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Nano Research 2021, 14(11): 4073-4078 https://doi.org/10.1007/s12274-021-3342-y
Research Article | Issue | Published: 01 March 2021

Cobalt tungsten phosphide with tunable W-doping as highly efficient electrocatalysts for hydrogen evolution reaction

Show Author's Information Bowei Zhang1,2,§,  Chaojiang Li3,§,  Jun Hu4( ),  Dongdong Peng2,  Kang Huang1,  Junsheng Wu1( ),  Zhong Chen2,  Yizhong Huang2( )
Institute for Advanced Materials and Technology University of Science and Technology BeijingBeijing 100083 China
School of Materials Science and EngineeringNanyang Technological University, 50 Nanyang AvenueSingapore 639798 Singapore
School of mechanical engineeringBeijing Institute of TechnologyZhongguancun AvenueHaidian districtBeijing 100081 China
School of Chemical EngineeringNorthwest UniversityXi'an 710069 China

§ Bowei Zhang and Chaojiang Li contributed equally to this work.

Keywords:
hydrogen evolution reaction, cobalt tungsten phosphide, W-doping, tunable composition, acid and alkaline media
Topics:
Hydrogen evolution reaction
Cite this article:
Zhang B, Li C, Hu J, et al. Cobalt tungsten phosphide with tunable W-doping as highly efficient electrocatalysts for hydrogen evolution reaction. Nano Research, 2021, 14(11): 4073-4078. https://doi.org/10.1007/s12274-021-3342-y
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Abstract Full text Electronic supplementary material About this article

It has been of interest in seeking electrocatalysts that could exercise equally high-efficient and durable hydrogen evolution upon nonselective electrolytes in both acidic and alkaline environments. Herein, we report a facile strategy to fabricate cobalt tungsten phosphides (CoxW2−xP2/C) hollow polyhedrons with tunable composition based on metal-organic frameworks (MOFs) template method. By the deliberate control of W doping, the synthesized catalyst with the composition of Co0.9W1.1P2/C is found to be able to achieve a current density of 10 mA·cm−2 at overpotentials of 35 and 54 mV in acidic and alkaline media, respectively. This combined electrochemical property stands atop the state-of-the-art electrocatalyst counterparts. To unveil the peculiar behavior of the structure, density functional theory (DFT) calculation was implemented and reveals that the surface W-doping facilitates the optimization of hydrogen absorption free energy (ΔGH*) as well as the thermodynamic and kinetics barriers for water dissociation, which is coupled with the hollow structure of Co-W phosphides, leading to the prominent HER catalytic performance.


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Electronic supplementary material
About this article

Cobalt tungsten phosphide with tunable W-doping as highly efficient electrocatalysts for hydrogen evolution reaction

Show Author's information Bowei Zhang1,2,§, Chaojiang Li3,§, Jun Hu4( ), Dongdong Peng2, Kang Huang1, Junsheng Wu1( ), Zhong Chen2, Yizhong Huang2( )
Institute for Advanced Materials and Technology University of Science and Technology BeijingBeijing 100083 China
School of Materials Science and EngineeringNanyang Technological University, 50 Nanyang AvenueSingapore 639798 Singapore
School of mechanical engineeringBeijing Institute of TechnologyZhongguancun AvenueHaidian districtBeijing 100081 China
School of Chemical EngineeringNorthwest UniversityXi'an 710069 China

§ Bowei Zhang and Chaojiang Li contributed equally to this work.

Abstract

It has been of interest in seeking electrocatalysts that could exercise equally high-efficient and durable hydrogen evolution upon nonselective electrolytes in both acidic and alkaline environments. Herein, we report a facile strategy to fabricate cobalt tungsten phosphides (CoxW2−xP2/C) hollow polyhedrons with tunable composition based on metal-organic frameworks (MOFs) template method. By the deliberate control of W doping, the synthesized catalyst with the composition of Co0.9W1.1P2/C is found to be able to achieve a current density of 10 mA·cm−2 at overpotentials of 35 and 54 mV in acidic and alkaline media, respectively. This combined electrochemical property stands atop the state-of-the-art electrocatalyst counterparts. To unveil the peculiar behavior of the structure, density functional theory (DFT) calculation was implemented and reveals that the surface W-doping facilitates the optimization of hydrogen absorption free energy (ΔGH*) as well as the thermodynamic and kinetics barriers for water dissociation, which is coupled with the hollow structure of Co-W phosphides, leading to the prominent HER catalytic performance.

Keywords: hydrogen evolution reaction, cobalt tungsten phosphide, W-doping, tunable composition, acid and alkaline media

References(43)

1

Zhao, G. Q.; Rui, K.; Dou, S. X.; Sun, W. P. Heterostructures for electrochemical hydrogen evolution reaction: A review. Adv. Funct. Mater. 2018, 28, 1803291.
DOI Google Scholar
2

Gong, M.; Wang, D. Y.; Chen, C. C.; Hwang, B. J.; Dai, H. J. A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Res. 2016, 9, 28–46.
DOI Google Scholar
3

Xu, Y.; Tu, W. G.; Zhang, B. W.; Yin, S. M.; Huang, Y. Z.; Kraft, M.; Xu, R. Nickel nanoparticles encapsulated in few-layer nitrogen- doped graphene derived from metal–organic frameworks as efficient bifunctional electrocatalysts for overall water splitting. Adv. Mater. 2017, 29, 1605957.
DOI Google Scholar
4

Tu, W. G.; Xu, Y.; Wang, J. J.; Zhang, B. W.; Zhou, T. H.; Yin, S. M.; Wu, S. Y.; Li, C. M.; Huang, Y. Z.; Zhou, Y. et al. Investigating the role of tunable nitrogen vacancies in graphitic carbon nitride nanosheets for efficient visible-light-driven H2 evolution and CO2 reduction. ACS Sustainable Chem. Eng. 2017, 5, 7260–7268.
DOI Google Scholar
5

Zhang, Y. Q.; Xia, X. H.; Cao, X.; Zhang, B. W.; Tiep, N. H.; He, H. Y.; Chen, S.; Huang, Y. Z.; Fan, H. J. Ultrafine metal nanoparticles/ N-doped porous carbon hybrids coated on carbon fibers as flexible and binder-free water splitting catalysts. Adv. Energy Mater. 2017, 7, 1700220.
DOI Google Scholar
6

Chen, Z. L.; Wu, R. B.; Liu, Y.; Ha, Y.; Guo, Y. H.; Sun, D. L.; Liu, M.; Fang, F. Ultrafine co nanoparticles encapsulated in carbon- nanotubes-grafted graphene sheets as advanced electrocatalysts for the hydrogen evolution reaction. Adv. Mater. 2018, 30, 1802011.
DOI Google Scholar
7

Zhang, X.; Yu, X. L.; Zhang, L. J.; Zhou, F.; Liang, Y. Y.; Wang, R. H. Molybdenum phosphide/carbon nanotube hybrids as pH-universal electrocatalysts for hydrogen evolution reaction. Adv. Funct. Mater. 2018, 28, 1706523.
DOI Google Scholar
8

Wang, R.; Dong, X. Y.; Du, J.; Zhao, J. Y.; Zang, S. Q. MOF- derived bifunctional Cu3P nanoparticles coated by a N, P-codoped carbon shell for hydrogen evolution and oxygen reduction. Adv. Mater. 2018, 30, 1703711.
DOI Google Scholar
9

Chen, G. B.; Wang, T.; Zhang, J.; Liu, P.; Sun, H. J.; Zhuang, X. D.; Chen, M. W.; Feng, X. L. Accelerated hydrogen evolution kinetics on nife-layered double hydroxide electrocatalysts by tailoring water dissociation active sites. Adv. Mater. 2018, 30, 1706279.
DOI Google Scholar
10

Ahn, W.; Park, M. G.; Lee, D. U.; Seo, M. H.; Jiang, G. P.; Cano, Z. P.; Hassan, F. M.; Chen, Z. W. Hollow multivoid nanocuboids derived from ternary Ni–Co–Fe prussian blue analog for dual-electrocatalysis of oxygen and hydrogen evolution reactions. Adv. Funct. Mater. 2018, 28, 1802129.
DOI Google Scholar
11

Zhang, B. W.; Yang, G.; Li, C. J.; Huang, K.; Wu, J. S.; Hao, S. J.; Feng, J. Y.; Peng, D. D.; Huang, Y. Z. Phase controllable fabrication of zinc cobalt sulfide hollow polyhedra as high-performance electrocatalysts for the hydrogen evolution reaction. Nanoscale 2018, 10, 1774–1778.
DOI Google Scholar
12

Xiao, J.; Zhang, Z. Y.; Zhang, Y.; Lv, Q. Y.; Jing, F.; Chi, K.; Wang, S. Large-scale printing synthesis of transition metal phosphides encapsulated in N, P co-doped carbon as highly efficient hydrogen evolution cathodes. Nano Energy 2018, 51, 223–230.
DOI Google Scholar
13

Ge, Y. C.; Dong, P.; Craig, S. R.; Ajayan, P. M.; Ye, M. X.; Shen, J. F. Transforming nickel hydroxide into 3D Prussian blue analogue array to obtain Ni2P/Fe2P for efficient hydrogen evolution reaction. Adv. Energy Mater. 2018, 8, 1800484.
DOI Google Scholar
14

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
15

Ouyang, C. B.; Wang, X.; Wang, S. Y. Phosphorus-doped CoS2 nanosheet arrays as ultra-efficient electrocatalysts for the hydrogen evolution reaction. Chem. Commun. 2015, 51, 14160–14163.
DOI Google Scholar
16

Fu, Q.; Wu, T.; Fu, G.; Gao, T. L.; Han, J. C.; Yao, T.; Zhang, Y. M.; Zhong, W. W.; Wang, X. J.; Song, B. Skutterudite-type ternary Co1–xNixP3 nanoneedle array electrocatalysts for enhanced hydrogen and oxygen evolution. ACS Energy Lett. 2018, 3, 1744–1752.
DOI Google Scholar
17

Jiang, H.; Gu, J. X.; Zheng, X. S.; Liu, M.; Qiu, X. Q.; Wang, L. B.; Li, W. Z.; Chen, Z. F.; Ji, X. B.; Li, J. Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER. Energy Environ. Sci. 2019, 12, 322– 333.
DOI Google Scholar
18

Gao, K.; Wang, B.; Tao, L.; Cunning, B. V.; Zhang, Z. P.; Wang, S. Y.; Ruoff, R. S.; Qu, L. T. Efficient metal-free electrocatalysts from N-doped carbon nanomaterials: Mono-doping and Co-doping. Adv. Mater. 2019, 31, 1805121.
DOI Google Scholar
19

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
20

Wang, T.; Jin, R. M.; Wu, X. Q.; Zheng, J.; Li, X. G.; Ostrikov, K. A highly efficient Ni–Mo bimetallic hydrogen evolution catalyst derived from a molybdate incorporated Ni-MOF. J. Mater. Chem. A 2018, 6, 9228–9235.
DOI Google Scholar
21

Chen, Y. J.; Dong, C. Q.; Zhang, J.; Zhang, C.; Zhang, Z. H. Hierarchically porous Mo-doped Ni–Fe oxide nanowires efficiently catalyzing oxygen/hydrogen evolution reactions. J. Mater. Chem. A 2018, 6, 8430–8440.
DOI Google Scholar
22

Guo, Y. P.; Dong, Z. P.; Cui, Z. K.; Zhang, X. J.; Ma, J. T. Promoting effect of W doped in electrodeposited Co–P catalysts for hydrogen generation from alkaline NaBH4 solution. Int. J. Hydrogen Energy 2012, 37, 1577–1583.
DOI Google Scholar
23

Jin, Z. Y.; Li, P. P.; Huang, X.; Zeng, G. F.; Jin, Y.; Zheng, B. Z.; Xiao, D. Three-dimensional amorphous tungsten-doped nickel phosphide microsphere as an efficient electrocatalyst for hydrogen evolution. J. Mater. Chem. A 2014, 2, 18593–18599.
DOI Google Scholar
24

Bhat, K. S.; Nagaraja, H. S. Effect of isoelectronic tungsten doping on molybdenum selenide nanostructures and their graphene hybrids for supercapacitors. Electrochim. Acta 2019, 302, 459–471.
DOI Google Scholar
25

Zhang, B.; Zheng, X. L.; Voznyy, O.; Comin, R.; Bajdich, M.; García-Melchor, M.; Han, L. L.; Xu, J. X.; Liu, M.; Zheng, L. R. et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science 2016, 352, 333–337.
DOI Google Scholar
26

Ma, Y. Y.; Wu, C. X.; Feng, X. J.; Tan, H. Q.; Yan, L. K.; Liu, Y.; Kang, Z. H.; Wang, E. B.; Li, Y. G. Highly efficient hydrogen evolution from seawater by a low-cost and stable CoMoP@C electrocatalyst superior to Pt/C. Energy Environ. Sci. 2017, 10, 788–798.
DOI Google Scholar
27

Wang, X. D.; Chen, H. Y.; Xu, Y. F.; Liao, J. F.; Chen, B. X.; Rao, H. S.; Kuang, D. B.; Su, C. Y. Self-supported NiMoP2 nanowires on carbon cloth as an efficient and durable electrocatalyst for overall water splitting. J. Mater. Chem. A 2017, 5, 7191–7199.
DOI Google Scholar
28

Weng, B. C.; Grice, C. R.; Meng, W. W.; Guan, L.; Xu, F. H.; Yu, Y.; Wang, C. L.; Zhao, D. W.; Yan, Y. F. Metal–organic framework- derived CoWP@C composite nanowire electrocatalyst for efficient water splitting. ACS Energy Lett. 2018, 3, 1434–1442.
DOI Google Scholar
29

Chen, Z. L.; Ha, Y.; Jia, H. X.; Yan, X. X.; Chen, M.; Liu, M.; Wu, R. B. Oriented transformation of Co-LDH into 2D/3D ZIF-67 to achieve Co–N–C hybrids for efficient overall water splitting. Adv. Energy Mater. 2019, 9, 1803918.
DOI Google Scholar
30

Lu, Q. P.; Wang, A. L.; Cheng, H. F.; Gong, Y.; Yun, Q. B.; Yang, N. L.; Li, B.; Chen, B.; Zhang, Q. H.; Zong, Y. et al. Synthesis of hierarchical 4H/fcc ru nanotubes for highly efficient hydrogen evolution in alkaline media. Small 2018, 14, 1801090.
DOI Google Scholar
31

Lu, X. F.; Yu, L.; Lou, X. W. D. Highly crystalline Ni-doped FeP/carbon hollow nanorods as all-pH efficient and durable hydrogen evolving electrocatalysts. Sci. Adv. 2019, 5, eaav6009.
DOI Google Scholar
32

Zhang, B. W.; Hao, S. J.; Xiao, D. R.; Wu, J. S.; Huang, Y. Z. Templated formation of porous Mn2O3 octahedra from Mn-MIL-100 for lithium-ion battery anode materials. Mater. Des. 2016, 98, 319–323.
DOI Google Scholar
33

Zhu, P. P.; Zhang, Z.; Hao, S. J.; Zhang, B. W.; Zhao, P. F.; Yu, J.; Cai, J. X.; Huang, Y. Z.; Yang, Z. Y. Multi-channel FeP@C octahedra anchored on reduced graphene oxide nanosheet with efficient performance for lithium-ion batteries. Carbon 2018, 139, 477–485.
DOI Google Scholar
34

Zhang, B. W.; Li, C. J.; Yang, G.; Huang, K.; Wu, J. S.; Li, Z.; Cao, X.; Peng, D. D.; Hao, S. J.; Huang, Y. Z. Nanostructured CuO/C hollow Shell@3D copper dendrites as a highly efficient electrocatalyst for oxygen evolution reaction. ACS Appl. Mater. Interfaces 2018, 10, 23807–23812.
DOI Google Scholar
35

Hao, S. J.; Ouyang, B.; Li, C. J.; Zhang, B. W.; Feng, J. Y.; Wu, J. S.; Srinivasan, M.; Huang, Y. Z. Hollow mesoporous Co(PO3)2@carbon polyhedra as high performance anode materials for lithium ion batteries. J. Phys. Chem. C 2019, 123, 8599–8606.
DOI Google Scholar
36

Zhang, H.; Liu, X. M.; Wu, Y.; Guan, C.; Cheetham, A. K.; Wang, J. MOF-derived nanohybrids for electrocatalysis and energy storage: Current status and perspectives. Chem. Commun. 2018, 54, 5268– 5288.
DOI Google Scholar
37

Zhang, M. D.; Dai, Q. B.; Zheng, H. G.; Chen, M. D.; Dai, L. M. Novel MOF-derived Co@N-C bifunctional catalysts for highly efficient Zn–air batteries and water splitting. Adv. Mater. 2018, 30, 1705431.
DOI Google Scholar
38

Gao, R. S.; Tang, J.; Yu, X. L.; Tang, S.; Ozawa, K.; Sasaki, T.; Qin, L. C. In situ synthesis of MOF-derived carbon shells for silicon anode with improved lithium-ion storage. Nano Energy 2020, 70, 104444.
DOI Google Scholar
39

Yang, Q. J.; Wang, Q. S.; Long, Y.; Wang, F.; Wu, L. L.; Pan, J.; Han, J.; Lei, Y.; Shi, W. D.; Song, S. Y. In situ formation of Co9S8 quantum dots in MOF-derived ternary metal layered double hydroxide nanoarrays for high-performance hybrid supercapacitors. Adv. Energy Mater. 2020, 10, 1903193.
DOI Google Scholar
40

Li, F.; Wang, C. R.; Han, X. C.; Feng, X. Q.; Qu, Y. Q.; Liu, J.; Chen, W. L.; Zhao, L. P.; Song, X. F.; Zhu, H. et al. Confinement effect of mesopores: In situ synthesis of cationic tungsten-vacancies for a highly ordered mesoporous tungsten phosphide electrocatalyst. ACS Appl. Mater. Interfaces 2020, 12, 22741–22750.
DOI Google Scholar
41

Huang, K.; Zhang, B. W.; Wu, J. S.; Zhang, T. Y.; Peng, D. D.; Cao, X.; Zhang, Z.; Li, Z.; Huang, Y. Z. Exploring the impact of atomic lattice deformation on oxygen evolution reactions based on a sub-5 nm pure face-centred cubic high-entropy alloy electrocatalyst. J. Mater. Chem. A 2020, 8, 11938–11947.
DOI Google Scholar
42

Peng, D. D.; Zhang, B. W.; Wu, J. S.; Huang, K.; Cao, X.; Lu, Y.; Zhang, Y.; Li, C. J.; Huang, Y. Z. Growth of lattice coherent Co9S8/Co3O4 nano- heterostructure for maximizing the catalysis of Co-based composites. ChemCatChem 2020, 12, 2431–2435.
DOI Google Scholar
43

Hu, J.; Zhao, X.; Chen, W.; Zheng, S. L.; Chen, Z. Mechanistic study of monolayer NiP2 (100) toward solar hydrogen production. Sol. RRL 2020, 4, 1900360.
DOI Google Scholar
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Acknowledgements

Publication history

Received: 07 September 2020
Revised: 12 January 2021
Accepted: 19 January 2021
Published: 01 March 2021
Issue date: November 2021

Copyright

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

Acknowledgements

Acknowledgements

This work was supported by the National Science Foundation for Young Scientists of China (No. 51901018), China Postdoctoral Science Foundation (No. 2019M660456), the National Natural Science Foundation of China (Nos. 51771027 and 21676216), Young Elite Scientists Sponsorship Program by China Association for Science and Technology (YESS, 2019QNRC001), the Fundamental Research Funds for the Central Universities (No. FRF-MP-19-001), National Key Research and Development Program of China (No. 2017YFB0702100) and Singapore MOE AcRF Tier 1 grant M4011528.

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