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

Charge-asymmetry Fe1Cu single-atom alloy catalyst for efficient oxygen reduction reaction

Xudong Niu1, Jian Wei2( ), Dongyao Xu1( ), Jiajing Pei3, Rui Sui4( )
School of Chemical & Environmental Engineering, China University of Mining and Technology, Beijing 100083, China
Institute of Water Ecology and Environment, Chinese Research Academy of Environmental Sciences, Beijing 100083, China
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China
Show Author Information

Graphical Abstract

We developed a novel incorporation of charge-asymmetry atomically dispersed Fe single atom with Cu nanoparticles on nitrogen-doped carbon nanosheet (denoted as Fe1Cu SAA/NC). The catalyst showed excellent catalytic performance in the oxygen reduction reaction (ORR) process.

Abstract

The development of high-efficient and low-cost oxygen reduction reaction (ORR) electrocatalysts is crucial for the practical applications of metal-air batteries. One promising way is to develop Fe single-atom catalysts. However, the single active center and inherent electronic structure of Fe single-atom catalysts lead to the undesirable adsorption of multiple ORR intermediates. Herein, a charge-asymmetry single-atom alloy (SAA) catalyst with Fe–Cu dual sites supported on nitrogen-doped carbon nanosheet (Fe1Cu SAA/NC) was constructed. Various characterizations manifest the existence of electron interaction between Fe and Cu in Fe1Cu SAA/NC, which facilitates the adsorption of ORR intermediate for fast kinetics. Consequently, the charge-asymmetry Fe1Cu SAA/NC exhibits much faster ORR kinetics with a half-wave potential of 0.917 V vs. reversible hydrogen electrode (RHE), outperforming its counterparts in the references. Furthermore, Fe1Cu SAA/NC still maintains a high half-wave potential with only a drop of 5 mV after 5000 cycles, indicating excellent stability. This work provides a new strategy to design highly active and non-noble metal ORR electrocatalysts, which hold great potential for various catalytic applications.

Keywords

Fe1Cu single-atom alloy (SAA)electrocatalysisoxygen reduction reactioncharge-asymmetry

Electronic Supplementary Material

Download File(s)
12274_2023_6317_MOESM1_ESM.pdf (2.7 MB)

References

[1]

Li, Y. G.; Dai, H. J. Recent advances in zinc-air batteries. Chem. Soc. Rev. 2014, 43, 5257–5275.
Crossref Google Scholar
[2]

Armand, M.; Tarascon, J. M. Building better batteries. Nature 2008, 451, 652–657.
Crossref Google Scholar
[3]

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. Sisyphus effects in hydrogen electrochemistry on metal silicides enabled by silicene subunit edge. Sci. Bull. 2019, 64, 617–624
Crossref Google Scholar
[4]

Li, C. J.; Shan, G. C.; Guo, C. X.; Ma, R. G. Design strategies of Pd-based electrocatalysts for efficient oxygen reduction. Rare Met. 2023, 42, 1778–1799.
Crossref Google Scholar
[5]

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., Int. Ed. 2023, 62, e202219191.
Crossref Google Scholar
[6]

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. Q.; 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.
Crossref Google Scholar
[7]

Cui, T. T.; Wang, Y. P.; Ye, T.; Wu, J.; Chen, Z. Q.; Li, J.; Lei, Y. P.; Wang, D. S.; Li, Y. D. Engineering dual single-atom sites on 2D ultrathin N-doped carbon nanosheets attaining ultra-low-temperature zinc-air battery. Angew. Chem., Int. Ed. 2022, 61, e202115219.
Crossref Google Scholar
[8]

Jiang, Z. L.; Sun, W. M.; Shang, H. S.; Chen, W. X.; Sun, T. T.; Li, H. J.; Dong, J. C.; Zhou, J.; Li, Z.; Wang, Y. et al. Atomic interface effect of a single atom copper catalyst for enhanced oxygen reduction reactions. Energy Environ. Sci. 2019, 12, 3508–3514.
Crossref Google Scholar
[9]

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
[10]

Chen, Y. P.; Zheng, X. S.; Cai, J. Y.; Zhao, G. Q.; Zhang, B. X.; Luo, Z. X.; Wang, G. M.; Pan, H. G.; Sun, W. P. Sulfur doping triggering enhanced Pt–N coordination in graphitic carbon nitride-supported Pt electrocatalysts toward efficient oxygen reduction reaction. ACS Catal. 2022, 12, 7406–7414.
Crossref Google Scholar
[11]

Zaman, S.; Su, Y. Q.; Dong, C. L.; Qi, R. J.; Huang, L.; Qin, Y. Y.; Huang, Y. C.; Li, F. M.; You, B.; Guo, W. et al. Scalable molten salt synthesis of platinum alloys planted in metal–nitrogen–graphene for efficient oxygen reduction. Angew. Chem., Int. Ed. 2022, 61, e202115835.
Crossref Google Scholar
[12]

Zaman, S.; Huang, L.; Douka, A. I.; Yang, H.; You, B.; Xia, B. Y. Oxygen reduction electrocatalysts toward practical fuel cells: Progress and perspectives. Angew. Chem., Int. Ed. 2021, 60, 17832–17852.
Crossref Google Scholar
[13]

Chen, G. B.; An, Y.; Liu, S. W.; Sun, F. F.; Qi, H. Y.; Wu, H. F.; He, Y. H.; Liu, P.; Shi, R.; Zhang, J. et al. Highly accessible and dense surface single metal FeN4 active sites for promoting the oxygen reduction reaction. Energy Environ. Sci. 2022, 15, 2619–2628.
Crossref Google Scholar
[14]

Wang, J.; Huang, Z. Q.; Liu, W.; Chang, C. R.; Tang, H. L.; Li, Z. J.; Chen, W. X.; Jia, C. J.; Yao, T.; Wei, S. Q. et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc. 2017, 139, 17281–17284.
Crossref Google Scholar
[15]

Wang, Y.; Wang, D. S.; Li, Y. D. A fundamental comprehension and recent progress in advanced Pt-based ORR nanocatalysts. SmartMat 2021, 2, 56–75.
Crossref Google Scholar
[16]

Xi, J. B.; Jung, H. S.; Xu, Y.; Xiao, F.; Bae, J. W.; Wang, S. Synthesis strategies, catalytic applications, and performance regulation of single-atom catalysts. Adv. Funct. Mater. 2021, 31, 2008318.
Crossref Google Scholar
[17]

Zhu, P.; Xiong, X.; Wang, X. L.; Ye, C. L.; Li, J. Z.; Sun, W. M.; Sun, X. H.; Jiang, J. J.; Zhuang, Z. B.; Wang, D. S. et al. Regulating the FeN4 moiety by constructing Fe–Mo dual-metal atom sites for efficient electrochemical oxygen reduction. Nano Lett. 2022, 22, 9507–9515.
Crossref Google Scholar
[18]

Kusada, K.; Wu, D. S.; Yamamoto, T.; Toriyama, T.; Matsumura, S.; Xie, W.; Koyama, M.; Kawaguchi, S.; Kubota, Y.; Kitagawa, H. Emergence of high ORR activity through controlling local density-of-states by alloying immiscible Au and Ir. Chem. Sci. 2019, 10, 652–656.
Crossref Google Scholar
[19]

Deng, C.; Wu, K. H.; Scott, J.; Zhu, S. M.; Amal, R.; Wang, D. W. Ternary MnO/CoMn alloy@N-doped graphitic composites derived from a bi-metallic pigment as bi-functional electrocatalysts. J. Mater. Chem. A 2019, 7, 20649–20657.
Crossref Google Scholar
[20]

Hao, J. C.; Zhuang, Z. C.; Cao, K. C.; Gao, G. H.; Wang, C.; Lai, F. L.; Lu, S. L.; Ma, P. M.; Dong, W. F.; Liu, T. X. et al. Unraveling the electronegativity-dominated intermediate adsorption on high-entropy alloy electrocatalysts. Nat. Commun. 2022, 13, 2662.
Crossref Google Scholar
[21]

Kim, M.; Kim, H.; Cho, M.; Kim, D. Theoretical understanding of oxygen stability in Mn–Fe binary layered oxides for sodium-ion batteries. J. Mater. Chem. A 2022, 10, 11101–11109.
Crossref Google Scholar
[22]

Lebechi, A. K.; Ipadeola, A. K.; Eid, K.; Abdullah, A. M.; Ozoemena, K. I. Porous spinel-type transition metal oxide nanostructures as emergent electrocatalysts for oxygen reduction reactions. Nanoscale 2022, 14, 10717–10737.
Crossref Google Scholar
[23]

Huang, X. X.; Shen, T.; Zhang, T.; Qiu, H. L.; Gu, X. X.; Ali, Z.; Hou, Y. L. Efficient oxygen reduction catalysts of porous carbon nanostructures decorated with transition metal species. Adv. Energy Mater. 2020, 10, 1900375.
Crossref Google Scholar
[24]

Zhu, J. W.; Huang, Y. P.; Mei, W. C.; Zhao, C. Y.; Zhang, C. T.; Zhang, J.; Amiinu, I. S.; Mu, S. C. Effects of intrinsic pentagon defects on electrochemical reactivity of carbon nanomaterials. Angew. Chem., Int. Ed. 2019, 58, 3859–3864.
Crossref Google Scholar
[25]

Li, Z. L.; Zhuang, Z. C.; Lv, F.; Zhu, H.; Zhou, L.; Luo, M. C.; Zhu, J. X.; Lang, Z. Q.; Feng, S. H.; Chen, W. et al. The marriage of the FeN4 moiety and MXene boosts oxygen reduction catalysis: Fe 3d electron delocalization matters. Adv. Mater. 2018, 30, 1803220.
Crossref Google Scholar
[26]

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.
Crossref Google Scholar
[27]

Gao, Y.; Liu, B. Z.; Wang, D. S. Microenvironment engineering of single/dual-atom catalysts for electrocatalytic application. Adv. Mater. 2023, 35, 2209654.
Crossref Google Scholar
[28]

Shen, J.; Wang, D. S. How to select heterogeneous CO2 reduction electrocatalyst. Nano Res. Energy 2024, 3, e9120096.
Crossref Google Scholar
[29]

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
[30]

Zhu, H.; Sun, S. H.; Hao, J. C.; Zhuang, Z. C.; Zhang, S. G.; Wang, T. D.; Kang, Q.; Lu, S. L.; Wang, X. F.; Lai, F. L. et al. A high-entropy atomic environment converts inactive to active sites for electrocatalysis. Energy Environ. Sci. 2023, 16, 619–628.
Crossref Google Scholar
[31]

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, e202303185.
Crossref Google Scholar
[32]

Wang, Z. F.; Wang, H. Y.; Liu, X. L.; Chen, Y. X.; Zhao, Y.; Zhang, Y. G.; Han, Q. Q.; Qin, C. L.; Bakenov, Z.; Wang, Y. C. et al. Single Zn atoms anchored on hollow carbon nanofiber network for dendrite-free lithium metal anode of flexible Li-S full cell. Rare Met. 2023, 42, 3705–3717.
Crossref Google Scholar
[33]

Hu, Y. M.; Chao, T. T.; Li, Y. P.; Liu, P. G.; Zhao, T. H.; Yu, G.; Chen, C.; Liang, X.; Jin, H. L.; Niu, S. W. et al. Cooperative Ni(Co)–Ru–P sites activate dehydrogenation for hydrazine oxidation assisting self-powered H2 production. Angew. Chem., Int. Ed. 2023, 62, e202308800.
Crossref Google Scholar
[34]

Zhang, T. J.; Walsh, A. G.; Yu, J. H.; Zhang, P. Single-atom alloy catalysts: Structural analysis, electronic properties and catalytic activities. Chem. Soc. Rev. 2021, 50, 569–588.
Crossref Google Scholar
[35]

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.
Crossref Google Scholar
[36]

Da, Y. M.; Jiang, R.; Tian, Z. L.; Han, X. P.; Chen, W.; Hu, W. B. The applications of single-atom alloys in electrocatalysis: Progress and challenges. SmartMat 2023, 4, e1136.
Crossref Google Scholar
[37]

Pei, G. X.; Liu, X. Y.; Yang, X. F.; Zhang, L. L.; Wang, A. Q.; Li, L.; Wang, H.; Wang, X. D.; Zhang, T. Performance of Cu-alloyed Pd single-atom catalyst for semihydrogenation of acetylene under simulated front-end conditions. ACS Catal. 2017, 7, 1491–1500.
Crossref Google Scholar
[38]

Chao, T. T.; Luo, X.; Chen, W. X.; Jiang, B.; Ge, J. J.; Lin, Y.; Wu, G.; Wang, X. Q.; Hu, Y. M.; Zhuang, Z. B. et al. Atomically dispersed copper–platinum dual sites alloyed with palladium nanorings catalyze the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2017, 56, 16047–16051.
Crossref Google Scholar
[39]

Jiang, J. C.; Chen, J. C.; Zhao, M. D.; Yu, Q.; Wang, Y. G.; Li, J. Rational design of copper-based single-atom alloy catalysts for electrochemical CO2 reduction. Nano Res. 2022, 15, 7116–7123.
Crossref Google Scholar
[40]

Marcinkowski, M. D.; Darby, M. T.; Liu, J. L.; Wimble, J. M.; Lucci, F. R.; Lee, S.; Michaelides, A.; Flytzani-Stephanopoulos, M.; Stamatakis, M.; Sykes, E. C. H. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation. Nat. Chem. 2018, 10, 325–332.
Crossref Google Scholar
[41]

Li, Z. T.; Yang, T. T.; Zhao, W. N.; Xu, T.; Wei, L. Q.; Feng, J. Z.; Yang, X. J.; Ren, H.; Wu, M. B. Structural modulation of Co catalyzed carbon nanotubes with Cu–Co bimetal active center to inspire oxygen reduction reaction. ACS Appl. Mater. Interfaces 2019, 11, 3937–3945.
Crossref Google Scholar
[42]

Gan, T.; Wang, D. S. Atomically dispersed materials: Ideal catalysts in atomic era. Nano Res. 2024, 17, 18–38
Crossref Google Scholar
[43]

Han, G. K.; Zhang, X.; Liu, W.; Zhang, Q. H.; Wang, Z. Q.; Cheng, J.; Yao, T.; Gu, L.; Du, C. Y.; Gao, Y. Z. et al. Substrate strain tunes operando geometric distortion and oxygen reduction activity of CuN2C2 single-atom sites. Nat. Commun. 2021, 12, 6335.
Crossref Google Scholar
[44]

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.
Crossref Google Scholar
[45]

Liu, Z. Y.; Parvez, K.; Li, R. J.; Dong, R. H.; Feng, X. L.; Müllen, K. Transparent conductive electrodes from graphene/PEDOT: PSS hybrid inks for ultrathin organic photodetectors. Adv. Mater. 2015, 27, 669–675.
Crossref Google Scholar
[46]

Luo, W. H.; Wang, Y.; Luo, L. X.; Gong, S.; Wei, M. N.; Li, Y. X.; Gan, X. P.; Zhao, Y. Y.; Zhu, Z. H.; Li, Z. Single-atom and bimetallic nanoalloy supported on nanotubes as a bifunctional electrocatalyst for ultrahigh-current-density overall water splitting. ACS Catal. 2022, 12, 1167–1179.
Crossref Google Scholar
[47]

Lu, X. Y.; Gao, S. S.; Lin, H.; Yu, L. D.; Han, Y. H.; Zhu, P.; Bao, W. C.; Yao, H. L.; Chen, Y.; Shi, J. L. Bioinspired copper single-atom catalysts for tumor parallel catalytic therapy. Adv. Mater. 2020, 32, 2002246.
Crossref Google Scholar
[48]

Yang, Z. H.; Jiang, K. Y.; Tong, G. S.; Ke, C. C.; Wu, H. F.; Liu, P.; Zhang, J. C.; Ji, H. P.; Zhu, J. H.; Lu, C. B. et al. Copper-involved highly efficient oxygen reduction reaction in both alkaline and acidic media. Chem. Eng. J. 2022, 437, 135377.
Crossref Google Scholar
[49]

Chen, P. Z.; Zhang, N.; Wang, S. B.; Zhou, T. P.; Tong, Y.; Ao, C. C.; Yan, W. S.; Zhang, L. D.; Chu, W. S.; Wu, C. Z. et al. Interfacial engineering of cobalt sulfide/graphene hybrids for highly efficient ammonia electrosynthesis. Proc. Natl. Acad. Sci. USA 2019, 116, 6635–6640.
Crossref Google Scholar
[50]

Tong, Y.; Chen, P. Z.; Zhou, T. P.; Xu, K.; Chu, W. S.; Wu, C. Z.; Xie, Y. A bifunctional hybrid electrocatalyst for oxygen reduction and evolution: Cobalt oxide nanoparticles strongly coupled to B,N-decorated graphene. Angew. Chem., Int. Ed. 2017, 56, 7121–7125.
Crossref Google Scholar
[51]

Nam, G.; Park, J.; Choi, M.; Oh, P.; Park, S.; Kim, M. G.; Park, N.; Cho, J.; Lee, J. S. Carbon-coated core–shell Fe–Cu nanoparticles as highly active and durable electrocatalysts for a Zn-air battery. ACS Nano 2015, 9, 6493–6501.
Crossref Google Scholar
[52]

Wang, Q.; Shang, L.; Sun-Waterhouse, D.; Zhang, T. R.; Waterhouse, G. Engineering local coordination environments and site densities for high-performance Fe-N-C oxygen reduction reaction electrocatalysis. SmartMat 2021, 2, 154–175.
Crossref Google Scholar
[53]

Qu, Y. T.; Li, Z. J.; Chen, W. X.; Lin, Y.; Yuan, T. W.; Yang, Z. K.; Zhao, C. M.; Wang, J.; Zhao, C.; Wang, X. et al. Direct transformation of bulk copper into copper single sites via emitting and trapping of atoms. Nat. Catal. 2018, 1, 781–786.
Crossref Google Scholar
[54]

Hung, S. F.; Xu, A. N.; Wang, X.; Li, F. W.; Hsu, S. H.; Li, Y. H.; Wicks, J.; Cervantes, E. G.; Rasouli, A. S.; Li, Y. C. et al. A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation. Nat. Commun. 2022, 13, 819.
Crossref Google Scholar
[55]

Pan, Y.; Ma, X. L.; Wang, M. M.; Yang, X.; Liu, S. J.; Chen, H. C.; Zhuang, Z. W.; Zhang, Y. H.; Cheong, W. C.; Zhang, C. et al. Construction of N,P co-doped carbon frames anchored with Fe single atoms and Fe2P nanoparticles as a robust coupling catalyst for electrocatalytic oxygen reduction. Adv. Mater. 2022, 34, 2203621.
Crossref Google Scholar
[56]

Shan, J. J.; Liu, J. L.; Li, M. W.; Lustig, S.; Lee, S.; Flytzani-Stephanopoulos, M. NiCu single atom alloys catalyze the C–H bond activation in the selective non-oxidative ethanol dehydrogenation reaction. Appl. Catal. B: Environ. 2018, 226, 534–543.
Crossref Google Scholar
[57]

Chen, Q. M.; Liu, Y.; Lu, Y. W.; Hou, Y. J.; Zhang, X. D.; Shi, W. B.; Huang, Y. M. Atomically dispersed Fe/Bi dual active sites single-atom nanozymes for cascade catalysis and peroxymonosulfate activation to degrade dyes. J. Hazard. Mater. 2022, 422, 126929.
Crossref Google Scholar
[58]

Li, P.; Qiang, F. Q.; Tan, X. H.; Li, Z.; Shi, J.; Liu, S.; Huang, M. H.; Chen, J. W.; Tian, W. Q.; Wu, J. Y. et al. Electronic modulation induced by decorating single-atomic Fe–Co pairs with Fe–Co alloy clusters toward enhanced ORR/OER activity. Appl. Catal. B: Environ. 2024, 340, 123231.
Crossref Google Scholar
[59]

Huang, Y. F.; Kong, F. T.; Tian, H.; Pei, F. L.; Chen, Y. F.; Meng, G.; Chang, Z. W.; Chen, C.; Cui, X. Z.; Shi, J. L. Ultrauniformly dispersed Cu nanoparticles embedded in N-doped carbon as a robust oxygen electrocatalyst. ACS Sustain. Chem. Eng. 2022, 10, 6370–6381.
Crossref Google Scholar
Nano Research
Volume 17 Issue 6,
June 2024
Pages 4702-4710
DOI: 10.1007/s12274-023-6317-3
Cite this article:
Niu X, Wei J, Xu D, et al. Charge-asymmetry Fe1Cu single-atom alloy catalyst for efficient oxygen reduction reaction. Nano Research, 2024, 17(6): 4702-4710. https://doi.org/10.1007/s12274-023-6317-3
Topics:
Catalytic

970

Views

8

Crossref

7

Web of Science

7

Scopus

0

CSCD

Altmetrics
Received: 20 September 2023
Revised: 29 October 2023
Accepted: 01 November 2023
Published: 23 February 2024
© Tsinghua University Press 2024
Return