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

Plasma-enabled synthesis of ordered PtFe alloy nanoparticles encapsulated with ultrathin N-doped carbon shells for efficient methanol electrooxidation

Xuxu Sun1,2, Zhijian Mao3, Ruiqi Wang1,2, Xiaohu Pi1,4, Changle Chen1,2, Junbo Zhong5, Qi Wang1,2( ), Kostya (Ken) Ostrikov6
Institute of Plasma Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China
University of Science and Technology of China, Hefei 230026, China
Rutgers Preparatory School, New Jersey, 1345 Easton Ave, Somerset, NJ 08873, USA
Institute of Intelligent Machines, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China
College of Chemical Engineering, Sichuan University of Science and Engineering, Zigong 643000, China
School of Chemistry and Physics and QUT Centre for Materials Science, Queensland University of Technology (QUT), Brisbane, QLD 4000, Australia
Show Author Information

Graphical Abstract

Benefiting from the reactive plasma-specific effects, the as-obtained PtFe alloys supported on N-doped carbon nanotubes (denoted as PtFe@NCNT-P) electrocatalyst were endowed with the ultrafine ordered PtFe alloy nanoparticles and ultrathin N-doped carbon shells, thereby exhibiting excellent catalytic activity and stability toward methanol oxidation reaction.

Abstract

Methanol oxidation reaction (MOR), the key reaction for clean energy generation in fuel cells, is kinetically sluggish and short-lasting because of insufficient catalytic activity and stability of the common Pt-based electrocatalysts. Ordered Pt alloy structures which promise to surmount these issues, are challenging and impractical to fabricate using common high-temperature annealing. To address the urgent need for simple and rapid synthesis methods for such alloys, here we report the versatile plasma-assisted thermal annealing synthesis of a robust electrocatalyst with PtFe alloys supported on N-doped carbon nanotubes (denoted as PtFe@NCNT-P). Benefiting from the reactive plasma-specific effects, the PtFe@NCNT-P electrocatalyst features ultrafine PtFe alloy nanoparticles (mean size ~ 2.88 nm, ordered degree ~ 87.07%) and ultrathin N-doped carbon (NC) shells (0.3–0.7 nm), leading to the excellent catalytic activity and stability toward MOR. The catalyst shows the specific and mass activities of 3.99 mA/cm2 and 2,148.5 mA/mg, which are 7.82 and 7.41 times higher than those for commercial Pt/C (0.51 mA/cm2, 290 mA/mg), and 2.18 and 2.59 times higher compared to the plasma-untreated PtFe@NCNT (1.83 mA/cm2, 829.5 mA/mg), respectively. The PtFe@NCNT-P further exhibits extraordinary stability during the long-term chronoamperometry test and 1,000-cycle cyclic voltammetry scanning, much better compared to PtFe@NCNT samples even after the longer thermal annealing. These findings show great potential of the plasma-enabled synthesis of high-performance carbon-supported metallic electrocatalysts for the emerging clean energy technologies.

Keywords

methanol oxidation reactionhighly ordered PtFe alloy nanoparticlesultrathin N-doped carbon shellN-doped carbon supportplasma nanotechnology

Electronic Supplementary Material

Download File(s)
12274_2022_4890_MOESM1_ESM.pdf (2.1 MB)

References

[1]

Ding, J. J.; Hu, W. L.; Ma, L.; Gan, M. Y.; Xie, F.; Zhan, W.; Lu W. Facile construction of mesoporous carbon enclosed with NiCoPx nanoparticles for desirable Pt-based catalyst support in methanol oxidation. J. Power Sources 2021, 481, 228888.
Crossref Google Scholar
[2]

Li, W.; Wang, D. D.; Zhang, Y. Q.; Tao, L.; Wang, T. H.; Zou, Y. Q.; Wang, Y. Y.; Chen, R.; Wang, S. Y. Defect engineering for fuel-cell electrocatalysts. Adv. Mater. 2020, 32, 1907879.
Crossref Google Scholar
[3]

Neaţu, Ş.; Neaţu, F.; Chirica, I. M.; Borbáth, I.; Tálas, E.; Tompos, A.; Somacescu, S.; Osiceanu, P.; Folgado, M. A.; Chaparro, A. M. et al. Recent progress in electrocatalysts and electrodes for portable fuel cells. J. Mater. Chem. A 2021, 9, 17065–17128.
Crossref Google Scholar
[4]

Tian, H.; Wu, D. X.; Li, J.; Luo, J. M.; Jia, C. M.; Liu, Z. X.; Huang, W.; Chen, Q.; Shim, C. M.; Deng, P. et al. Rational design ternary platinum based electrocatalysts for effective methanol oxidation reaction. J. Energy Chem. 2022, 70, 230–235.
Crossref Google Scholar
[5]

Luo, X. L.; Liu, C.; Wang, X. L.; Shao, Q.; Pi, Y. C.; Zhu, T.; Li, Y. Y.; Huang, X. Q. Spin regulation on 2D Pd-Fe-Pt nanomeshes promotes fuel electrooxidations. Nano Lett. 2020, 20, 1967–1973.
Crossref Google Scholar
[6]

Scofield, M. E.; Koenigsmann, C.; Wang, L.; Liu, H. Q.; Wong, S. S. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction. Energy Environ. Sci. 2015, 8, 350–363.
Crossref Google Scholar
[7]

Ren, X. F.; Wang, Y. R.; Liu, A. M.; Zhang, Z. H.; Lv, Q. Y.; Liu, B. H. Current progress and performance improvement of Pt/C catalysts for fuel cells. J. Mater. Chem. A 2020, 8, 24284–24306.
Crossref Google Scholar
[8]

Zhu, J. Y.; Chen, S. Q.; Xue, Q.; Li, F. M.; Yao, H. C.; Xu, L.; Chen, Y. Hierarchical porous Rh nanosheets for methanol oxidation reaction. Appl. Catal. B:Environ. 2020, 264, 118520.
Crossref Google Scholar
[9]

Yang, J.; Hübner, R.; Zhang, J. W.; Wan, H.; Zheng, Y. Y.; Wang, H. L.; Qi, H. Y.; He, L. Q.; Li, Y.; Dubale, A. A. et al. A robust PtNi nanoframe/N-doped graphene aerogel electrocatalyst with both high activity and stability. Angew. Chem., Int. Ed. 2021, 60, 9590–9597.
Crossref Google Scholar
[10]

Zou, X.; Chen, S. G.; Wang, Q. M.; Gao, X. Y.; Li, J.; Li, J.; Li, L.; Ding, W.; Wei, Z. D. Leaching- and sintering-resistant hollow or structurally ordered intermetallic PtFe alloy catalysts for oxygen reduction reactions. Nanoscale 2019, 11, 20115–20122.
Crossref Google Scholar
[11]

Xue, S. F.; Deng, W. T.; Yang, F.; Yang, J. L.; Amiinu, I. S.; He, D. P.; Tang, H. L.; Mu, S. C. Hexapod PtRuCu nanocrystalline alloy for highly efficient and stable methanol oxidation. ACS Catal. 2018, 8, 7578–7584.
Crossref Google Scholar
[12]

Lee, D.; Gok, S.; Kim, Y.; Sung, Y. E.; Lee, E.; Jang, J. H.; Hwang, J. Y.; Kwon, O. J.; Lim, T. Methanol tolerant Pt–C core–shell cathode catalyst for direct methanol fuel cells. ACS Appl. Mater. Interfaces 2020, 12, 44588–44596.
Crossref Google Scholar
[13]

Zhao, W.; Ma, L.; Gan, M. Y.; Li, X. D.; Zhang, Y. C.; Hua, X. L.; Wang, L. Engineering intermetallic–metal oxide interface with low platinum loading for efficient methanol electrooxidation. J. Colloid Interface Sci. 2021, 604, 52–60.
Crossref Google Scholar
[14]

Li, X. G.; Bi, W. T.; Zhang, L.; Tao, S.; Chu, W. S.; Zhang, Q.; Luo, Y.; Wu, C. Z.; Xie, Y. Single-atom Pt as co-catalyst for enhanced photocatalytic H2 evolution. Adv. Mater. 2016, 28, 2427–2431.
Crossref Google Scholar
[15]

Zhang, Z. Q.; Liu, J. P.; Wang, J.; Wang, Q.; Wang, Y. H.; Wang, K.; Wang, Z.; Gu, M.; Tang, Z. H.; Lim, J. et al. Single-atom catalyst for high-performance methanol oxidation. Nat. Commun. 2021, 12, 5235.
Crossref Google Scholar
[16]

Zhu, C. Z.; Fu, S. F.; Shi, Q. R.; Du, D.; Lin, Y. H. Single-atom electrocatalysts. Angew. Chem., Int. Ed. 2017, 56, 13944–13960.
Crossref Google Scholar
[17]

Shang, L.; Bian, T.; Zhang, B. H.; Zhang, D. H.; Wu, L. Z.; Tung, C. H.; Yin, Y. D.; Zhang, T. R. Graphene-supported ultrafine metal nanoparticles encapsulated by mesoporous silica: Robust catalysts for oxidation and reduction reactions. Angew. Chem., Int. Ed. 2014, 53, 250–254.
Crossref Google Scholar
[18]

Han, A. L.; Wang, X. J.; Tang, K.; Zhang, Z. D.; Ye, C. L.; Kong, K. J.; Hu, H. B.; Zheng, L. R.; Jiang, P.; Zhao, C. X. et al. An adjacent atomic platinum site enables single-atom iron with high oxygen reduction reaction performance. Angew. Chem., Int. Ed. 2021, 60, 19262–19271.
Crossref Google Scholar
[19]

Zhu, Z. J.; Zhai, Y. L.; Dong, S. J. Facial synthesis of PtM (M = Fe, Co, Cu, Ni) bimetallic alloy nanosponges and their enhanced catalysis for oxygen reduction reaction. ACS Appl. Mater. Interfaces. 2014, 6, 16721–16726.
Crossref Google Scholar
[20]

Deng, J.; Deng, D. H.; Bao, X. H. Robust catalysis on 2D materials encapsulating metals: Concept, application, and perspective. Adv. Mater. 2017, 29, 1606967.
Crossref Google Scholar
[21]

Yoo, T. Y.; Yoo, J. M.; Sinha, A. K.; Bootharaju, M. S.; Jung, E.; Lee, H. S.; Lee, B. H.; Kim, J.; Antink, W. H.; Kim, Y. M. et al. Direct synthesis of intermetallic platinum-alloy nanoparticles highly loaded on carbon supports for efficient electrocatalysis. J. Am. Chem. Soc. 2020, 142, 14190–14200.
Crossref Google Scholar
[22]

Wu, D. F.; Zhang, W.; Lin, A. J.; Cheng, D. J. Low Pt-content ternary PtNiCu nanoparticles with hollow interiors and accessible surfaces as enhanced multifunctional electrocatalysts. ACS Appl. Mater. Interfaces 2020, 12, 9600–9608.
Crossref Google Scholar
[23]

Xiao, Y. X.; Ying, J.; Tian, G.; Zhang, X. Q.; Janiak, C.; Ozoemena, K. I.; Yang, X. Y. PtPd hollow nanocubes with enhanced alloy effect and active facets for efficient methanol oxidation reaction. Chem. Commun. 2021, 57, 986–989.
Crossref Google Scholar
[24]

Yue, X. Y.; Pu, Y. G.; Zhang, W.; Zhang, T.; Gao, W. Ultrafine Pt nanoparticles supported on double-shelled C/TiO2 hollow spheres material as highly efficient methanol oxidation catalysts. J. Energy Chem. 2020, 49, 275–282.
Crossref Google Scholar
[25]

Ouyang, Y. R.; Cao, H. J.; Wu, H. J.; Wu, D. B.; Wang, F. Q.; Fan, X. J.; Yuan, W. Y.; He, M. X.; Zhang, L. Y.; Li, C. M. Tuning Pt-skinned PtAg nanotubes in nanoscales to efficiently modify electronic structure for boosting performance of methanol electrooxidation. Appl. Catal. B:Environ. 2020, 265, 118606.
Crossref Google Scholar
[26]

Long, X. Y.; Yin, P.; Lei, T.; Wang, K. C.; Zhan, Z. X. Methanol electro-oxidation on Cu@Pt/C core–shell catalyst derived from Cu-MOF. Appl. Catal. B:Environ. 2020, 260, 118187.
Crossref Google Scholar
[27]

Lei, W. J.; Li, M. G.; He, L.; Meng X.; Mu, Z. J.; Yu, Y. S.; Ross, F. M.; Yang, W. W. A general strategy for bimetallic Pt-based nano-branched structures as highly active and stable oxygen reduction and methanol oxidation bifunctional catalysts. Nano Res. 2020, 13, 638–645.
Crossref Google Scholar
[28]

Zhang, Y. P.; Gao, F.; Song, T. X.; Wang, C.; Chen, C. Y.; Du, Y. K. Novel networked wicker-like PtFe nanowires with branch-rich exteriors for efficient electrocatalysis. Nanoscale 2019, 11, 15561–15566.
Crossref Google Scholar
[29]

Li, H. Y.; Wu, X. S.; Tao, X. L.; Lu, Y.; Wang, Y. W. Direct synthesis of ultrathin Pt nanowire arrays as catalysts for methanol oxidation. Small 2020, 16, 2001135.
Crossref Google Scholar
[30]

Li, Z. J.; Jiang, X.; Wang, X. R.; Hu, J. R.; Liu, Y. Y.; Fu, G. T.; Tang, Y. W. Concave PtCo nanocrosses for methanol oxidation reaction. Appl. Catal. B:Environ. 2020, 277, 119135.
Crossref Google Scholar
[31]

Wang, L. J.; Tian, X. L.; Xu, Y. Y.; Zaman, S.; Qi, K.; Liu, H. F.; Xia, B. Y. Engineering one-dimensional and hierarchical PtFe alloy assemblies towards durable methanol electrooxidation. J. Mater. Chem. A 2019, 7, 13090–13095.
Crossref Google Scholar
[32]

Shan, A. X.; Huang, S. Y.; Zhao, H. F.; Jiang, W. G.; Teng, X. A.; Huang, Y. C.; Chen, C.; Wang, R. M.; Lau, W. M. Atomic-scaled surface engineering Ni-Pt nanoalloys towards enhanced catalytic efficiency for methanol oxidation reaction. Nano Res. 2020, 13, 3088–3097.
Crossref Google Scholar
[33]

Yang, C. Z.; Jiang, Q. G.; Liu, H.; Yang, L.; He, H. Y.; Huang, H. J.; Li, W. H. Pt-on-Pd bimetallic nanodendrites stereoassembled on MXene nanosheets for use as high-efficiency electrocatalysts toward the methanol oxidation reaction. J. Mater. Chem. A 2021, 9, 15432–15440.
Crossref Google Scholar
[34]

He, S. Q.; Liu, Y.; Zhan, H. B.; Guan, L. H. Direct thermal annealing synthesis of ordered Pt alloy nanoparticles coated with a thin N-doped carbon shell for the oxygen reduction reaction. ACS Catal. 2021, 11, 9355–9365.
Crossref Google Scholar
[35]

Yang, C. L.; Wang, L. N.; Yin, P.; Liu, J. Y.; Chen, M. X.; Yan, Q. Q.; Wang, Z. S.; Xu, S. L.; Chu, S. Q.; Cui, C. H. et al. Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells. Science 2021, 374, 459–464.
Crossref Google Scholar
[36]

Tu, Y. C.; Ren, P. J.; Deng, D. H.; Bao, X. H. Structural and electronic optimization of graphene encapsulating binary metal for highly efficient water oxidation. Nano Energy 2018, 52, 494–500.
Crossref Google Scholar
[37]

Yu, L.; Deng, D. H.; Bao, X. H. Chain mail for catalysts. Angew. Chem., Int. Ed. 2020, 59, 15294–15297.
Crossref Google Scholar
[38]

Tu, Y. C.; Deng, J.; Ma, C.; Yu, L.; Bao, X. H.; Deng, D. H. Double-layer hybrid chainmail catalyst for high-performance hydrogen evolution. Nano Energy 2020, 72, 104700.
Crossref Google Scholar
[39]

Chen, Y. J.; Ji, S. F.; Wang, Y. G.; Dong, J. C.; Chen, W. X.; Li, Z.; Shen, R. A.; Zheng, L. R.; Zhuang, Z. B.; Wang, D. S. et al. Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2017, 56, 6937–6941.
Crossref Google Scholar
[40]

Deng, J.; Ren, P. J.; Deng, D. H.; Bao, X. H. Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2015, 54, 2100–2104.
Crossref Google Scholar
[41]

Cui, X. J.; Ren, P. J.; Deng, D. H.; Deng, J.; Bao, X. H. Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation. Energy Environ. Sci. 2016, 9, 123–129.
Crossref Google Scholar
[42]

van Deelen, T. W.; Hernández Mejía, C.; de Jong, K. P. Control of metal–support interactions in heterogeneous catalysts to enhance activity and selectivity. Nat. Catal. 2019, 2, 955–970.
Crossref Google Scholar
[43]

Yang, J. R.; Li, W. H.; Wang, D. S.; Li, Y. D. Electronic metal–support interaction of single-atom catalysts and applications in electrocatalysis. Adv. Mater. 2020, 32, 2003300.
Crossref Google Scholar
[44]

Jang, M. H.; Agarwal, R.; Nukala, P.; Choi, D.; Johnson, A. T. C.; Chen, I. W.; Agarwal, R. Observing oxygen vacancy driven electroforming in Pt-TiO2-Pt device via strong metal support interaction. Nano Lett. 2016, 16, 2139–2144.
Crossref Google Scholar
[45]

Lin, G. X.; Ju, Q. J.; Jin, Y.; Qi, X. H.; Liu, W. J.; Huang, F. Q.; Wang, J. C. Suppressing dissolution of Pt-based electrocatalysts through the electronic metal–support interaction. Adv. Energy Mater. 2021, 11, 2101050.
Crossref Google Scholar
[46]

Zhou, Y. W.; Chen, Y. F.; Jiang, K.; Liu, Z.; Mao, Z. J.; Zhang, W. Y.; Lin, W. F.; Cai, W. B. Probing the enhanced methanol electrooxidation mechanism on platinum-metal oxide catalyst. Appl. Catal. B:Environ. 2021, 280, 119393.
Crossref Google Scholar
[47]

Wang, Q.; Wang, X. K.; Chai, Z. F.; Hu, W. P. Low-temperature plasma synthesis of carbon nanotubes and graphene based materials and their fuel cell applications. Chem. Soc. Rev. 2013, 42, 8821–8834.
Crossref Google Scholar
[48]

Dou, S.; Tao, L.; Wang, R. L.; El Hankari, S.; Chen, R.; Wang, S. Y. Plasma-assisted synthesis and surface modification of electrode materials for renewable energy. Adv. Mater. 2018, 30, 1705850.
Crossref Google Scholar
[49]

Ma, Y. L.; Wang, Q.; Miao, Y. L.; Lin, Y.; Li, R. Y. Plasma synthesis of Pt nanoparticles on 3D reduced graphene oxide-carbon nanotubes nanocomposites towards methanol oxidation reaction. Appl. Surf. Sci. 2018, 450, 413–421.
Crossref Google Scholar
[50]

Sun, H. M.; Miao, Y. L.; Wu, T.; Wang, Q. Exfoliation of bimetallic (Ni, Co) carbonate hydroxide nanowires by Ar plasma for enhanced oxygen evolution. Chem. Commun. 2020, 56, 872–875.
Crossref Google Scholar
[51]

Niu, Z. Q.; Becknell, N.; Yu, Y.; Kim, D.; Chen, C.; Kornienko, N.; Somorjai, G. A.; Yang, P. D. Anisotropic phase segregation and migration of Pt in nanocrystals en route to nanoframe catalysts. Nat. Mater. 2016, 15, 1188–1194.
Crossref Google Scholar
[52]

Chung, D. Y.; Jun, S. W.; Yoon, G.; Kwon, S. G.; Shin, D. Y.; Seo, P.; Yoo, J. M.; Shin, H.; Chung, Y. H.; Kim, H. et al. Highly durable and active PtFe nanocatalyst for electrochemical oxygen reduction reaction. J. Am. Chem. Soc. 2015, 137, 15478–15485.
Crossref Google Scholar
[53]

Wang, Y.; Ren, P. J.; Hu, J. T.; Tu, Y. C.; Gong, Z. M.; Cui, Y.; Zheng, Y. P.; Chen, M. S.; Zhang, W. J.; Ma, C. et al. Electron penetration triggering interface activity of Pt-graphene for CO oxidation at room temperature. Nat. Commun. 2021, 12, 5814.
Crossref Google Scholar
[54]

Luo, X.; Wei, X. Q.; Wang, H. J.; Gu, W. L.; Kaneko, T.; Yoshida, Y.; Zhao, X.; Zhu, C. Z. Secondary-atom-doping enables robust Fe-N-C single-atom catalysts with enhanced oxygen reduction reaction. Nano-Micro Lett. 2020, 12, 163.
Crossref Google Scholar
Nano Research
Volume 16 Issue 2,
February 2023
Pages 2065-2075
DOI: 10.1007/s12274-022-4890-5
Cite this article:
Sun X, Mao Z, Wang R, et al. Plasma-enabled synthesis of ordered PtFe alloy nanoparticles encapsulated with ultrathin N-doped carbon shells for efficient methanol electrooxidation. Nano Research, 2023, 16(2): 2065-2075. https://doi.org/10.1007/s12274-022-4890-5
Topics:
Direct ethanol fuel cells (DEFC)Electrocatalysis Structural optimization

953

Views

8

Crossref

11

Web of Science

8

Scopus

0

CSCD

Altmetrics
Received: 06 May 2022
Revised: 03 August 2022
Accepted: 09 August 2022
Published: 21 October 2022
© Tsinghua University Press 2022
Return