Journal Home > Volume 15 , Issue 7
Nano Research 2022, 15(7): 5873-5883 https://doi.org/10.1007/s12274-022-4230-9
Research Article | Issue | Published: 08 April 2022

Microwave-assisted molybdenum-nickel alloy for efficient water electrolysis under large current density through spillover and Fe doping

Show Author's Information Ya-Nan Zhou,  Hai-Jun Liu,  Zhuo-Ning Shi,  Jian-Cheng Zhou,  Bin Dong( ),  Hui-Ying Zhao,  Feng-Ge Wang,  Jian-Feng Yu,  Yong-Ming Chai( )
State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
Keywords:
overall water splitting, spillover, high-pressure microwave, Fe doping, MoNi4
Topics:
Electrocatalysts
Cite this article:
Zhou Y-N, Liu H-J, Shi Z-N, et al. Microwave-assisted molybdenum-nickel alloy for efficient water electrolysis under large current density through spillover and Fe doping. Nano Research, 2022, 15(7): 5873-5883. https://doi.org/10.1007/s12274-022-4230-9
Download citation
EndNote(RIS)
BibTeX

748

Views

26

Downloads

Citations

20

Crossref

15

WoS

16

Scopus

2

CSCD

Abstract Full text Electronic supplementary material About this article

The development of high-efficiency electrocatalysts for overall water splitting under large current density is significant and challenging. Herein, a high-performing Fe-doped MoNi alloy catalyst (M-H-MoNiFe-50) abundant with flower-like nanorods assemblies has been prepared by high-pressure microwave reaction and hydrogen reduction. Firstly, Fe doped NiMoO4 precursor (M-MoNiFe-50) was synthesized by microwave fast heating, ensuring the robustness of nanorods, which owns larger area and improved catalytic activity than that by conventional hydrothermal method. Secondly, M-MoNiFe-50 was reduced in H2/Ar to fabricate Fe-incorporated MoNi4 alloys (M-H-MoNiFe-50), greatly enhancing the conductivity and facilitating hydrogen/oxygen spillover. The final M-H-MoNiFe-50 exhibits remarkable activity for alkaline/acidic hydrogen evolution reaction and oxygen evolution reaction with low overpotential of 208 (alkaline), 254 (acid) and 347 mV at 1,000 mA·cm−2. Moreover, an alkaline water electrolyzer is established using M-H-MoNiFe-50 as anode and cathode, generating a current density of 100 mA·cm−2 at 1.58 V with encouraging durability of 50 h at 1,000 mA·cm−2. The extraordinary water splitting performance can be chalked up to the large surface area, favorable charge transfer, modified electron distribution, intrinsic robustness as well as an efficient gas spillover of M-H-MoNiFe-50. The final electrocatalyst has great prospects for practical application and confirms the significance of Fe doping, microwave method and spillover effect for catalytic performance improvement.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Microwave-assisted molybdenum-nickel alloy for efficient water electrolysis under large current density through spillover and Fe doping

Show Author's information Ya-Nan Zhou, Hai-Jun Liu, Zhuo-Ning Shi, Jian-Cheng Zhou, Bin Dong( ), Hui-Ying Zhao, Feng-Ge Wang, Jian-Feng Yu, Yong-Ming Chai( )
State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China

Abstract

The development of high-efficiency electrocatalysts for overall water splitting under large current density is significant and challenging. Herein, a high-performing Fe-doped MoNi alloy catalyst (M-H-MoNiFe-50) abundant with flower-like nanorods assemblies has been prepared by high-pressure microwave reaction and hydrogen reduction. Firstly, Fe doped NiMoO4 precursor (M-MoNiFe-50) was synthesized by microwave fast heating, ensuring the robustness of nanorods, which owns larger area and improved catalytic activity than that by conventional hydrothermal method. Secondly, M-MoNiFe-50 was reduced in H2/Ar to fabricate Fe-incorporated MoNi4 alloys (M-H-MoNiFe-50), greatly enhancing the conductivity and facilitating hydrogen/oxygen spillover. The final M-H-MoNiFe-50 exhibits remarkable activity for alkaline/acidic hydrogen evolution reaction and oxygen evolution reaction with low overpotential of 208 (alkaline), 254 (acid) and 347 mV at 1,000 mA·cm−2. Moreover, an alkaline water electrolyzer is established using M-H-MoNiFe-50 as anode and cathode, generating a current density of 100 mA·cm−2 at 1.58 V with encouraging durability of 50 h at 1,000 mA·cm−2. The extraordinary water splitting performance can be chalked up to the large surface area, favorable charge transfer, modified electron distribution, intrinsic robustness as well as an efficient gas spillover of M-H-MoNiFe-50. The final electrocatalyst has great prospects for practical application and confirms the significance of Fe doping, microwave method and spillover effect for catalytic performance improvement.

Keywords: overall water splitting, spillover, high-pressure microwave, Fe doping, MoNi4

References(49)

1

Rong, H. P.; Ji, S. F.; Zhang, J. T.; Wang, D. S.; Li, Y. D. Synthetic strategies of supported atomic clusters for heterogeneous catalysis. Nat. Commun. 2020, 11, 5884.
DOI Google Scholar
2

Zhang, N. Q.; Ye, C. L.; Yan, H.; Li, L. C.; He, H.; Wang, D. S.; Li, Y. D. Single-atom site catalysts for environmental catalysis. Nano Res. 2020, 13, 3165–3182.
DOI Google Scholar
3

Gao, X. Q.; Chen, Y. D.; Sun, T.; Huang, J. M.; Zhang, W.; Wang, Q.; Cao, R. Karst landform-featured monolithic electrode for water electrolysis in neutral media. Energy Environ. Sci. 2020, 13, 174–182.
DOI Google Scholar
4

Zhou, Y. N.; Wang, F. L.; Dou, S. Y.; Shi, Z. N.; Dong, B.; Yu, W. L.; Zhao, H. Y.; Wang, F. G.; Yu, J. F.; Chai, Y. M. Motivating high-valence Nb doping by fast molten salt method for NiFe hydroxides toward efficient oxygen evolution reaction. Chem. Eng. J. 2022, 427, 131643.
DOI Google Scholar
5

Yin, J.; Jin, J.; Lu, M.; Huang, B. L.; Zhang, H.; Peng, Y.; Xi, P. X.; Yan, C. H. Iridium single atoms coupling with oxygen vacancies boosts oxygen evolution reaction in acid media. J. Am. Chem. Soc. 2020, 142, 18378–18386.
DOI Google Scholar
6

Zhang, J. Y.; Yan, Y.; Mei, B. B.; Qi, R. J.; He, T.; Wang, Z. T.; Fang, W. S.; Zaman, S.; Su, Y. Q.; Ding, S. J. et al. Local spin-state tuning of cobalt-iron selenide nanoframes for the boosted oxygen evolution. Energy Environ. Sci. 2021, 14, 365–373.
DOI Google Scholar
7

Zou, X.; Liu, Y. P.; Li, G. D.; Wu, Y. Y.; Liu, D. P.; Li, W.; Li, H. W.; Wang, D. J.; Zhang, Y.; Zou, X. X. Ultrafast formation of amorphous bimetallic hydroxide films on 3D conductive sulfide nanoarrays for large-current-density oxygen evolution electrocatalysis. Adv. Mater. 2017, 29, 1700404.
DOI Google Scholar
8

Lagadec, M. F.; Grimaud, A. Water electrolysers with closed and open electrochemical systems. Nat. Mater. 2020, 19, 1140–1150.
DOI Google Scholar
9

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.
DOI Google Scholar
10

Gao, X. Q.; Chen, D. D.; Qi, J.; Li, F.; Song, Y. J.; Zhang, W.; Cao, R. NiFe oxalate nanomesh array with homogenous doping of Fe for electrocatalytic water oxidation. Small 2019, 15, 1904579.
DOI Google Scholar
11

Zhang, W.; Wu, Y. Z.; Qi, J.; Chen, M. X.; Cao, R. A thin NiFe hydroxide film formed by stepwise electrodeposition strategy with significantly improved catalytic water oxidation efficiency. Adv. Energy Mater. 2017, 7, 1602547.
DOI Google Scholar
12

Highfield, J. G.; Claude, E.; Oguro, K. Electrocatalytic synergism in Ni/Mo cathodes for hydrogen evolution in acid medium: A new model. Electrochim. Acta 1999, 44, 2805–2814.
DOI Google Scholar
13

Kamp, C. J.; Garza, H. H. P.; Fredriksson, H.; Kasemo, B.; Andersson, B.; Skoglundh, M. Nanofabricated catalyst particles for the investigation of catalytic carbon oxidation by oxygen spillover. Langmuir 2017, 33, 4903–4912.
DOI Google Scholar
14

Ananyev, M. V.; Porotnikova, N. M.; Eremin, V. A.; Kurumchin, E. K. Interaction of O2 with LSM-YSZ composite materials and oxygen spillover effect. ACS Catal. 2021, 11, 4247–4262.
DOI Google Scholar
15

Zhao, D. H.; Pan, Y. M.; Zang, Y. R.; Zhao, X. Z. A kinetic and quantum chemical investigation of oxygen spillover from α-Sb2O4 to MoO3. Chin. J. Catal. 1996, 17, 133–138.
Google Scholar
16

Slocombe, D. R. Cool water splitting by microwaves. Nat. Energy 2020, 5, 830–831.
DOI Google Scholar
17

Zhang, H. M.; Lee, J. S. Hybrid microwave annealing synthesizes highly crystalline nanostructures for (photo)electrocatalytic water splitting. Acc. Chem. Res. 2019, 52, 3132–3142.
DOI Google Scholar
18

Serra, J. M.; Borrás-Morell, J. F.; García-Baños, B.; Balaguer, M.; Plaza-González, P.; Santos-Blasco, J.; Catalán-Martínez, D.; Navarrete, L.; Catalá-Civera, J. M. Hydrogen production via microwave-induced water splitting at low temperature. Nat. Energy 2020, 5, 910–919.
DOI Google Scholar
19

Zhang, J.; Wang, T.; Liu, P.; Liao, Z. Q.; Liu, S. H.; Zhuang, X. D.; Chen, M. W.; Zschech, E.; Feng, X. L. Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics. Nat. Commun. 2017, 8, 15437.
DOI Google Scholar
20

Qin, J. F.; Yang, M.; Chen, T. S.; Dong, B.; Hou, S.; Ma, X.; Zhou, Y. N.; Yang, X. L.; Nan, J.; Chai, Y. M. Ternary metal sulfides MoCoNiS derived from metal organic frameworks for efficient oxygen evolution. Int. J. Hydrogen Energy 2020, 45, 2745–2753.
DOI Google Scholar
21

Yan, X. X.; Gu, M. Y.; Wang, Y.; Xu, L.; Tang, Y. W.; Wu, R. B. In-situ growth of Ni nanoparticle-encapsulated N-doped carbon nanotubes on carbon nanorods for efficient hydrogen evolution electrocatalysis. Nano Res. 2020, 13, 975–982.
DOI Google Scholar
22

Zhang, W.; Qi, J.; Liu, K. Q.; Cao, R. A nickel-based integrated electrode from an autologous growth strategy for highly efficient water oxidation. Adv. Energy Mater. 2016, 6, 1502489.
DOI Google Scholar
23

Gong, L. Q.; Yang, H.; Wang, H. M.; Qi, R. J.; Wang, J. L.; Chen, S. H.; You, B.; Dong, Z. H.; Liu, H. F.; Xia, B. Y. Corrosion formation and phase transformation of nickel-iron hydroxide nanosheets array for efficient water oxidation. Nano Res. 2021, 14, 4528–4533.
DOI Google Scholar
24

Hu, W. B.; Liu, Y.; Withers, R. L.; Frankcombe, T. J.; Norén, L.; Snashall, A.; Kitchin, M.; Smith, P.; Gong, B.; Chen, H. et al. Electron-pinned defect-dipoles for high-performance colossal permittivity materials. Nat. Mater. 2013, 12, 821–826.
DOI Google Scholar
25

Wang, Z.; Wang, W. Z.; Zhang, L.; Jiang, D. Surface oxygen vacancies on Co3O4 mediated catalytic formaldehyde oxidation at room temperature. Catal. Sci. Technol. 2016, 6, 3845–3853.
DOI Google Scholar
26

Mao, C. L.; Wang, J. X.; Zou, Y. J.; Qi, G. D.; Loh, J. Y. Y.; Zhang, T. H.; Xia, M. K.; Xu, J.; Deng, F.; Ghoussoub, M. et al. Hydrogen spillover to oxygen vacancy of TiO2-xHy/Fe: Breaking the scaling relationship of ammonia synthesis. J. Am. Chem. Soc. 2020, 142, 17403–17412.
DOI Google Scholar
27

Fang, Y. H.; Liu, Z. P. Tafel kinetics of electrocatalytic reactions: From experiment to first-principles. ACS Catal. 2014, 4, 4364–4376.
DOI Google Scholar
28

Anantharaj, S.; Noda, S.; Driess, M.; Menezes, P. W. The pitfalls of using potentiodynamic polarization curves for Tafel analysis in electrocatalytic water splitting. ACS Energy Lett. 2021, 6, 1607–1611.
DOI Google Scholar
29

De Chialvo, M. R. G.; Chialvo, A. C. Kinetics of hydrogen evolution reaction with Frumkin adsorption: Re-examination of the Volmer-Heyrovsky and Volmer-Tafel routes. Electrochim. Acta 1998, 44, 841–851.
DOI Google Scholar
30

Shinagawa, T.; Garcia-Esparza, A. T.; Takanabe, K. Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion. Sci. Rep. 2015, 5, 13801.
DOI Google Scholar
31

Guan, C.; Xiao, W.; Wu, H. J.; Liu, X. M.; Zang, W. J.; Zhang, H.; Ding, J.; Feng, Y. P.; Pennycook, S. J.; Wang, J. Hollow Mo-doped CoP nanoarrays for efficient overall water splitting. Nano Energy 2018, 48, 73–80.
DOI Google Scholar
32

Chi, J. Q.; Zhang, X. Y.; Ma, X.; Dong, B.; Zhang, J. Q.; Guo, B. Y.; Yang, M.; Wang, L.; Chai, Y. M.; Liu, C. G. Interface charge engineering of ultrafine Ru/Ni2P nanoparticles encapsulated in N, P-codoped hollow carbon nanospheres for efficient hydrogen evolution. ACS Sustainable Chem. Eng. 2019, 7, 17714–17722.
DOI Google Scholar
33

Tian, X. Y.; Zhao, P. C.; Sheng, W. C. Hydrogen evolution and oxidation: Mechanistic studies and material advances. Adv. Mater. 2019, 31, 1808066.
DOI Google Scholar
34

Yu, L.; Zhou, T. T.; Cao, S. H.; Tai, X. S.; Liu, L. L.; Wang, Y. Suppressing the surface passivation of Pt-Mo nanowires via constructing Mo-Se coordination for boosting HER performance. Nano Res. 2021, 14, 2659–2665.
DOI Google Scholar
35

Duan, Y.; Yu, Z. Y.; Hu, S. J.; Zheng, X. S.; Zhang, C. T.; Ding, H. H.; Hu, B. C.; Fu, Q. Q.; Yu, Z. L.; Zheng, X. et al. Scaled-up synthesis of amorphous NiFeMo oxides and their rapid surface reconstruction for superior oxygen evolution catalysis. Angew. Chem., Int. Ed. 2019, 58, 15772–15777.
DOI Google Scholar
36

Cui, B. H.; Hu, Z.; Liu, C.; Liu, S. L.; Chen, F. S.; Hu, S.; Zhang, J. F.; Zhou, W.; Deng, Y. D.; Qin, Z. B. et al. Heterogeneous lamellar-edged Fe-Ni(OH)2/Ni3S2 nanoarray for efficient and stable seawater oxidation. Nano Res. 2021, 14, 1149–1155.
DOI Google Scholar
37

Yan, M. L.; Zhao, Z. Y.; Cui, P. X.; Mao, K.; Chen, C.; Wang, X. Z.; Wu, Q.; Yang, H.; Yang, L. J.; Hu, Z. Construction of hierarchical FeNi3@(Fe, Ni)S2 core-shell heterojunctions for advanced oxygen evolution. Nano Res. 2021, 14, 4220–4226.
DOI Google Scholar
38

Wang, T. J.; Liu, X. Y.; Li, Y.; Li, F. M.; Deng, Z. W.; Chen, Y. Ultrasonication-assisted and gram-scale synthesis of Co-LDH nanosheet aggregates for oxygen evolution reaction. Nano Res. 2020, 13, 79–85.
DOI Google Scholar
39

Wei, Z. W.; Wang, H. J.; Zhang, C.; Xu, K.; Lu, X. L.; Lu, T. B. Reversed charge transfer and enhanced hydrogen spillover in platinum nanoclusters anchored on titanium oxide with rich oxygen vacancies boost hydrogen evolution reaction. Angew. Chem., Int. Ed. 2021, 60, 16622–16627.
DOI Google Scholar
40

Sun, S. F.; Zhou, X.; Cong, B. W.; Hong, W. Z.; Chen, G. Tailoring the d-band centers endows (NixFe1−x)2P nanosheets with efficient oxygen evolution catalysis. ACS Catal. 2020, 10, 9086–9097.
DOI Google Scholar
41

Du, W.; Shi, Y. M.; Zhou, W.; Yu, Y. F.; Zhang, B. Unveiling the in situ dissolution and polymerization of Mo in Ni4Mo alloy for promoting the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2021, 60, 7051–7055.
DOI Google Scholar
42

Liu, Z. Z.; Shang, X.; Dong, B.; Chai, Y. M. Triple Ni-Co-Mo metal sulfides with one-dimensional and hierarchical nanostructures towards highly efficient hydrogen evolution reaction. J. Catal. 2018, 361, 204–213.
DOI Google Scholar
43

Schalenbach, M.; Speck, F. D.; Ledendecker, M.; Kasian, O.; Goehl, D.; Mingers, A. M.; Breitbach, B.; Springer, H.; Cherevko, S.; Mayrhofer, K. J. J. Nickel-molybdenum alloy catalysts for the hydrogen evolution reaction: Activity and stability revised. Electrochim. Acta 2018, 259, 1154–1161.
DOI Google Scholar
44

Brito, J. L.; Laine, J. Reducibility of Ni-Mo/Al2O3 catalysts: A TPR study. J. Catal. 1993, 139, 540–550.
DOI Google Scholar
45

Shang, H. Y.; Xu, Y. Q.; Zhao, H. J.; Liu, C. G. Study of carbon nanotube supported Co-Mo HDS catalysts. J. Mol. Catal. 2004, 18, 41–46.
DOI Google Scholar
46

Nabaho, D.; Niemantsverdriet, J. W.; Claeys, M.; Van Steen, E. Hydrogen spillover in the Fischer-Tropsch synthesis: An analysis of platinum as a promoter for cobalt-alumina catalysts. Catal. Today 2016, 261, 17–27.
DOI Google Scholar
47

Yao, Y. X.; Goodman, D. W. Direct evidence of hydrogen spillover from Ni to Cu on Ni-Cu bimetallic catalysts. J. Mol. Catal. A: Chem. 2014, 383–384, 239–242.
Google Scholar
48

Li, W. M.; Liu, H. D.; Zhang, M.; Chen, Y. F. Comparative study of mesoporous NixMn6−xCe4 composite oxides for NO catalytic oxidation. RSC Adv. 2019, 9, 31035–31042.
DOI Google Scholar
49

Geng, S.; Liu, Y. Q.; Yu, Y. S.; Yang, W. W.; Li, H. B. Engineering defects and adjusting electronic structure on S doped MoO2 nanosheets toward highly active hydrogen evolution reaction. Nano Res. 2020, 13, 121–126.
DOI Google Scholar
File
12274_2022_4230_MOESM1_ESM.pdf (2.7 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 27 November 2021
Revised: 11 February 2022
Accepted: 13 February 2022
Published: 08 April 2022
Issue date: July 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 52174283) and Qingdao Science and Technology Benefiting People Special Project (No. 20-3-4-8-nsh), the Fundamental Research Funds for the Central Universities (No. 20CX02212A), the Development Fund of State Key Laboratory of Heavy Oil Processing and the Postgraduate Innovation Project of China University of Petroleum (No. YCX2020046).

Return