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Nano Research 2022, 15(4): 2870-2876 https://doi.org/10.1007/s12274-021-3879-9
Research Article | Issue | Published: 20 October 2021

Cobalt doping boosted electrocatalytic activity of CaMn3O6 for hydrogen evolution reaction

Show Author's Information Qun Li1,§,  Kaisi Liu1,§,  Siwei Gui3,  Jiabin Wu1,  Xiaogang Li3,  Zaifang Li2( ),  Hongrun Jin1,  Hui Yang3( ),  Zhimi Hu1,  Wenxi Liang1( ),  Liang Huang1( )
Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, China
China-Australia Institute for Advanced Materials and Manufacturing, Jiaxing University, Jiaxing 314001, China
State Key Laboratory of Material Processing and Die & Mold Technology, Department of Mechanics, School of Aerospace Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

§ Qun Li and Kaisi Liu contributed equally to this work.

Keywords:
electronic structure, hydrogen evolution reaction, dopant, CMCO nanowires
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Catalyst activity
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Li Q, Liu K, Gui S, et al. Cobalt doping boosted electrocatalytic activity of CaMn3O6 for hydrogen evolution reaction. Nano Research, 2022, 15(4): 2870-2876. https://doi.org/10.1007/s12274-021-3879-9
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Abstract Full text Electronic supplementary material About this article

The development of earth-abundant-metal-based electrocatalysts with high efficiency and long-term stability for hydrogen evolution reaction (HER) is crucial for the clean and renewable energy application. Herein, we report a molten-salt method to synthesize Co-doped CaMn3O6 (CMO) nanowires (NWs) as effective electrocatalyst for HER. The as-obtained CaMn3−xCoxO6 (CMCO) exhibits a small onset overpotential of 70 mV, a required overpotential of 140 mV at a current density of 10 mA·cm−2, a Tafel slope of 39 mV·dec−1 in 0.1 M HClO4, and a satisfying long-term stability. Experimental characterizations combined with density functional theory (DFT) calculations demonstrate that the obtained HER performance can be attributed to the Co-doping which altered CMO’s surface electronic structures and properties. Considering the simplicity of synthesis route and the abundance of the pertinent elements, the synthesized CMCO shows a promising prospect as a candidate for the development of earth-abundant, metal-based, and cost-effective electrocatalyst with superior HER activity. Our results also establish a strategy of rational design and construction of novel electrocatalyst toward HER by tailoring band structures of transition metal oxides (TMOs).


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Electronic supplementary material
About this article

Cobalt doping boosted electrocatalytic activity of CaMn3O6 for hydrogen evolution reaction

Show Author's information Qun Li1,§, Kaisi Liu1,§, Siwei Gui3, Jiabin Wu1, Xiaogang Li3, Zaifang Li2( ), Hongrun Jin1, Hui Yang3( ), Zhimi Hu1, Wenxi Liang1( ), Liang Huang1( )
Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, China
China-Australia Institute for Advanced Materials and Manufacturing, Jiaxing University, Jiaxing 314001, China
State Key Laboratory of Material Processing and Die & Mold Technology, Department of Mechanics, School of Aerospace Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

§ Qun Li and Kaisi Liu contributed equally to this work.

Abstract

The development of earth-abundant-metal-based electrocatalysts with high efficiency and long-term stability for hydrogen evolution reaction (HER) is crucial for the clean and renewable energy application. Herein, we report a molten-salt method to synthesize Co-doped CaMn3O6 (CMO) nanowires (NWs) as effective electrocatalyst for HER. The as-obtained CaMn3−xCoxO6 (CMCO) exhibits a small onset overpotential of 70 mV, a required overpotential of 140 mV at a current density of 10 mA·cm−2, a Tafel slope of 39 mV·dec−1 in 0.1 M HClO4, and a satisfying long-term stability. Experimental characterizations combined with density functional theory (DFT) calculations demonstrate that the obtained HER performance can be attributed to the Co-doping which altered CMO’s surface electronic structures and properties. Considering the simplicity of synthesis route and the abundance of the pertinent elements, the synthesized CMCO shows a promising prospect as a candidate for the development of earth-abundant, metal-based, and cost-effective electrocatalyst with superior HER activity. Our results also establish a strategy of rational design and construction of novel electrocatalyst toward HER by tailoring band structures of transition metal oxides (TMOs).

Keywords: electronic structure, hydrogen evolution reaction, dopant, CMCO nanowires

References(49)

1

Blankenship, R. E.; Tiede, D. M.; Barber, J.; Brudvig, G. W.; Fleming, G.; Ghirardi, M.; Gunner, M. R.; Junge, W.; Kramer, D. M.; Melis, A. et al. Comparing photosynthetic and photovoltaic efficiencies and recognizing the potential for improvement. Science 2011, 332, 805–809.
DOI Google Scholar
2

Niu, S. W.; Cai, J. Y.; Wang, G. M. Two-dimensional MoS2 for hydrogen evolution reaction catalysis: The electronic structure regulation. Nano Res. 2021, 14, 1985–2002.
DOI Google Scholar
3

Dresselhaus, M. S.; Thomas, I. L. Alternative energy technologies. Nature 2001, 414, 332–337.
DOI Google Scholar
4

Jiang, K.; Luo, M.; Liu, Z. X.; Peng, M.; Chen, D. C.; Lu, Y. R.; Chan, T. S.; de Groot, F. M. F.; Tan, Y. W. Rational strain engineering of single-atom ruthenium on nanoporous MoS2 for highly efficient hydrogen evolution. Nat. Commun. 2021, 12, 1687.
DOI Google Scholar
5

Han, L. L.; Guo, L. M.; Dong, C. Q.; Zhang, C.; Gao, H.; Niu, J. Z.; Peng, Z. Q.; Zhang, Z. H. Ternary mesoporous cobalt-iron-nickel oxide efficiently catalyzing oxygen/hydrogen evolution reactions and overall water splitting. Nano Res. 2019, 12, 2281–2287.
DOI Google Scholar
6

Li, S. W.; Yang, C.; Yin, Z.; Yang, H. J.; Chen, Y. F.; Lin, L. L.; Li, M. Z.; Li, W. Z.; Hu, G.; Ma, D. Wet-chemistry synthesis of cobalt carbide nanoparticles as highly active and stable electrocatalyst for hydrogen evolution reaction. Nano Res. 2017, 10, 1322–1328.
DOI Google Scholar
7

Zheng, Y.; Jiao, Y.; Jaroniec, M.; Qiao, S. Z. Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. Angew. Chem., Int. Ed. 2015, 54, 52–65.
DOI Google Scholar
8

Sultan, S.; Tiwari, J. N.; Singh, A. N.; Zhumagali, S.; Ha, M. R.; Myung, C. W.; Thangavel, P.; Kim, K. S. Single atoms and clusters based nanomaterials for hydrogen evolution, oxygen evolution reactions, and full water splitting. Adv. Energy Mater. 2019, 9, 1900624.
DOI Google Scholar
9

Zhu, B. J.; Zou, R. Q.; Xu, Q. Metal-organic framework based catalysts for hydrogen evolution. Adv. Energy Mater. 2018, 8, 1801193.
DOI Google Scholar
10

Huang, X.; Zeng, Z. Y.; Bao, S. Y.; Wang, M. F.; Qi, X. Y.; Fan, Z. X.; Zhang, H. Solution-phase epitaxial growth of noble metal nanostructures on dispersible single-layer molybdenum disulfide nanosheets. Nat. Commun. 2013, 4, 1444.
DOI Google Scholar
11
Wu, J. B.; Li, Q.; Shuck, C. E.; Maleski, K.; Alshareef, H. N.; Zhou J.; Gogotsi, Y.; Huang L. An aqueous 2.1 V pseudocapacitor with MXene and V-MnO2 electrodes. Nano Res., in press, DOI: 10.1007/s12274-021-3513-x.https://doi.org/10.1007/s12274-021-3513-x
DOI
12

Wu, J. B.; Zhou, H.; Li, Q.; Chen, M.; Wan, J.; Zhang, N.; Xiong, L. K.; Li, S.; Xia, B. Y.; Feng, G. et al. Densely-populated isolated single Co-N site for efficient oxygen electrocatalysis. Adv. Energy Mater. 2019, 9, 1900149.
DOI Google Scholar
13

Wu, J. B.; Xiong, L. K.; Zhao, B. T.; Liu, M. L.; Huang, L. Densely populated single atom catalysts. Small Methods 2020, 4, 1900540.
DOI Google Scholar
14

Voiry, D.; Yamaguchi, H.; Li, J. W.; Silva, R.; Alves, D. C. B.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 2013, 12, 850–855.
DOI Google Scholar
15

Shi, Y. M.; Zhang, B. Recent advances in transition metal phosphide nanomaterials: Synthesis and applications in hydrogen evolution reaction. Chem. Soc. Rev. 2016, 45, 1529–1541.
DOI Google Scholar
16

Maiyalagan, T.; Jarvis, K. A.; Therese, S.; Ferreira, P. J.; Manthiram, A. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions. Nat. Commun. 2014, 5, 3949.
DOI Google Scholar
17

Gorlin, Y.; Jaramillo, T. F. A bifunctional nonprecious metal catalyst for oxygen reduction and water oxidation. J. Am. Chem. Soc. 2010, 132, 13612–13614.
DOI Google Scholar
18

Ong, W. J.; Tan, L. L.; Chai, S. P.; Yong, S. T.; Mohamed, A. R. Facet-dependent photocatalytic properties of TiO2-based composites for energy conversion and environmental remediation. ChemSusChem 2014, 7, 690–719.
DOI Google Scholar
19

Sun, Y.; Zhou, Y. J.; Liu, Y.; Wu, Q. Y.; Zhu, M. M.; Huang, H.; Liu, Y.; Shao, M. W.; Kang, Z. H. A photoactive process cascaded electrocatalysis for enhanced methanol oxidation over Pt-MXene-TiO2 composite. Nano Res. 2020, 13, 2683–2690.
DOI Google Scholar
20

Wang, J. M.; Guo, L. L.; Xu, L.; Zeng, P.; Li, R. J.; Peng, T. Y. Z-scheme photocatalyst based on porphyrin derivative decorated few-layer BiVO4 nanosheets for efficient visible-light-driven overall water splitting. Nano Res. 2021, 14, 1294–1304.
DOI Google Scholar
21

Yang, M. Q.; Wang, J.; Wu, H.; Ho, G. W. Noble metal-free nanocatalysts with vacancies for electrochemical water splitting. Small 2018, 14, 1703323.
DOI Google Scholar
22

Hadermann, J.; Abakumov, A. M.; Gillie, L. J.; Martin, C.; Hervieu, M. Coupled cation and charge ordering in the CaMn3O6 tunnel structure. Chem. Mater. 2006, 18, 5530–5536.
DOI Google Scholar
23

Fukabori, A.; Awaka, J.; Takahashi, Y.; Kijima, N.; Hayakawa, H.; Akimoto, J. Single crystal growth of CaMn2O4 and CaMn3O6 in molten CaCl2. Chem. Lett. 2008, 37, 978–979.
DOI Google Scholar
24

Li, M. F.; Zhao, Z. P.; Cheng, T.; Fortunelli, A.; Chen, C. Y.; Yu, R.; Zhang, Q. H.; Gu, L.; Merinov, B. V,; Lin, Z. Y. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 2016, 354, 1414–1419.
DOI Google Scholar
25

Xu, J.; Lai, S. H.; Qi, D. F.; Hu, M.; Peng, X. Y.; Liu, Y. F.; Liu, W.; Hu, G. Z.; Xu, H.; Li, F. et al. Atomic Fe-Zn dual-metal sites for high-efficiency pH-universal oxygen reduction catalysis. Nano Res. 2021, 14, 1374–1381.
DOI Google Scholar
26

Tian, X. L.; Zhao, X.; Su, Y. Q.; Wang, L. J.; Wang, H. M.; Dang, D.; Chi, B.; Liu, H. F.; Hensen, E. J. M.; Lou, X. W. D. et al. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 2019, 366, 850–856.
DOI Google Scholar
27

Xiong, Q. Z.; Zhang, X.; Cheng, Q. P.; Liu, G. Q.; Xu, G.; Li, J. L.; Ye, X. X.; Gao, H. J. Highly selective electrocatalytic Cl− oxidation reaction by oxygen-modified cobalt nanoparticles immobilized carbon nanofibers for coupling with brine water remediation and H2 production. Nano Res. 2021, 14, 1443–1449.
DOI Google Scholar
28

Huang, B. B.; Chen, L. Y.; Wang, Y.; Ouyang, L. Z.; Ye, J. S. Paragenesis of palladium-cobalt nanoparticle in nitrogen-rich carbon nanotubes as a bifunctional electrocatalyst for hydrogen-evolution reaction and oxygen-reduction reaction. Chem.—Eur. J. 2017, 23, 7710–7718.
DOI Google Scholar
29

Huang, N.; Yang, L.; Zhang, M. Y.; Yan, S. F.; Ding, Y. Y.; Sun, P. P.; Sun, X. H. Cobalt-embedded N-doped carbon arrays derived in situ as trifunctional catalyst toward hydrogen and oxygen evolution, and oxygen reduction. ChemElectroChem 2019, 6, 4522–4532.
DOI Google Scholar
30

Kim, T. S.; Song, H. J.; Dar, M. A.; Shim, H. W.; Kim, D. W. Thermally reduced rGO-wrapped CoP/Co2P hybrid microflower as an electrocatalyst for hydrogen evolution reaction. J. Am. Ceram. Soc. 2018, 101, 3749–3754.
DOI Google Scholar
31

Yu, J. Y.; Huang, K.; Wu, H. Y.; Feng, Y.; Wang, L.; Tang, Z.; Zhang, L. Exchange bias and magnetic properties induced by intrinsic structural distortion in CaMn3O6 nanoribbons. Appl. Phys. Lett. 2014, 104, 022407.
DOI Google Scholar
32

Najafpour, M. M. Mixed-valence manganese calcium oxides as efficient catalysts for water oxidation. Dalton Trans. 2011, 40, 3793–3795.
DOI Google Scholar
33

Yang, Y.; Fei, H. L.; Ruan, G. D.; Tour, J. M. Porous cobalt-based thin film as a bifunctional catalyst for hydrogen generation and oxygen generation. Adv. Mater. 2015, 27, 3175–3180.
DOI Google Scholar
34

Russell, A. E. Electrocatalysis: Theory and experiment at the interface. Preface. Faraday Discuss. 2008, 140, 9–10.
DOI Google Scholar
35

Sun, H. N.; Xu, X. M.; Hu, Z. W.; Tjeng, L. H.; Zhao, J.; Zhang, Q.; Lin, H. J.; Chen, C. T.; Chan, T. S.; Zhou, W. et al. Boosting the oxygen evolution reaction activity of a perovskite through introducing multi-element synergy and building an ordered structure. J. Mater. Chem. A 2019, 7, 9924–9932.
DOI Google Scholar
36

McCrory, C. C. L.; Jung, S.; Peters, J. C.; Jaramillo, T. F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 2013, 135, 16977–16987.
DOI Google Scholar
37

Zhang, H. J.; Guan, D. Q.; Gao, X. C.; Yu, J.; Chen, G.; Zhou, W.; Shao, Z. P. Morphology, crystal structure and electronic state one-step co-tuning strategy towards developing superior perovskite electrocatalysts for water oxidation. J. Mater. Chem. A 2019, 7, 19228–19233.
DOI Google Scholar
38

Qiao, R. M.; Chin, T.; Harris, S. J.; Yan, S. S.; Yang, W. L. Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides. Curr. Appl. Phys. 2013, 13, 544–548.
DOI Google Scholar
39

Suntivich, J.; Hong, W. T.; Lee, Y. L.; Rondinelli, J. M.; Yang, W. L.; Goodenough, J. B.; Dabrowski, B.; Freeland, J. W.; Shao-Horn, Y. Estimating hybridization of transition metal and oxygen states in perovskites from O K-edge X-ray absorption spectroscopy. J. Phys. Chem. C 2014, 118, 1856–1863.
DOI Google Scholar
40

Xu, X. M.; Chen, Y. B.; Zhou, W.; Zhu, Z. H.; Su, C.; Liu, M. L.; Shao, Z. P. A perovskite electrocatalyst for efficient hydrogen evolution reaction. Adv. Mater. 2016, 28, 6442–6448.
DOI Google Scholar
41

Grinberg, I.; West, D. V.; Torres, M.; Gou, G. Y.; Stein, D. M.; Wu, L. Y.; Chen, G. N.; Gallo, E. M.; Akbashev, A. R.; Davies, P. K. et al. Perovskite oxides for visible-light-absorbing ferroelectric and photovoltaic materials. Nature 2013, 503, 509–512.
DOI Google Scholar
42

Guan, D.; Zhou, J.; Huang, Y. C.; Dong, C. L.; Wang, J. Q.; Zhou, W.; Shao, Z. P. Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor. Nat. Commun. 2019, 10, 1–8.
DOI Google Scholar
43

Guan, D. Q.; Zhou, J.; Hu, Z. W.; Zhou, W.; Xu, X. M.; Zhong, Y. J.; Liu, B.; Chen, Y. H.; Xu, M. G.; Lin, H. J. et al. Searching general sufficient-and-necessary conditions for ultrafast hydrogen-evolving electrocatalysis. Adv. Funct. Mater. 2019, 29, 1900704.
DOI Google Scholar
44

Bennett, J. W.; Grinberg, I.; Rappe, A. M. New highly polar semiconductor ferroelectrics through d8 Cation-O vacancy substitution into PbTiO3: A theoretical study. J. Am. Chem. Soc. 2008, 130, 17409–17412.
DOI Google Scholar
45

Li, Q.; Wu J. B.; Wu T.; Jin, H. R.; Zhang, N.; Li, J.; Liang, W. X.; Liu, M. L.; Huang, L.; Zhou, J. Phase engineering of atomically thin perovskite oxide for highly active oxygen evolution. Adv. Funct. Mater. 2021, 31, 2102002.
DOI Google Scholar
46

Dong, H. F.; Liu, C. H.; Ye, H. T.; Hu, L. P.; Fugetsu, B.; Dai, W. H.; Cao, Y.; Qi, X. Q.; Lu, H. T.; Zhang, X. J. Three-dimensional nitrogen-doped graphene supported molybdenum disulfide nanoparticles as an advanced catalyst for hydrogen evolution reaction. Sci. Rep. 2015, 5, 17542.
DOI Google Scholar
47

Greeley, J.; Nørskov, J. K. Large-scale, density functional theory-based screening of alloys for hydrogen evolution. Surf. Sci. 2007, 601, 1590–1598.
DOI Google Scholar
48

Vij, V.; Sultan, S.; Harzandi, A. M.; Meena, A.; Tiwari, J. N.; Lee, W. G.; Yoon, T.; Kim, K. S. Nickel-based electrocatalysts for energy-related applications: Oxygen reduction, oxygen evolution, and hydrogen evolution reactions. ACS Catal. 2017, 7, 7196–7225.
DOI Google Scholar
49

Qu, K. G.; Zheng, Y.; Zhang, X. X.; Davey, K.; Dai, S.; Qiao, S. Z. Promotion of electrocatalytic hydrogen evolution reaction on nitrogen-doped carbon nanosheets with secondary heteroatoms. ACS Nano 2017, 11, 7293–7300.
DOI Google Scholar
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Publication history
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Publication history

Received: 01 July 2021
Revised: 06 September 2021
Accepted: 09 September 2021
Published: 20 October 2021
Issue date: April 2022

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© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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