Journal Home > Volume 10 , Issue 4
Nano Research 2017, 10(4): 1178-1188 https://doi.org/10.1007/s12274-017-1421-x
Review Article | Issue | Published: 07 March 2017

Defect-rich MoS2 nanowall catalyst for efficient hydrogen evolution reaction

Show Author's Information Junfeng Xie1,2( ),  Haichao Qu1,  Jianping Xin1,  Xinxia Zhang1,  Guanwei Cui1,  Xiaodong Zhang2,  Jian Bao2,  Bo Tang1,  Yi Xie2( )
College of ChemistryChemical Engineering and Materials ScienceCollaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of ShandongKey Laboratory of Molecular and Nano ProbesMinistry of EducationInstitute of Molecular and Nano ScienceShandong Normal UniversityJinan250014China
Hefei National Laboratory for Physical Sciences at the MicroscaleDepartment of ChemistryUniversity of Science and Technology of ChinaHefei230026China
Keywords:
electrocatalysis, water splitting, hydrogen evolution reaction, molybdenum disulfide (MoS2), nanowall
Cite this article:
Xie J, Qu H, Xin J, et al. Defect-rich MoS2 nanowall catalyst for efficient hydrogen evolution reaction. Nano Research, 2017, 10(4): 1178-1188. https://doi.org/10.1007/s12274-017-1421-x
Download citation
EndNote(RIS)
BibTeX

738

Views

53

Downloads

Citations

172

Crossref

N/A

WoS

168

Scopus

5

CSCD

Abstract Full text Electronic supplementary material About this article

Designing efficient electrocatalysts for the hydrogen evolution reaction (HER) has attracted substantial attention owing to the urgent demand for clean energy to face the energy crisis and subsequent environmental issues in the near future. Among the large variety of HER catalysts, molybdenum disulfide (MoS2) has been regarded as the most famous catalyst owing to its abundance, low price, high efficiency, and definite catalytic mechanism. In this study, defect-engineered MoS2 nanowall (NW) catalysts with controllable thickness were fabricated and exhibited a significantly enhanced HER performance. Benefiting from the highly exposed active edge sites and the rough surface accompanied by the robust NW structure, the defect-rich MoS2 NW catalyst with an optimized thickness showed an ultralow onset overpotential of 85 mV, a high current density of 310.6 mA·cm-2 at η = 300 mV, and a low potential of 95 mV to drive a 10 mA·cm-2 cathodic current. Additionally, excellent electrochemical stability was realized, making this freestanding NW catalyst a promising candidate for practical water splitting and hydrogen production.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Defect-rich MoS2 nanowall catalyst for efficient hydrogen evolution reaction

Show Author's information Junfeng Xie1,2( ), Haichao Qu1, Jianping Xin1, Xinxia Zhang1, Guanwei Cui1, Xiaodong Zhang2, Jian Bao2, Bo Tang1, Yi Xie2( )
College of ChemistryChemical Engineering and Materials ScienceCollaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of ShandongKey Laboratory of Molecular and Nano ProbesMinistry of EducationInstitute of Molecular and Nano ScienceShandong Normal UniversityJinan250014China
Hefei National Laboratory for Physical Sciences at the MicroscaleDepartment of ChemistryUniversity of Science and Technology of ChinaHefei230026China

Abstract

Designing efficient electrocatalysts for the hydrogen evolution reaction (HER) has attracted substantial attention owing to the urgent demand for clean energy to face the energy crisis and subsequent environmental issues in the near future. Among the large variety of HER catalysts, molybdenum disulfide (MoS2) has been regarded as the most famous catalyst owing to its abundance, low price, high efficiency, and definite catalytic mechanism. In this study, defect-engineered MoS2 nanowall (NW) catalysts with controllable thickness were fabricated and exhibited a significantly enhanced HER performance. Benefiting from the highly exposed active edge sites and the rough surface accompanied by the robust NW structure, the defect-rich MoS2 NW catalyst with an optimized thickness showed an ultralow onset overpotential of 85 mV, a high current density of 310.6 mA·cm-2 at η = 300 mV, and a low potential of 95 mV to drive a 10 mA·cm-2 cathodic current. Additionally, excellent electrochemical stability was realized, making this freestanding NW catalyst a promising candidate for practical water splitting and hydrogen production.

Keywords: electrocatalysis, water splitting, hydrogen evolution reaction, molybdenum disulfide (MoS2), nanowall

References(46)

1

Turner, J. A. Sustainable hydrogen production. Science 2004, 305, 972–974.
DOI Google Scholar
2

Morales-Guio, C. G.; Stern, L. -A.; Hu, X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 2014, 43, 6555–6569.
DOI Google Scholar
3

Xie, J.; Xie, Y. Structural engineering of electrocatalysts for the hydrogen evolution reaction: Order or disorder? ChemCatChem 2015, 7, 2568–2580.
DOI Google Scholar
4

Xie, J.; Xie, Y. Transition metal nitrides for electrocatalytic energy conversion: Opportunities and challenges. Chem. Eur. J. 2016, 22, 3588–3598.
DOI Google Scholar
5

Hinnemann, B.; Moses, P. G.; Bonde, J.; Jørgensen, K. P.; Nielsen, J. H.; Horch, S.; Chorkendorff, I.; Nørskov, J. K. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 2005, 127, 5308–5309.
DOI Google Scholar
6

Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.; Chorkendorff, I. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 2007, 317, 100–102.
DOI Google Scholar
7

Kibsgaard, J.; Chen, Z.; Reinecke, B. N.; Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 2012, 11, 963–969.
DOI Google Scholar
8

Kong, D.; Wang, H.; Cha, J. J.; Pasta, M.; Koski, K. J.; Yao, J.; Cui, Y. Synthesis of MoS2 and MoSe2 films with vertically aligned layers. Nano Lett. 2013, 13, 1341–1347.
DOI Google Scholar
9

Wang, H.; Kong, D.; Johanes, P.; Cha, J. J.; Zheng, G.; Yan, K.; Liu, N.; Cui, Y. MoSe2 and WSe2 nanofilms with vertically aligned molecular layers on curved and rough surfaces. Nano Lett. 2013, 13, 3426–3433.
DOI Google Scholar
10

Wang, H.; Lu, Z.; Xu, S.; Kong, D.; Cha, J. J.; Zheng, G.; Hsu, P. -C.; Yan, K.; Bradshaw, D.; Prinz, F. B.; Cui, Y. Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, 19701–19706.
DOI Google Scholar
11

Xie, J.; Zhang, H.; Li, S.; Wang, R.; Sun, X.; Zhou, M.; Zhou, J.; Lou, X. W.; Xie, Y. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 2013, 25, 5807–5813.
DOI Google Scholar
12

Xie, J.; Zhang, J.; Li, S.; Grote, F.; Zhang, X.; Zhang, H.; Wang, R.; Lei, Y.; Pan, B.; Xie, Y. Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J. Am. Chem. Soc. 2013, 135, 17881–17888.
DOI Google Scholar
13

Yang, L.; Zhou, W.; Lu, J.; Hou, D.; Ke, Y.; Li, G.; Tang, Z.; Kang, X.; Chen, S. Hierarchical spheres constructed by defect-rich MoS2/carbon nanosheets for efficient electrocatalytic hydrogen evolution. Nano Energy 2016, 22, 490–498.
DOI Google Scholar
14

Zhou, W.; Zhou, K.; Hou, D.; Liu, X.; Li, G.; Sang, Y.; Liu, H.; Li, L.; Chen, S. Three-dimensional hierarchical frameworks based on MoS2 nanosheets self-assembled on graphene oxide for efficient electrocatalytic hydrogen evolution. ACS Appl. Mater. Interfaces 2014, 6, 21534–21540.
DOI Google Scholar
15

Zhou, W.; Hou, D.; Sang, Y.; Yao, S.; Zhou, J.; Li, G.; Li, L.; Liu, H.; Chen, S. MoO2 nanobelts@nitrogen self-doped MoS2 nanosheets as effective electrocatalysts for hydrogen evolution reaction. J. Mater. Chem. A 2014, 2, 11358–11364.
DOI Google Scholar
16

Yang, L.; Zhou, W.; Hou, D.; Zhou, K.; Li, G.; Tang, Z.; Li, L.; Chen, S. Porous metallic MoO2-supported MoS2 nanosheets for enhanced electrocatalytic activity in the hydrogen evolution reaction. Nanoscale 2015, 7, 5203–5208.
DOI Google Scholar
17

Xie, J.; Xin, J.; Cui, G.; Zhang, X.; Zhou, L.; Wang, Y.; Liu, W.; Wang, C.; Ning, M.; Xia, X.; Zhao, Y.; Tang, B. Vertically aligned oxygen-doped molybdenum disulfide nanosheets grown on carbon cloth realizing robust hydrogen evolution reaction. Inorg. Chem. Front. 2016, 3, 1160–1166.
DOI Google Scholar
18

Ye, G.; Gong, Y.; Lin, J.; Li, B.; He, Y.; Pantelides, S. T.; Zhou, W.; Vajtai, R.; Ajayan, P. M. Defects engineered monolayer MoS2 for improved hydrogen evolution reaction. Nano Lett. 2016, 16, 1097–1103.
DOI Google Scholar
19

Guo, Y.; Zhang, X.; Zhang, X.; You, T. Defect- and S-rich ultrathin MoS2 nanosheet embedded N-doped carbon nanofibers for efficient hydrogen evolution. J. Mater. Chem. A 2015, 3, 15927–15934.
DOI Google Scholar
20

Lu, Z.; Zhu, W.; Yu, X.; Zhang, H.; Li, Y.; Sun, X.; Wang, X.; Wang, H.; Wang, J.; Luo, J.; Lei, X.; Jiang, L. Ultrahigh hydrogen evolution performance of under-water "superaerophobic" MoS2 nanostructured electrodes. Adv. Mater. 2014, 26, 2683–2687.
DOI Google Scholar
21

Yang, Y.; Fei, H.; Ruan, G.; Xiang, C.; Tour, J. M. Edge- oriented MoS2 nanoporous films as flexible electrodes for hydrogen evolution reactions and supercapacitor devices. Adv. Mater. 2014, 26, 8163–8168.
DOI Google Scholar
22

Xie, J.; Li, S.; Zhang, X.; Zhang, J.; Wang, R.; Zhang, H.; Pan, B.; Xie, Y. Atomically-thin molybdenum nitride nanosheets with exposed active surface sites for efficient hydrogen evolution. Chem. Sci. 2014, 5, 4615–4620.
DOI Google Scholar
23

Chang, Y. -H.; Nikam, R. D.; Lin, C. -T.; Huang, J. -K.; Tseng, C. -C.; Hsu, C. -L.; Cheng, C. -C.; Su, C. -Y.; Li, L. -J.; Chua, D. H. C. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction. ACS Appl. Mater. Interfaces 2014, 6, 17679–17685.
DOI Google Scholar
24

Chang, Y. -H.; Lin, C. -T.; Chen, T. -Y.; Hsu, C. -L.; Lee, Y. -H.; Zhang, W.; Wei, K. -H.; Li, L. -J. Highly efficient electrocatalytic hydrogen production by MoSx grown on grapheme-protected 3D Ni foams. Adv. Mater. 2013, 25, 756–760.
DOI Google Scholar
25

Merki, D.; Fierro, S.; Vrubel, H.; Hu, X. Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water. Chem. Sci. 2011, 2, 1262– 1267.
DOI Google Scholar
26

Zhao, X.; Ma, X.; Sun, J.; Li, D.; Yang, X. Enhanced catalytic activities of surfactant-assisted exfoliated WS2 nanodots for hydrogen evolution. ACS Nano 2016, 10, 2159–2166.
DOI Google Scholar
27

Smith, A. J.; Chang, Y. H.; Raidongia, K.; Chen, T. Y.; Li, L. J.; Huang, J. Molybdenum sulfide supported on crumpled graphene balls for electrocatalytic hydrogen production. Adv. Energy Mater. 2014, 4, 1400398.
DOI Google Scholar
28

Jiang, Y.; Li, X.; Yu, S.; Jia, L.; Zhao, X.; Wang, C. Reduced graphene oxide-modified carbon nanotube/polyimide film supported MoS2 nanoparticles for electrocatalytic hydrogen evolution. Adv. Funct. Mater. 2015, 25, 2693–2700.
DOI Google Scholar
29

Xing, Z.; Liu, Q.; Asiri, A. M.; Sun, X. Closely interconnected network of molybdenum phosphide nanoparticles: A highly efficient electrocatalyst for generating hydrogen from water. Adv. Mater. 2014, 26, 5702–5707.
DOI Google Scholar
30

Li, X.; Zhang, L.; Huang, M.; Wang, S.; Li, X.; Zhu, H. Cobalt and nickel selenide nanowalls anchored on graphene as bifunctional electrocatalysts for overall water splitting. J. Mater. Chem. A 2016, 4, 14789–14795.
DOI Google Scholar
31

Li, Y.; Zhang, L.; Xiang, X.; Yan, D.; Li, F. Engineering of ZnCo-layered double hydroxide nanowalls toward high- efficiency electrochemical water oxidation. J. Mater. Chem. A 2014, 2, 13250–13258.
DOI Google Scholar
32

Coleman, J. N.; Lotya, M.; O'Neill, A.; Bergin, S. D.; King, P. J.; Khan, U.; Young, K.; Gaucher, A.; De, S.; Smith, R. J. et al. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science 2011, 331, 568–571.
DOI Google Scholar
33

Xie, J.; Sun, X.; Zhang, N.; Xu, K.; Zhou, M.; Xie, Y. Layer- by-layer β-Ni(OH)2/graphene nanohybrids for ultraflexible all-solid-state thin-film supercapacitors with high electrochemical performance. Nano Energy 2013, 2, 65–74.
DOI Google Scholar
34

Xu, M.; Liang, T.; Shi, M.; Chen, H. Graphene-like two- dimensional materials. Chem. Rev. 2013, 113, 3766–3798.
DOI Google Scholar
35

Zhang, X.; Xie, Y. Recent advances in free-standing two- dimensional crystals with atomic thickness: Design, assembly and transfer strategies. Chem. Soc. Rev. 2013, 42, 8187–8199.
DOI Google Scholar
36

Xie, J.; Wang, R.; Bao, J.; Zhang, X.; Zhang, H.; Li, S.; Xie, Y. Zirconium trisulfide ultrathin nanosheets as efficient catalysts for water oxidation in both alkaline and neutral solutions. Inorg. Chem. Front. 2014, 1, 751–756.
DOI Google Scholar
37

Xie, J.; Zhang, X.; Zhang, H.; Zhang, J.; Li, S.; Wang, R.; Pan, B.; Xie, Y. Intralayered Ostwald ripening to ultrathin nanomesh catalyst with robust oxygen-evolving performance. Adv. Mater. 2016, DOI: 10.1002/adma.201604765.
DOI Google Scholar
38

Benck, J. D.; Chen, Z.; Kuritzky, L. Y.; Forman, A. J.; Jaramillo, T. F. Amorphous molybdenum sulfide catalysts for electrochemical hydrogen production: Insights into the origin of their catalytic activity. ACS Catal. 2012, 2, 1916–1923.
DOI Google Scholar
39

Liao, L.; Zhu, J.; Bian, X.; Zhu, L.; Scanlon, M. D.; Girault, H. H.; Liu, B. MoS2 formed on mesoporous graphene as a highly active catalyst for hydrogen evolution. Adv. Funct. Mater. 2013, 23, 5326–5333.
DOI Google Scholar
40

Lu, Z.; Zhang, H.; Zhu, W.; Yu, X.; Kuang, Y.; Chang, Z.; Lei, X.; Sun, X. In situ fabrication of porous MoS2 thin-films as high-performance catalysts for electrochemical hydrogen evolution. Chem. Commun. 2013, 49, 7516–7518.
DOI Google Scholar
41

Merki, D.; Hu, X. Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts. Energy Environ. Sci. 2011, 4, 3878–3888.
DOI Google Scholar
42

Vrubel, H.; Merki, D.; Hu, X. Hydrogen evolution catalyzed by MoS3 and MoS2 particles. Energy Environ. Sci. 2012, 5, 6136–6144.
DOI Google Scholar
43

Lukowski, M. A.; Daniel, A. S.; Meng, F.; Forticaux, A.; Li, L.; Jin, S. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J. Am. Chem. Soc. 2013, 135, 10274–10277.
DOI Google Scholar
44

Chen, Z.; Cummins, D.; Reinecke, B. N.; Clark, E.; Sunkara, M. K.; Jaramillo, T. F. Core–shell MoO3–MoS2 nanowires for hydrogen evolution: A functional design for electrocatalytic materials. Nano Lett. 2011, 11, 4168–4175.
DOI Google Scholar
45

Voiry, D.; Salehi, M.; Silva, R.; Fujita, T.; Chen, M.; Asefa, T.; Shenoy, V. B.; Eda, G.; Chhowalla, M. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 2013, 13, 6222–6227.
DOI Google Scholar
46

Chen, W. -F.; Sasaki, K.; Ma, C.; Frenkel, A. I.; Marinkovic, N.; Muckerman, J. T.; Zhu, Y.; Adzic, R. R. Hydrogen- evolution catalysts based on non-noble metal nickel– molybdenum nitride nanosheets. Angew., Chem., Int. Ed. 2012, 51, 6131–6135.
DOI Google Scholar
File
nr-10-4-1178_ESM.pdf (1.1 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 20 November 2016
Revised: 10 December 2016
Accepted: 15 December 2016
Published: 07 March 2017
Issue date: April 2017

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2017

Acknowledgements

Acknowledgements

This work was financially supported by the National Basic Research Program of China (No. 2015CB932302), the National Natural Science Foundation of China (Nos. 21501112, 21331005, 21401181, U1532265, U1632149, 91422303, and 11321503), and Natural Science Foundation of Shandong Province (No. ZR2014BQ007).

Return