient oxygen electroreduction nanoreactor. Adv. Mater. 2023, 35, 2208942.
Crossref Google Scholar
[48]

Liang, H. W.; Zhuang, X. D.; Brüller, S.; Feng, X. L.; Müllen, K. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction. Nat. Commun. 2014, 5, 4973.
Crossref Google Scholar
[49]

Li, O. L.; Chiba, S.; Wada, Y.; Panomsuwan, G.; Ishizaki, T. Synthesis of graphitic-N and amino-N in nitrogen-doped carbon via a solution plasma process and exploration of their synergic effect for advanced oxygen reduction reaction. J. Mater. Chem. A 2017, 5, 2073–2082.
Crossref Google Scholar
[50]

Li, J.; Chen, S. G.; Yang, N.; Deng, M. M.; Ibraheem, S.; Deng, J. H.; Li, J.; Li, L.; Wei, Z. D. Ultrahigh-loading zinc single-atom catalyst for highly efficient oxygen reduction in both acidic and alkaline media. Angew. Chem., Int. Ed. 2019, 58, 7035–7039.
Crossref Google Scholar
[51]

Chen, Z. Y.; Su, X. Z.; Ding, J.; Yang, N.; Zuo, W. B.; He, Q. Y.; Wei, Z. M.; Zhang, Q.; Huang, J.; Zhai, Y. M. Boosting oxygen reduction reaction with Fe and Se dual-atom sites supported by nitrogen-doped porous carbon. Appl. Catal. B Environ. 2022, 308, 121206.
Crossref Google Scholar
[52]

Deng, D. J.; Qian, J. C.; Liu, X. Z.; Li, H. P.; Su, D.; Li, H. N.; Li, H. M.; Xu, L. Non-covalent interaction of atomically dispersed Cu and Zn pair sites for efficient oxygen reduction reaction. Adv. Funct. Mater. 2022, 32, 2203471.
Crossref Google Scholar
[53]

Li, J. C.; Qin, X. P.; Xiao, F.; Liang, C. H.; Xu, M. J.; Meng, Y.; Sarnello, E.; Fang, L. Z.; Li, T.; Ding, S. C. et al. Highly dispersive cerium atoms on carbon nanowires as oxygen reduction reaction electrocatalysts for Zn-air batteries. Nano Lett. 2021, 21, 4508–4515.
Crossref Google Scholar
[54]

Chu, Y. Y.; Luo, E. G.; Wei, Y.; Zhu, S. Y.; Wang, X.; Yang, L. T.; Gao, N. X.; Wang, Y.; Jiang, Z.; Liu, C. P. et a. Dual single-atom catalyst design to build robust oxygen reduction electrode via free radical scavenging. Chem Catal. 2023, 3, 100532.
Crossref Google Scholar
[55]

Zhao, Y. J.; Wang, H.; Li, J.; Fang, Y.; Kang, Y. S.; Zhao, T. Y.; Zhao, C. Y. Regulating the spin-state of rare-earth Ce single atom catalyst for boosted oxygen reduction in neutral medium. Adv. Funct. Mater. 2023, 33, 2305268.
Crossref Google Scholar
[56]

Jiang, K.; Wang, H. T. Electrocatalysis over graphene-defect-coordinated transition-metal single-atom catalysts. Chem 2018, 4, 194–195.
Crossref Google Scholar
[57]

Xiong, T. Z.; Zhu, Z. X.; He, Y. X.; Balogun, M. S.; Huang, Y. C. Phase evolution on the hydrogen adsorption kinetics of NiFe-based heterogeneous catalysts for efficient water electrolysis. Small Methods 2023, 7, 2201472.
Crossref Google Scholar
[58]

Han, Y. H.; Wang, Y. G.; Xu, R. R.; Chen, W. X.; Zheng, L. R.; Han, A. J.; Zhu, Y. Q.; Zhang, J.; Zhang, H. B. et al. Electronic structure engineering to boost oxygen reduction activity by controlling the coordination of the central metal. Energy Environ. Sci. 2018, 11, 2348–2352.
Crossref Google Scholar
Nano Research
Volume 17 Issue 6,
June 2024
Pages 4753-4763
DOI: 10.1007/s12274-024-6416-9
Cite this article:
Yin L, Zhang S, Sun M, et al. Non-bonding modulations between single atomic cerium and monodispersed selenium sites towards efficient oxygen reduction. Nano Research, 2024, 17(6): 4753-4763. https://doi.org/10.1007/s12274-024-6416-9
Topics:
NanocatalystsOxygen evolution reaction

1063

Views

4

Crossref

6

Web of Science

7

Scopus

0

CSCD

Altmetrics
Received: 08 November 2023
Revised: 11 November 2023
Accepted: 14 December 2023
Published: 13 January 2024
© Tsinghua University Press 2024
Return