Journal Home > Volume 17 , Issue 3
Nano Research 2024, 17(3): 1035-1041 https://doi.org/10.1007/s12274-023-5994-2
Communication | Issue | Published: 19 August 2023

Controlling of coordination state of RuxNy clusters for efficient oxygen reduction electrocatalysis

Show Author's Information Weiyang Fu1,2,§,  Yihuan Yu1,2,§,  Tongtong Liu1,2,  Yinliang Cao3,  Zhengping Zhang1,2( ),  Feng Wang1,2( )
State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, China
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Zhejiang Tianneng Hydrogen Energy Technology Co., Ltd., Huzhou 313100, China

§ Weiyang Fu and Yihuan Yu contributed equally to this work.

Keywords:
oxygen reduction reaction, electrocatalysis, coordination environment, ruthenium clusters, sandwich compounds
Topics:
Electrocatalysts
Cite this article:
Fu W, Yu Y, Liu T, et al. Controlling of coordination state of RuxNy clusters for efficient oxygen reduction electrocatalysis. Nano Research, 2024, 17(3): 1035-1041. https://doi.org/10.1007/s12274-023-5994-2
Download citation
EndNote(RIS)
BibTeX

479

Views

96

Downloads

Citations

1

Crossref

1

WoS

0

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Ruthenium (Ru) is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction (ORR), in virtue of its high catalytic selectivity and relatively low price. In this work, a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black (RuxNy/C) were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources. The higher thermal stability of these complexed sandwich precursors (bis(1,2,3,4,5-pentamethylcyclopentadienyl) Ru(II) monomer, dichloro(p-cymene) Ru(II) dimer, and chloro(1,2,3,4,5-pentamethylcyclopentadienyl) Ru(II) tetramer) affords the control of coordinated state for the resulting Ru-clusters, in comparison of that derived from ruthenium chlorides. After the pyrolysis treatment, the Ru coordinated state in RuxNy/C, with the Ru–N and Ru–Ru bonds, still showed the structural inheritance from the Ru(II) monomer, dimer, and tetramer, but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations. The ORR testing exhibited that the RuxNy/C sample derived from the Ru(II) tetramer (RuxNy/C-T) presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes. Even in the acidic electrolyte, RuxNy/C-T shows the comparable ORR activity to that of Pt/C catalysts, and it shows the superior tolerance against methanol and CO. The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals, and their favorable Yeager-type adsorption of O2-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Controlling of coordination state of RuxNy clusters for efficient oxygen reduction electrocatalysis

Show Author's information Weiyang Fu1,2,§, Yihuan Yu1,2,§, Tongtong Liu1,2, Yinliang Cao3, Zhengping Zhang1,2( ), Feng Wang1,2( )
State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, China
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Zhejiang Tianneng Hydrogen Energy Technology Co., Ltd., Huzhou 313100, China

§ Weiyang Fu and Yihuan Yu contributed equally to this work.

Abstract

Ruthenium (Ru) is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction (ORR), in virtue of its high catalytic selectivity and relatively low price. In this work, a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black (RuxNy/C) were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources. The higher thermal stability of these complexed sandwich precursors (bis(1,2,3,4,5-pentamethylcyclopentadienyl) Ru(II) monomer, dichloro(p-cymene) Ru(II) dimer, and chloro(1,2,3,4,5-pentamethylcyclopentadienyl) Ru(II) tetramer) affords the control of coordinated state for the resulting Ru-clusters, in comparison of that derived from ruthenium chlorides. After the pyrolysis treatment, the Ru coordinated state in RuxNy/C, with the Ru–N and Ru–Ru bonds, still showed the structural inheritance from the Ru(II) monomer, dimer, and tetramer, but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations. The ORR testing exhibited that the RuxNy/C sample derived from the Ru(II) tetramer (RuxNy/C-T) presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes. Even in the acidic electrolyte, RuxNy/C-T shows the comparable ORR activity to that of Pt/C catalysts, and it shows the superior tolerance against methanol and CO. The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals, and their favorable Yeager-type adsorption of O2-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.

Keywords: oxygen reduction reaction, electrocatalysis, coordination environment, ruthenium clusters, sandwich compounds

References(38)

[1]

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.
DOI Google Scholar
[2]

Xia, W.; Mahmood, A.; Liang, Z. B.; Zou, R. Q.; Guo, S. J. Earth-abundant nanomaterials for oxygen reduction. Angew. Chem., Int. Ed. 2016, 55, 2650–2676.
DOI Google Scholar
[3]

Wang, X. X.; Swihart, M. T.; Wu, G. Achievements, challenges, and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation. Nat. Catal. 2019, 2, 578–589.
DOI Google Scholar
[4]

Sui, S.; Wang, X. Y.; Zhou, X. T.; Su, Y. H.; Riffat, S.; Liu, C. J. A comprehensive review of Pt electrocatalysts for the oxygen reduction reaction: Nanostructure, activity, mechanism, and carbon support in PEM fuel cells. J. Mater. Chem. A 2017, 5, 1808–1825.
DOI Google Scholar
[5]

Li, C. L.; Tan, H. B.; Lin, J. J.; Luo, X. L.; Wang, S. P.; You, J.; Kang, Y. M.; Bando, Y.; Yamauchi, Y.; Kim, J. Emerging Pt-based electrocatalysts with highly open nanoarchitectures for boosting oxygen reduction reaction. Nano Today 2018, 21, 91–105.
DOI Google Scholar
[6]

Miao, Z. P.; Wang, X. M.; Tsai, M. C.; Jin, Q. Q.; Liang, J. S.; Ma, F.; Wang, T. Y.; Zheng, S. J.; Hwang, B. J.; Huang, Y. H. et al. Atomically dispersed Fe-Nx/C electrocatalyst boosts oxygen catalysis via a new metal–organic polymer supramolecule strategy. Adv. Energy Mater. 2018, 8, 1801226.
DOI Google Scholar
[7]

Yang, H.; Chen, X.; Chen, W. T.; Wang, Q.; Cuello, N. C.; Nafady, A.; Al-Enizi, A. M.; Waterhouse, G. I. N.; Goenaga, G. A.; Zawodzinski, T. A. et al. Tunable synthesis of hollow metal-nitrogen-carbon capsules for efficient oxygen reduction catalysis in proton exchange membrane fuel cells. ACS Nano 2019, 13, 8087–8098.
DOI Google Scholar
[8]

Zhu, W.; Chen, C. Reaction: Open up the era of atomically precise catalysis. Chem 2019, 5, 2737–2739.
DOI Google Scholar
[9]

Zhao, D.; Zhuang, Z. W.; Cao, X.; Zhang, C.; Peng, Q.; Chen, C.; Li, Y. D. Atomic site electrocatalysts for water splitting, oxygen reduction, and selective oxidation. Chem. Soc. Rev. 2020, 49, 2215–2264.
DOI Google Scholar
[10]

Mitsudome, T.; Takahashi, Y.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. Hydrogenation of sulfoxides to sulfides under mild conditions using ruthenium nanoparticle catalysts. Angew. Chem., Int. Ed. 2014, 53, 8348–8351.
DOI Google Scholar
[11]

Kitano, M.; Kanbara, S.; Inoue, Y.; Kuganathan, N.; Sushko, P. V.; Yokoyama, T.; Hara, M.; Hosono, H. Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis. Nat. Commun. 2015, 6, 6731.
DOI Google Scholar
[12]

Laha, S.; Lee, Y.; Podjaski, F.; Weber, D.; Duppel, V.; Schoop, L. M.; Pielnhofer, F.; Scheurer, C.; Müller, K.; Starke, U. et al. Ruthenium oxide nanosheets for enhanced oxygen evolution catalysis in acidic medium. Adv. Energy Mater. 2019, 9, 1803795.
DOI Google Scholar
[13]

Mahmood, J.; Li, F.; Jung, S. M.; Okyay, M. S.; Ahmad, I.; Kim, S. J.; Park, N.; Jeong, H. Y.; Baek, J. B. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. Nat. Nanotechnol. 2017, 12, 441–446.
DOI Google Scholar
[14]

Li, F.; Han, G. F.; Noh, H. J.; Ahmad, I.; Jeon, I. Y.; Baek, J. B. Mechanochemically assisted synthesis of a Ru catalyst for hydrogen evolution with performance superior to Pt in both acidic and alkaline media. Adv. Mater. 2018, 30, 1803676.
DOI Google Scholar
[15]

Zhou, Y. Y.; Xie, Z. Y.; Jiang, J. X.; Wang, J.; Song, X. Y.; He, Q.; Ding, W.; Wei, Z. D. Lattice-confined Ru clusters with high CO tolerance and activity for the hydrogen oxidation reaction. Nat. Catal. 2020, 3, 454–462.
DOI Google Scholar
[16]

Kuznetsov, D. A.; Naeem, M. A.; Kumar, P. V.; Abdala, P. M.; Fedorov, A.; Müller, C. R. Tailoring lattice oxygen binding in ruthenium pyrochlores to enhance oxygen evolution activity. J. Am. Chem. Soc. 2020, 42, 7883–7888.
DOI Google Scholar
[17]

Peng, X. Y.; Zhao, S. Z.; Mi, Y. Y.; Han, L. L.; Liu, X. J.; Qi, D. F.; Sun, J. Q.; Liu, Y. F.; Bao, H. H.; Zhuo, L. C. et al. Trifunctional single-atomic Ru sites enable efficient overall water splitting and oxygen reduction in acidic media. Small 2020, 16, 2002888.
DOI Google Scholar
[18]

Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Nørskov, J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 2017, 355, eaad4998.
DOI Google Scholar
[19]

Zagal, J. H.; Koper, M. T. M. Reactivity descriptors for the activity of molecular MN4 catalysts for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2016, 55, 14510–14521.
DOI Google Scholar
[20]

Ao, X.; Zhang, W.; Li, Z. S.; Li, J. G.; Soule, L.; Huang, X.; Chiang, W. H.; Chen, H. M.; Wang, C. D.; Liu, M. L. et al. Markedly enhanced oxygen reduction activity of single-atom Fe catalysts via integration with Fe nanoclusters. ACS Nano 2019, 13, 11853–11862.
DOI Google Scholar
[21]

Hammer, B.; Norskov, J. K. Why gold is the noblest of all the metals. Nature 1995, 376, 238–240.
DOI Google Scholar
[22]

Raja, M. U.; Sindhuja, E.; Ramesh, R. Arene ruthenium(II) p-chloroacetophenone phenylthiosemicarbazone complex mediated transfer hydrogenation of ketones. Inorg. Chem. Commun. 2010, 13, 1321–1324.
DOI Google Scholar
[23]

Guan, L. H.; Shi, Z. J.; Li, M. X.; Gu, Z. N. Ferrocene-filled single-walled carbon nanotubes. Carbon 2005, 43, 2780–2785.
DOI Google Scholar
[24]

Li, W. D.; Liu, Y.; Wu, M.; Feng, X. L.; Redfern, S. A. T.; Shang, Y.; Yong, X.; Feng, T. L.; Wu, K. F.; Liu, Z. Y. et al. Carbon-quantum-dots-loaded ruthenium nanoparticles as an efficient electrocatalyst for hydrogen production in alkaline media. Adv. Mater. 2018, 30, 1800676.
DOI Google Scholar
[25]

Li, Z. Y.; Young, N. P.; Di Vece, M.; Palomba, S.; Palmer, R. E.; Bleloch, A. L.; Curley, B. C.; Johnston, R. L.; Jiang, J.; Yuan, J. Three-dimensional atomic-scale structure of size-selected gold nanoclusters. Nature 2008, 451, 46–48.
DOI Google Scholar
[26]

Ji, S. F.; Chen, Y. J.; Fu, Q.; Chen, Y. F.; Dong, J. C.; Chen, W. X.; Li, Z.; Wang, Y.; Gu, L.; He, W. et al. Confined pyrolysis within metal–organic frameworks to form uniform Ru3 clusters for efficient oxidation of alcohols. J. Am. Chem. Soc. 2017, 139, 9795–9798.
DOI Google Scholar
[27]

Bai, L. C.; Hsu, C. S.; Alexander, D. T. L.; Chen, H. M.; Hu, X. L. A cobalt-iron double-atom catalyst for the oxygen evolution reaction. J. Am. Chem. Soc. 2019, 141, 14190–14199.
DOI Google Scholar
[28]

Peters, S.; Peredkov, S.; Neeb, M.; Eberhardt, W.; Al-Hada, M. Size-dependent XPS spectra of small supported Au-clusters. Surf. Sci. 2013, 608, 129–134.
DOI Google Scholar
[29]

Li, P. S.; Wang, M. Y.; Duan, X. X.; Zheng, L. R.; Cheng, X. P.; Zhang, Y. F.; Kuang, Y.; Li, Y. P.; Ma, Q.; Feng, Z. X. et al. Boosting oxygen evolution of single-atomic ruthenium through electronic coupling with cobalt-iron layered double hydroxides. Nat. Commun. 2019, 10, 1711.
DOI Google Scholar
[30]

Xiao, M. L.; Chen, Y. T.; Zhu, J. B.; Zhang, H.; Zhao, X.; Gao, L. Q.; Wang, X.; Zhao, J.; Ge, J. J.; Jiang, Z. et al. Climbing the apex of the ORR volcano plot via binuclear site construction: Electronic and geometric engineering. J. Am. Chem. Soc. 2019, 141, 17763–17770.
DOI Google Scholar
[31]

Yang, S.; Tak, Y. J.; Kim, J.; Soon, A.; Lee, H. Support effects in single-atom platinum catalysts for electrochemical oxygen reduction. ACS Catal. 2017, 7, 1301–1307.
DOI Google Scholar
[32]

Yang, S.; Kim, J.; Tak, Y. J.; Soon, A.; Lee, H. Single-atom catalyst of platinum supported on titanium nitride for selective electrochemical reactions. Angew. Chem., Int. Ed. 2016, 55, 2058–2062.
DOI Google Scholar
[33]

Hammer, B.; Nørskov, J. K. Theoretical surface science and catalysis—Calculations and concepts. Adv. Catal. 2000, 45, 71–129.
DOI Google Scholar
[34]

Cui, L. X.; Fan, K. C.; Zong, L. B.; Lu, F. H.; Zhou, M.; Li, B.; Zhang, L. C.; Feng, L. Y.; Li, X.; Chen, Y. N. et al. Sol-gel pore-sealing strategy imparts tailored electronic structure to the atomically dispersed Ru sites for efficient oxygen reduction reaction. Energy Storage Mater. 2022, 44, 469–476.
DOI Google Scholar
[35]

Wu, L. Q.; Su, L. X.; Liang, Q.; Zhang, W.; Men, Y.; Luo, W. Boosting hydrogen oxidation kinetics by promoting interfacial water adsorption on d-p hybridized Ru catalysts. ACS Catal. 2023, 13, 4127–4133.
DOI Google Scholar
[36]

Jiang, W. J.; Gu, L.; Li, L.; Zhang, Y.; Zhang, X.; Zhang, L. J.; Wang, J. Q.; Hu, J. S.; Wei, Z. D.; Wan, L. J. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe-Nx. J. Am. Chem. Soc. 2016, 138, 3570–3578.
DOI Google Scholar
[37]

Liu, S. S.; Wang, M. F.; Sun, X. Y.; Xu, N.; Liu, J.; Wang, Y. Z.; Qian, T.; Yan, C. L. Facilitated oxygen chemisorption in heteroatom-doped carbon for improved oxygen reaction activity in all-solid-state zinc-air batteries. Adv. Mater. 2018, 30, 1704898.
DOI Google Scholar
[38]

Tang, C.; Zhang, Q. Nanocarbon for oxygen reduction electrocatalysis: Dopants, edges, and defects. Adv. Mater. 2017, 29, 1604103.
DOI Google Scholar
File
12274_2023_5994_MOESM1_ESM.pdf (2 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 22 May 2023
Revised: 05 July 2023
Accepted: 08 July 2023
Published: 19 August 2023
Issue date: March 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the National Key Research and Development Program of China (No. 2022YFE0110400), the National Natural Science Foundation of China (Nos. 52122207, 52173245, 52130206, U20A20337, and 52221006), and the Fundamental Research Funds for the Central Universities (No. CLYY2022). The authors are grateful to the Beijing Synchrotron Radiation Facility (BSRF) for the XAFS measurements.

Return