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Research Article | Open Access | Online First

RuOx clusters anchored on self-assembled SnO2 cubic nanocage for boosting sustainable acidic water oxidation

Jingjing Zhang1,4,§, Fatimah Kehinde Busari1,4,§, Yifei Zhang2, Song Guo1( ), Yang Zhao1, Binli Wang3( ), Qiong Zeng1, Zhen Zhao2( ), Gao Li1,2,4( )
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China
University of Chinese Academy of Sciences, Beijing 100039, China

§ Jingjing Zhang and Fatimah Kehinde Busari contributed equally to this work.

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Abstract

Electrochemical water splitting in acid has been emerging as a powerful, sustainable and green protocol to produce hydrogen gas sources. In this study, we propose a novel strategy to fabricate RuOx clusters anchored on self-assembled SnO2 cubic nanocages (RuOx-SnO2 composites), which is substantiated by a combination of spectroscopy and microscopy. The resulting RuOx-SnO2 composite catalysts exhibit boosting oxygen evolution reaction (OER) performance: A Tafel slope of 41.2 mV·dec−1 and a low overpotential of 225 mV@10 mA·cm−2 in a 0.5 M H2SO4 (pH=0) electrolyte are achieved, outperforming the state-of-art OER catalyst of commercial RuO2 (com-RuO2). Notably, RuOx-SnO2 gives an extraordinarily large mass activity of 6873.4 A·gRu−1 at the overpotential of 270 mV, which is approximately 170 times higher than that of com-RuO2 (40.2 A·gRu−1). The RuOx-SnO2 exhibits a good durability for at least 100 h@50 mA·cm−2 and > 500 h@10 mA·cm−2 and a stability of 30 hours at 100 mA·cm−2 in an assembled proton exchange membrane water electrolysis, indicating that the engineered microstructure possesses significant potential for practical applications. The high intrinsic OER performance is attributed to the increasing density of exposed catalytic sites by downsizing RuOx clusters with abundant oxygen vacancies (Ov, 1.02×10−12 spin·mgcat.−1 determined by electron paramagnetic resonance). Furthermore, a Ru5c-Ov dual-active site mechanism is proposed by density functional theory calculations, that is, the moderate surface migration between five-coordinated surface Ru site (Ru5c) and Ov makes the *O→*OOH rate-determining step feasible. Moreover, this strategy provides a novel route for enhancing acidic OER activity and highly encouraging for their future applications of ruthenium-based composite catalysts.

Keywords

RuOx clustersSnO2 cubic nanocageacidic water oxidationoxygen evolution reaction

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References

[1]

Gao, F.; He, J. Q.; Wang, H. W.; Lin, J. H.; Chen, R. X.; Yi, K.; Huang, F.; Lin, Z.; Wang, M. Y. Te-mediated electro-driven oxygen evolution reaction. Nano Res. Energy 2022, 1, e9120029.
Crossref Google Scholar
[2]

Sanwal, P.; Raza, A.; Miao, Y. X.; Lumbers, B.; Li, G. Advances in coinage metal nanoclusters: From synthesis strategies to electrocatalytic performance. Polyoxometalates 2024, 3, 9140057.
Crossref Google Scholar
[3]

Chen, S. Y.; Zhang, T.; Han, J. Y.; Qi, H.; Jiao, S. H.; Hou, C. M.; Guan, J. Q. Interface engineering of Fe–Sn–Co sulfide/oxyhydroxide heterostructural electrocatalyst for synergistic water splitting. Nano Res. Energy 2024, 3, e9120106.
Crossref Google Scholar
[4]

Wang, C. M.; Geng, Q. H.; Fan, L. L.; Li, J. X.; Ma, L.; Li, C. L. Phase engineering oriented defect-rich amorphous/crystalline RuO2 nanoporous particles for boosting oxygen evolution reaction in acid media. Nano Res. Energy 2023, 2, e9120070.
Crossref Google Scholar
[5]

Cao, Y. H.; Guo, S.; Yu, C. L.; Zhang, J. W.; Pan, X. L.; Li, G. Ionic liquid-assisted one-step preparation of ultrafine amorphous metallic hydroxide nanoparticles for the highly efficient oxygen evolution reaction. J. Mater. Chem. A 2020, 8, 15767–15773.
Crossref Google Scholar
[6]

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.
Crossref Google Scholar
[7]
Gu, X. R.; Guo, S.; Zhang, Y. F.; Zhang, J. J.; Sanwal, P.; Xu, L. L.; Zhao, Z.; Jin, R. C.; Li, G. Boosting oxygen evolution performance over synergistic tiara nickel clusters and thin layered double hydroxides. Nano Res. Energy, in press, DOI: 10.26599/NRE.2024.9120134.
Crossref
[8]

Carmo, M.; Fritz, D. L.; Mergel, J.; Stolten, D. A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 2013, 38, 4901–4934.
Crossref Google Scholar
[9]

Wang, C. Y.; Schechter, A.; Feng, L. G. Iridium-based catalysts for oxygen evolution reaction in acidic media: Mechanism, catalytic promotion effects and recent progress. Nano Res. Energy 2023, 2, e9120056.
Crossref Google Scholar
[10]

Shan, J. Q.; Guo, C. X.; Zhu, Y. H.; Chen, S. M.; Song, L.; Jaroniec, M.; Zheng, Y.; Qiao, S. Z. Charge-redistribution-enhanced nanocrystalline Ru@IrO x electrocatalysts for oxygen evolution in acidic media. Chem 2019, 5, 445–459.
Crossref Google Scholar
[11]

Yao, Q.; Huang, B. L.; Zhang, N.; Sun, M. Z.; Shao, Q.; Huang, X. Q. Channel-rich RuCu nanosheets for pH-universal overall water splitting electrocatalysis. Angew. Chem., Int. Ed. 2019, 58, 13983–13988.
Crossref Google Scholar
[12]

Su, J. W.; Yang, Y.; Xia, G. L.; Chen, J. T.; Jiang, P.; Chen, Q. W. Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media. Nat. Commun. 2017, 8, 14969.
Crossref Google Scholar
[13]

Gloag, L.; Benedetti, T. M.; Cheong, S.; Li, Y. B.; Chan, X. H.; Lacroix, L. M.; Chang, S. L. Y.; Arenal, R.; Florea, I.; Barron, H. et al. Three-dimensional branched and faceted gold-ruthenium nanoparticles: Using nanostructure to improve stability in oxygen evolution electrocatalysis. Angew. Chem., Int. Ed. 2018, 57, 10241–10245.
Crossref Google Scholar
[14]

Zhu, Y. L.; Tahini, H. A.; Hu, Z. W.; Chen, Z. G.; Zhou, W.; Komarek, A. C.; Lin, Q.; Lin, H. J.; Chen, C. T.; Zhong, Y. J. et al. Boosting oxygen evolution reaction by creating both metal ion and lattice-oxygen active sites in a complex oxide. Adv. Mater. 2020, 32, 1905025.
Crossref Google Scholar
[15]

Zhao, Z. L.; Wang, Q.; Huang, X.; Feng, Q.; Gu, S.; Zhang, Z.; Xu, H.; Zeng, L.; Gu, M.; Li, H. Boosting the oxygen evolution reaction using defect-rich ultra-thin ruthenium oxide nanosheets in acidic media. Energy Environ. Sci. 2020, 13, 5143–5151.
Crossref Google Scholar
[16]

Li, W. Q.; Zhang, H.; Hong, M. Z.; Zhang, L. L.; Feng, X.; Shi, M. F.; Hu, W. X.; Mu, S. C. Defective RuO2/TiO2 nano-heterostructure advances hydrogen production by electrochemical water splitting. Chem. Eng. J. 2022, 431, 134072.
Crossref Google Scholar
[17]

Yan, H. H.; Jiang, Z. Q.; Deng, B. L.; Wang, Y. J.; Jiang, Z. J. Ultrathin carbon coating and defect engineering promote RuO2 as an efficient catalyst for acidic oxygen evolution reaction with super-high durability. Adv. Energy Mater. 2023, 13, 2300152.
Crossref Google Scholar
[18]

Ge, R. X.; Li, L.; Su, J. W.; Lin, Y. C.; Tian, Z. Q.; Chen, L. Ultrafine defective RuO2 electrocatayst integrated on carbon cloth for robust water oxidation in acidic media. Adv. Energy Mater. 2019, 9, 1901313.
Crossref Google Scholar
[19]

Liang, F. L.; Yu, Y.; Zhou, W.; Xu, X. Y.; Zhu, Z. H. Highly defective CeO2 as a promoter for efficient and stable water oxidation. J. Mater. Chem. A 2015, 3, 634–640.
Crossref Google Scholar
[20]

Martínez-Séptimo, A.; Valenzuela, M. A.; Del Angel, P. ; de G González-Huerta, R. IrRuO x /TiO2 a stable electrocatalyst for the oxygen evolution reaction in acidic media. Int. J. Hydrogen Energy 2021, 46, 25918–25928.
Crossref Google Scholar
[21]

Park, S. Y.; An, J. W.; Baek, J. H.; Woo, H. J.; Lee, W. J.; Kwon, S. H.; Bera, S. Activity-stability trends of the Sb–SnO2@RuO x heterostructure toward acidic water oxidation. ACS Appl. Mater. Interfaces 2023, 15, 15332–15343.
Crossref Google Scholar
[22]

Qiao, L.; Bing, Y. F.; Wang, Y. Z.; Yu, S. S.; Liang, Z. Z.; Zeng, Y. Enhanced toluene sensing performances of Pd-loaded SnO2 cubic nanocages with porous nanoparticle-assembled shells. Sen. Actuators B: Chem. 2017, 241, 1121–1129.
Crossref Google Scholar
[23]

Reier, T.; Nong, H. N.; Teschner, D.; Schlögl, R.; Strasser, P. Electrocatalytic oxygen evolution reaction in acidic environments - reaction mechanisms and catalysts. Adv. Energy Mater. 2017, 7, 1601275.
Crossref Google Scholar
[24]

Danilovic, N.; Subbaraman, R.; Chang, K. C.; Chang, S. H.; Kang, Y. J.; Snyder, J.; Paulikas, A. P.; Strmcnik, D.; Kim, Y. T.; Myers, D. et al. Activity-stability trends for the oxygen evolution reaction on monometallic oxides in acidic environments. J. Phys. Chem. Lett. 2014, 5, 2474–2478.
Crossref Google Scholar
[25]

Abbou, S.; Chattot, R.; Martin, V.; Claudel, F.; Solà-Hernandez, L.; Beauger, C.; Dubau, L.; Maillard, F. Manipulating the corrosion resistance of SnO2 aerogels through doping for efficient and durable oxygen evolution reaction electrocatalysis in acidic media. ACS Catal. 2020, 10, 7283–7294.
Crossref Google Scholar
[26]

Lee, J. H. Gas sensors using hierarchical and hollow oxide nanostructures: Overview. Sen. Actuators B: Chem. 2009, 140, 319–336.
Crossref Google Scholar
[27]

Wang, X. J.; Feng, J.; Bai, Y. C.; Zhang, Q.; Yin, Y. D. Synthesis, properties, and applications of hollow micro-/nanostructures. Chem. Rev. 2016, 116, 10983–11060.
Crossref Google Scholar
[28]

Wang, Y. Z.; Yang, M.; Ding, Y. M.; Li, N. W.; Yu, L. Recent advances in complex hollow electrocatalysts for water splitting. Adv. Funct. Mater. 2022, 32, 2108681.
Crossref Google Scholar
[29]

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
Crossref Google Scholar
[30]

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
Crossref Google Scholar
[31]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
[32]

Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188–5192.
Crossref Google Scholar
[33]

Yin, J. Z.; Gao, F.; Wei, C. Z.; Lu, Q. Y. Controlled growth and applications of complex metal oxide ZnSn(OH)6 polyhedra. Inorg. Chem. 2012, 51, 10990–10995.
Crossref Google Scholar
[34]

Xu, J. Y.; Liu, G. Y.; Li, J. L.; Wang, X. D. The electrocatalytic properties of an IrO2/SnO2 catalyst using SnO2 as a support and an assisting reagent for the oxygen evolution reaction. Electrochim. Acta 2012, 59, 105–112.
Crossref Google Scholar
[35]

Li, Z. W.; Xie, Y.; Gao, J. X.; Zhang, X. K.; Zhang, J.; Liu, Y.; Li, G. The promotional effect of multiple active sites on Fe-based oxygen reduction electrocatalysts for a zinc-air battery. J. Mater. Chem. A 2023, 11, 26573–26579.
Crossref Google Scholar
[36]

Liu, L. L.; An, M. Z.; Yang, P. X.; Zhang, J. Q. Superior cycle performance and high reversible capacity of SnO2/graphene composite as an anode material for lithium-ion batteries. Sci. Rep. 2015, 5, 9055.
Crossref Google Scholar
[37]

Wang, X. L.; Lan, G. J.; Liu, H. Z.; Zhu, Y. H.; Li, Y. Effect of acidity and ruthenium species on catalytic performance of ruthenium catalysts for acetylene hydrochlorination. Catal. Sci. Technol. 2018, 8, 6143–6149.
Crossref Google Scholar
[38]

Morgan, D. J. Resolving ruthenium: XPS studies of common ruthenium materials. Surf. Interface Anal. 2015, 47, 1072–1079.
Crossref Google Scholar
[39]

Zhang, Y. F.; Li, Z. W.; Zhang, J. J.; Xu, L. L.; Han, Z. K.; Baiker, A.; Li, G. Nanostructured Ni–MoC x : An efficient non-noble metal catalyst for the chemoselective hydrogenation of nitroaromatics. Nano Res. 2023, 16, 8919–8928.
Crossref Google Scholar
[40]

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.
Crossref Google Scholar
[41]

Lee, Y.; Suntivich, J.; May, K. J.; Perry, E. E.; Shao-Horn, Y. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett. 2012, 3, 399–404.
Crossref Google Scholar
[42]

Shi, Q. Q.; Zhang, Y. F.; Li, Z. W.; Han, Z. K.; Xu, L. L.; Baiker, A.; Li, G. Morphology effects in MnCeO x solid solution-catalyzed NO reduction with CO: Active sites, water tolerance, and reaction pathway. Nano Res. 2023, 16, 6951–6959.
Crossref Google Scholar
[43]

Zhang, J. J.; Raza, A.; Zhao, Y.; Guo, S.; Babar, Z. U. D.; Xu, L. L.; Cao, C. H.; Li, G. Intrinsically robust cubic MnCoO x solid solution: Achieving high activity for sustainable acidic water oxidation. J. Mater. Chem. A 2023, 11, 25345–25355.
Crossref Google Scholar
[44]

Cao, Y. H.; Su, Y.; Xu, L. L.; Yang, X. H.; Han, Z. K.; Cao, R.; Li, G. Oxygen vacancy-rich amorphous FeNi hydroxide nanoclusters as an efficient electrocatalyst for water oxidation. J. Energy Chem. 2022, 71, 167–173.
Crossref Google Scholar
[45]

Zhang, J. J.; Xu, L. L.; Yang, X. X.; Guo, S.; Zhang, Y. F.; Zhao, Y.; Wu, G.; Li, G. Amorphous MnRuO x containing microcrystalline for enhanced acidic oxygen-evolution activity and stability. Angew. Chem., Int. Ed. 2024, 63, e202405641.
Crossref Google Scholar
[46]

Jin, H. Y.; Liu, X. Y.; An, P. F.; Tang, C.; Yu, H. M.; Zhang, Q. H.; Peng, H. J.; Gu, L.; Zheng, Y.; Song, T. et al. Dynamic rhenium dopant boosts ruthenium oxide for durable oxygen evolution. Nat. Commun. 2023, 14, 354.
Crossref Google Scholar
[47]

Hao, Y. X.; Hung, S. F.; Zeng, W. J.; Wang, Y.; Zhang, C. C.; Kuo, C. H.; Wang, L. Q.; Zhao, S.; Zhang, Y.; Chen, H. Y. et al. Switching the oxygen evolution mechanism on atomically dispersed Ru for enhanced acidic reaction kinetics. J. Am. Chem. Soc. 2023, 145, 23659–23669.
Crossref Google Scholar
[48]
Li, Z. W.; Xu, M. Q.; Wang, J. Q.; Zhang, Y. F.; Liu, W.; Gu, X. R.; Han, Z. K.; Ye, W.; Li, G. Boosting up electrosynthesis of urea with nitrate and carbon dioxide via synergistic effect of metallic iron cluster and single-atom. Small, in press, DOI: 10.1002/smll.202400036.
Crossref
Nano Research Energy
DOI: 10.26599/NRE.2024.9120140
Cite this article:
Zhang J, Busari FK, Zhang Y, et al. RuOx clusters anchored on self-assembled SnO2 cubic nanocage for boosting sustainable acidic water oxidation. Nano Research Energy, 2024, https://doi.org/10.26599/NRE.2024.9120140

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Received: 22 August 2024
Revised: 09 September 2024
Accepted: 12 September 2024
Published: 15 October 2024
© The Author(s) 2024. Published by Tsinghua University Press.

The articles published in this open access journal are distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
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