Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties
The layered structure of molybdenum disulfide (MoS2) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2: basal and edge planes. The edge plane w...
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sg-ntu-dr.10356-1073542019-12-06T22:29:13Z Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties Tan, Shu Min Ambrosi, Adriano Sofer, Zdenĕk Huber, Štěpán Sedmidubský, David Pumera, Martin School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Physical chemistry::Electrochemistry The layered structure of molybdenum disulfide (MoS2) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2: basal and edge planes. The edge plane was theoretically predicted to be more electroactive than the basal plane, but evidence from direct experimental comparison is elusive. Herein, the first study comparing the two surfaces of MoS2 by using macroscopic crystals is presented. A careful investigation of the electrochemical properties of macroscopic MoS2 pristine crystals with precise control over the exposure of one plane surface, that is, basal plane or edge plane, was performed. These crystals were characterized thoroughly by AFM, Raman spectroscopy, X-ray photoelectron spectroscopy, voltammetry, digital simulation, and DFT calculations. In the Raman spectra, the basal and edge planes show anisotropy in the preferred excitation of E2g and A1g phonon modes, respectively. The edge plane exhibits a much larger heterogeneous electron transfer rate constant k0 of 4.96×10−5 and 1.1×10−3 cm s−1 for [Fe(CN)6]3−/4− and [Ru(NH3)6]3+/2+ redox probes, respectively, compared to the basal plane, which yielded k0 tending towards zero for [Fe(CN)6]3−/4− and about 9.3×10−4 cm s−1 for [Ru(NH3)6]3+/2+. The industrially important hydrogen evolution reaction follows the trend observed for [Fe(CN)6]3−/4− in that the basal plane is basically inactive. The experimental comparison of the edge and basal planes of MoS2 crystals is supported by DFT calculations. 2015-05-18T06:37:22Z 2019-12-06T22:29:13Z 2015-05-18T06:37:22Z 2019-12-06T22:29:13Z 2015 2015 Journal Article Tan, S. M., Ambrosi, A., Sofer, Z., Huber, Š., Sedmidubský, D., & Pumera, M. (2015). Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties. Chemistry - a European journal, 21(19), 7170-7178. 0947-6539 https://hdl.handle.net/10356/107354 http://hdl.handle.net/10220/25578 http://dx.doi.org/10.1002/chem.201500435 en Chemistry - a European journal © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
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DRNTU::Science::Chemistry::Physical chemistry::Electrochemistry Tan, Shu Min Ambrosi, Adriano Sofer, Zdenĕk Huber, Štěpán Sedmidubský, David Pumera, Martin Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties |
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The layered structure of molybdenum disulfide (MoS2) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2: basal and edge planes. The edge plane was theoretically predicted to be more electroactive than the basal plane, but evidence from direct experimental comparison is elusive. Herein, the first study comparing the two surfaces of MoS2 by using macroscopic crystals is presented. A careful investigation of the electrochemical properties of macroscopic MoS2 pristine crystals with precise control over the exposure of one plane surface, that is, basal plane or edge plane, was performed. These crystals were characterized thoroughly by AFM, Raman spectroscopy, X-ray photoelectron spectroscopy, voltammetry, digital simulation, and DFT calculations. In the Raman spectra, the basal and edge planes show anisotropy in the preferred excitation of E2g and A1g phonon modes, respectively. The edge plane exhibits a much larger heterogeneous electron transfer rate constant k0 of 4.96×10−5 and 1.1×10−3 cm s−1 for [Fe(CN)6]3−/4− and [Ru(NH3)6]3+/2+ redox probes, respectively, compared to the basal plane, which yielded k0 tending towards zero for [Fe(CN)6]3−/4− and about 9.3×10−4 cm s−1 for [Ru(NH3)6]3+/2+. The industrially important hydrogen evolution reaction follows the trend observed for [Fe(CN)6]3−/4− in that the basal plane is basically inactive. The experimental comparison of the edge and basal planes of MoS2 crystals is supported by DFT calculations. |
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School of Physical and Mathematical Sciences |
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School of Physical and Mathematical Sciences Tan, Shu Min Ambrosi, Adriano Sofer, Zdenĕk Huber, Štěpán Sedmidubský, David Pumera, Martin |
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Article |
author |
Tan, Shu Min Ambrosi, Adriano Sofer, Zdenĕk Huber, Štěpán Sedmidubský, David Pumera, Martin |
author_sort |
Tan, Shu Min |
title |
Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties |
title_short |
Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties |
title_full |
Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties |
title_fullStr |
Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties |
title_full_unstemmed |
Pristine basal- and edge-plane-oriented molybdenite MoS2 exhibiting highly anisotropic properties |
title_sort |
pristine basal- and edge-plane-oriented molybdenite mos2 exhibiting highly anisotropic properties |
publishDate |
2015 |
url |
https://hdl.handle.net/10356/107354 http://hdl.handle.net/10220/25578 http://dx.doi.org/10.1002/chem.201500435 |
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1681040959715934208 |