skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Magnetic and electrocatalytic properties of transition metal doped MoS2 nanocrystals

Abstract

In this paper, the magnetic and electrocatalytic properties of hydrothermally grown transition metal doped (10% of Co, Ni, Fe, and Mn) 2H-MoS2 nanocrystals (NCs) with a particle size 25–30 nm are reported. The pristine 2H-MoS2 NCs showed a mixture of canted anti-ferromagnetic and ferromagnetic behavior. While Co, Ni, and Fe doped MoS2 NCs revealed room temperature ferromagnetism, Mn doped MoS2 NCs showed room temperature paramagnetism, predominantly. The ground state of all the materials is found to be canted-antiferromagnetic phase. To study electrocatalytic performance for hydrogen evolution reaction, polarization curves were measured for undoped and the doped MoS2 NCs. At the overpotential of η = –300 mV, the current densities, listed from greatest to least, are FeMoS2, CoMoS2, MoS2, NiMoS2, and MnMoS2, and the order of catalytic activity found from Tafel slopes is CoMoS2 > MoS2 > NiMoS2 > FeMoS2 > MnMoS2. The increasing number of catalytically active sites in Co doped MoS2 NCs might be responsible for their superior electrocatalytic activity. In conclusion, the present results show that the magnetic order-disorder behavior and catalytic activity can be modulated by choosing the suitable dopants in NCs of 2D materials.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [3];  [2];  [1]
  1. The Univ. of Texas at El Paso, El Paso, TX (United States)
  2. Ames Lab., Ames, IA (United States)
  3. Boise State Univ., Boise, ID (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1481874
Report Number(s):
IS-J-9761
Journal ID: ISSN 0021-8979
Grant/Contract Number:  
AC02-07CH11358; DMR-1205302
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 124; Journal Issue: 15; Journal ID: ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Martinez, L. M., Delgado, J. A., Saiz, C. L., Cosio, A., Wu, Y., Villagrán, D., Gandha, K., Karthik, C., Nlebedim, I. C., and Singamaneni, S. R. Magnetic and electrocatalytic properties of transition metal doped MoS2 nanocrystals. United States: N. p., 2018. Web. doi:10.1063/1.5043208.
Martinez, L. M., Delgado, J. A., Saiz, C. L., Cosio, A., Wu, Y., Villagrán, D., Gandha, K., Karthik, C., Nlebedim, I. C., & Singamaneni, S. R. Magnetic and electrocatalytic properties of transition metal doped MoS2 nanocrystals. United States. doi:10.1063/1.5043208.
Martinez, L. M., Delgado, J. A., Saiz, C. L., Cosio, A., Wu, Y., Villagrán, D., Gandha, K., Karthik, C., Nlebedim, I. C., and Singamaneni, S. R. Wed . "Magnetic and electrocatalytic properties of transition metal doped MoS2 nanocrystals". United States. doi:10.1063/1.5043208. https://www.osti.gov/servlets/purl/1481874.
@article{osti_1481874,
title = {Magnetic and electrocatalytic properties of transition metal doped MoS2 nanocrystals},
author = {Martinez, L. M. and Delgado, J. A. and Saiz, C. L. and Cosio, A. and Wu, Y. and Villagrán, D. and Gandha, K. and Karthik, C. and Nlebedim, I. C. and Singamaneni, S. R.},
abstractNote = {In this paper, the magnetic and electrocatalytic properties of hydrothermally grown transition metal doped (10% of Co, Ni, Fe, and Mn) 2H-MoS2 nanocrystals (NCs) with a particle size 25–30 nm are reported. The pristine 2H-MoS2 NCs showed a mixture of canted anti-ferromagnetic and ferromagnetic behavior. While Co, Ni, and Fe doped MoS2 NCs revealed room temperature ferromagnetism, Mn doped MoS2 NCs showed room temperature paramagnetism, predominantly. The ground state of all the materials is found to be canted-antiferromagnetic phase. To study electrocatalytic performance for hydrogen evolution reaction, polarization curves were measured for undoped and the doped MoS2 NCs. At the overpotential of η = –300 mV, the current densities, listed from greatest to least, are FeMoS2, CoMoS2, MoS2, NiMoS2, and MnMoS2, and the order of catalytic activity found from Tafel slopes is CoMoS2 > MoS2 > NiMoS2 > FeMoS2 > MnMoS2. The increasing number of catalytically active sites in Co doped MoS2 NCs might be responsible for their superior electrocatalytic activity. In conclusion, the present results show that the magnetic order-disorder behavior and catalytic activity can be modulated by choosing the suitable dopants in NCs of 2D materials.},
doi = {10.1063/1.5043208},
journal = {Journal of Applied Physics},
number = 15,
volume = 124,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: The temperature dependent magnetic susceptibility and magnetic field-dependent magnetic behavior of MoS2 NCs. Inset of Fig. 1(a) also included the applicability of modified Curie-Weiss model.

Save / Share:

Works referenced in this record:

Unsupported transition metal sulfide catalysts: 100 years of science and application
journal, October 2009


Ferromagnetism in MnX2 (X = S, Se) monolayers
journal, January 2014

  • Kan, Min; Adhikari, Subash; Sun, Qiang
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 10
  • DOI: 10.1039/c3cp55146f

Electronic structures of defects and magnetic impurities in MoS2 monolayers
journal, December 2014


Structure and Function of the Catalyst and the Promoter in Co—Mo Hydrodesulfurization Catalysts
journal, February 1989


Charge and magnetic states of Mn-, Fe-, and Co-doped monolayer MoS 2
journal, July 2014

  • Lin, Xianqing; Ni, Jun
  • Journal of Applied Physics, Vol. 116, Issue 4
  • DOI: 10.1063/1.4891495

Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene
journal, March 2013

  • Butler, Sheneve Z.; Hollen, Shawna M.; Cao, Linyou
  • ACS Nano, Vol. 7, Issue 4, p. 2898-2926
  • DOI: 10.1021/nn400280c

Effect of promoters on the HDS activity of alumina-supported Co–Mo sulfide catalysts
journal, January 2015

  • Wang, Xilong; Fang, He; Zhao, Zhen
  • RSC Advances, Vol. 5, Issue 121
  • DOI: 10.1039/C5RA17414G

Magnetic properties of nonmetal atoms absorbed MoS2 monolayers
journal, February 2010

  • He, Jiangang; Wu, Kechen; Sa, Rongjian
  • Applied Physics Letters, Vol. 96, Issue 8
  • DOI: 10.1063/1.3318254

Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution
journal, January 2015


Prediction of two-dimensional diluted magnetic semiconductors: Doped monolayer MoS 2 systems
journal, March 2013


Magnetic edge states in MoS 2 characterized using density-functional theory
journal, September 2009


Experimental Relationships between Catalysis and Magnetism
conference, January 1974

  • Voorhoeve, R. J. H.
  • MAGNETISM AND MAGNETIC MATERIALS — 1973: Nineteenth Annual Conference
  • DOI: 10.1063/1.2947317

Biomedical Uses for 2D Materials Beyond Graphene: Current Advances and Challenges Ahead
journal, April 2016

  • Kurapati, Rajendra; Kostarelos, Kostas; Prato, Maurizio
  • Advanced Materials, Vol. 28, Issue 29
  • DOI: 10.1002/adma.201506306

Room-temperature ferromagnetism in Co doped MoS 2 sheets
journal, January 2015

  • Xiang, ZhongCheng; Zhang, Zhong; Xu, XiJin
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 24
  • DOI: 10.1039/C5CP01509J

Synthesis, Properties, and Applications of Transition Metal-Doped Layered Transition Metal Dichalcogenides
journal, March 2016


Robust ferromagnetism in Mn-doped MoS 2 nanostructures
journal, August 2016

  • Wang, Jieqiong; Sun, Fan; Yang, Sen
  • Applied Physics Letters, Vol. 109, Issue 9
  • DOI: 10.1063/1.4961883

Complete 'Melting' of Charge Order in Hydrothermally Grown Pr 0.57 Ca 0.41 Ba 0.02 MnO 3 Nanowires
journal, June 2007

  • Anuradha, K. N.; Rao, S. S.; Bhat, S. V.
  • Journal of Nanoscience and Nanotechnology, Vol. 7, Issue 6
  • DOI: 10.1166/jnn.2007.713

Fe, Co, and Ni ions promote the catalytic activity of amorphous molybdenum sulfide films for hydrogen evolution
journal, January 2012

  • Merki, Daniel; Vrubel, Heron; Rovelli, Lorenzo
  • Chemical Science, Vol. 3, Issue 8
  • DOI: 10.1039/c2sc20539d

Magnetism and catalysis
journal, March 1978

  • Richardson, James T.
  • Journal of Applied Physics, Vol. 49, Issue 3
  • DOI: 10.1063/1.324865

Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates
journal, February 2018


MoS 2 Nanoribbons: High Stability and Unusual Electronic and Magnetic Properties
journal, December 2008

  • Li, Yafei; Zhou, Zhen; Zhang, Shengbai
  • Journal of the American Chemical Society, Vol. 130, Issue 49
  • DOI: 10.1021/ja805545x

Magnetism and Catalysis.
journal, February 1946


Modulation of Gas Adsorption and Magnetic Properties of Monolayer-MoS 2 by Antisite Defect and Strain
journal, June 2016

  • Sahoo, Mpk; Wang, Jie; Zhang, Yajun
  • The Journal of Physical Chemistry C, Vol. 120, Issue 26
  • DOI: 10.1021/acs.jpcc.6b03284

Room temperature ferromagnetic and ambipolar behaviors of MoS 2 doped by manganese oxide using an electrochemical method
journal, May 2017

  • Park, Chang-Soo; Chu, Dongil; Shon, Yoon
  • Applied Physics Letters, Vol. 110, Issue 22
  • DOI: 10.1063/1.4984951

MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction
journal, March 2017

  • Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung
  • Nature Chemistry, Vol. 9, Issue 8
  • DOI: 10.1038/NCHEM.2740

Defect engineering of two-dimensional transition metal dichalcogenides
journal, April 2016


Monolayer MoS 2 with S vacancies from interlayer spacing expanded counterparts for highly efficient electrochemical hydrogen production
journal, January 2016

  • Xu, Yuzi; Wang, Longlu; Liu, Xia
  • Journal of Materials Chemistry A, Vol. 4, Issue 42
  • DOI: 10.1039/C6TA06534A

Room temperature weak ferromagnetism in Sn 1−x Mn x Se 2 2D films grown by molecular beam epitaxy
journal, March 2016

  • Dong, Sining; Liu, Xinyu; Li, Xiang
  • APL Materials, Vol. 4, Issue 3
  • DOI: 10.1063/1.4942637

Adsorption of gas molecules on monolayer MoS2 and effect of applied electric field
journal, January 2013

  • Yue, Qu; Shao, Zhengzheng; Chang, Shengli
  • Nanoscale Research Letters, Vol. 8, Issue 1
  • DOI: 10.1186/1556-276X-8-425

Enhancement of the Electroreduction of Oxygen on Pt Alloys with Fe, Ni, and Co
journal, January 1999

  • Toda, Takako; Igarashi, Hiroshi; Uchida, Hiroyuki
  • Journal of The Electrochemical Society, Vol. 146, Issue 10, p. 3750-3756
  • DOI: 10.1149/1.1392544

Strong spin-orbit splitting and magnetism of point defect states in monolayer WS 2
journal, November 2016


Manganese Doping of Monolayer MoS 2 : The Substrate Is Critical
journal, September 2015


Adjustable ferromagnetic behavior in iron-doped two-dimensional MoS 2 multilayer nanosheets
journal, August 2017


Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals
journal, April 2017


Vacancy-Induced Ferromagnetism of MoS 2 Nanosheets
journal, February 2015

  • Cai, Liang; He, Jingfu; Liu, Qinghua
  • Journal of the American Chemical Society, Vol. 137, Issue 7
  • DOI: 10.1021/ja5120908

Long-range ferromagnetic ordering in manganese-doped two-dimensional dichalcogenides
journal, October 2013


Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS 2 surface via single-atom metal doping
journal, January 2015

  • Deng, Jiao; Li, Haobo; Xiao, Jianping
  • Energy & Environmental Science, Vol. 8, Issue 5
  • DOI: 10.1039/C5EE00751H

Tunable magnetic properties of transition metal doped MoS 2
journal, September 2014


One-step hydrothermal synthesis of monolayer MoS 2 quantum dots for highly efficient electrocatalytic hydrogen evolution
journal, January 2015

  • Ren, Xianpei; Pang, Liuqing; Zhang, Yunxia
  • Journal of Materials Chemistry A, Vol. 3, Issue 20
  • DOI: 10.1039/C5TA02198G

Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets
journal, June 2016

  • Yin, Ying; Han, Jiecai; Zhang, Yumin
  • Journal of the American Chemical Society, Vol. 138, Issue 25
  • DOI: 10.1021/jacs.6b03714

Magnetic Molybdenum Disulfide Nanosheet Films
journal, August 2007

  • Zhang, Jia; Soon, Jia Mei; Loh, Kian Ping
  • Nano Letters, Vol. 7, Issue 8
  • DOI: 10.1021/nl071016r

Ni-doped MoS 2 nanoparticles as highly active hydrogen evolution electrocatalysts
journal, January 2016

  • Wang, Dezhi; Zhang, Xiangyong; Shen, Yilin
  • RSC Advances, Vol. 6, Issue 20
  • DOI: 10.1039/C6RA02610A

Electronics and optoelectronics of two-dimensional transition metal dichalcogenides
journal, November 2012

  • Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras
  • Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712
  • DOI: 10.1038/nnano.2012.193

Recent Advances in Two-Dimensional Materials beyond Graphene
journal, October 2015


Enhancement of magnetism by structural phase transition in MoS 2
journal, January 2015

  • Yan, Shiming; Qiao, Wen; He, Xueming
  • Applied Physics Letters, Vol. 106, Issue 1
  • DOI: 10.1063/1.4905656

Ferromagnetism in Graphene Nanoribbons: Split versus Oxidative Unzipped Ribbons
journal, February 2012

  • Rao, S. S.; Jammalamadaka, S. Narayana; Stesmans, A.
  • Nano Letters, Vol. 12, Issue 3
  • DOI: 10.1021/nl203512c

Co-Doped MoS 2 Nanosheets with the Dominant CoMoS Phase Coated on Carbon as an Excellent Electrocatalyst for Hydrogen Evolution
journal, December 2015

  • Dai, Xiaoping; Du, Kangli; Li, Zhanzhao
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 49
  • DOI: 10.1021/acsami.5b08420

Substrate induced changes in atomically thin 2-dimensional semiconductors: Fundamentals, engineering, and applications
journal, March 2017

  • Sun, Yinghui; Wang, Rongming; Liu, Kai
  • Applied Physics Reviews, Vol. 4, Issue 1
  • DOI: 10.1063/1.4974072

Magnetic Defects in Transitional Metal Di-Chalcogenide Semiconducting Layers
journal, January 2018

  • Martinez, L. M.; Teran, M. D.; Chianelli, R. R.
  • MRS Advances, Vol. 3, Issue 6-7
  • DOI: 10.1557/adv.2018.110

Polycrystalline graphene and other two-dimensional materials
journal, August 2014


Layer-Dependent Electrocatalysis of MoS 2 for Hydrogen Evolution
journal, January 2014

  • Yu, Yifei; Huang, Sheng-Yang; Li, Yanpeng
  • Nano Letters, Vol. 14, Issue 2
  • DOI: 10.1021/nl403620g

Mn-doped monolayer MoS 2 : An atomically thin dilute magnetic semiconductor
journal, May 2013


Electrocatalysis and fuel Cells
journal, January 1971


Atomic-Scale Insights into Hydrodesulfurization
journal, April 2000

  • Kushmerick, J. G.; Kandel, S. A.; Han, P.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 14
  • DOI: 10.1021/jp993319i

Weakening of charge order and antiferromagnetic to ferromagnetic switch over in Pr0.5Ca0.5MnO3 nanowires
journal, October 2005

  • Rao, S. S.; Anuradha, K. N.; Sarangi, S.
  • Applied Physics Letters, Vol. 87, Issue 18
  • DOI: 10.1063/1.2125129

Intrinsic and extrinsic origin of room temperature ferromagnetism in ZnO:Co (5at.%)
journal, May 2007

  • Bhatti, Kanwal Preet; Chaudhary, Sujeet; Pandya, Dinesh K.
  • Journal of Applied Physics, Vol. 101, Issue 10
  • DOI: 10.1063/1.2740343

Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit
journal, June 2017

  • Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén
  • Nature, Vol. 546, Issue 7657
  • DOI: 10.1038/nature22391

Modulating Carrier Density and Transport Properties of MoS 2 by Organic Molecular Doping and Defect Engineering
journal, November 2016


Edge-states ferromagnetism of WS 2 nanosheets
journal, May 2014

  • Huo, Nengjie; Li, Yan; Kang, Jun
  • Applied Physics Letters, Vol. 104, Issue 20
  • DOI: 10.1063/1.4875582

Paramagnetic defects in hydrothermally grown few-layered MoS 2 nanocrystals
journal, June 2018

  • Martinez, Luis M.; Karthik, Chinnathambi; Kongara, Madhu
  • Journal of Materials Research, Vol. 33, Issue 11
  • DOI: 10.1557/jmr.2018.149

Enhanced electrocatalysis of oxygen reduction on platinum alloys in proton exchange membrane fuel cells
journal, October 1993

  • Mukerjee, Sanjeev; Srinivasan, Supramaniam
  • Journal of Electroanalytical Chemistry, Vol. 357, Issue 1-2, p. 201-224
  • DOI: 10.1016/0022-0728(93)80380-Z

Atomic Defects in Two Dimensional Materials
journal, May 2015

  • Rasool, Haider I.; Ophus, Colin; Zettl, Alex
  • Advanced Materials, Vol. 27, Issue 38
  • DOI: 10.1002/adma.201500231

Dislocation motion and grain boundary migration in two-dimensional tungsten disulphide
journal, September 2014

  • Azizi, Amin; Zou, Xiaolong; Ercius, Peter
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5867

Gate-controlled reversible rectifying behaviour in tunnel contacted atomically-thin MoS2 transistor
journal, October 2017


Inducing High Coercivity in MoS 2 Nanosheets by Transition Element Doping
journal, October 2017


Ferromagnetism in freestanding MoS2 nanosheets
journal, January 2013


High Energy Product Developed from Cobalt Nanowires
journal, June 2014

  • Gandha, Kinjal; Elkins, Kevin; Poudyal, Narayan
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep05345

Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts
journal, July 2007

  • Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J.
  • Science, Vol. 317, Issue 5834, p. 100-102
  • DOI: 10.1126/science.1141483

Intrinsic Magnetism of Grain Boundaries in Two-Dimensional Metal Dichalcogenides
journal, November 2013

  • Zhang, Zhuhua; Zou, Xiaolong; Crespi, Vincent H.
  • ACS Nano, Vol. 7, Issue 12
  • DOI: 10.1021/nn4052887

Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017


Efficient Electrocatalytic Hydrogen Evolution from MoS 2 -Functionalized Mo 2 N Nanostructures
journal, August 2016

  • Ojha, Kasinath; Saha, Soumen; Banerjee, Shivali
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 23
  • DOI: 10.1021/acsami.6b10717

High temperature ferromagnetism in Cu-doped MoS 2 nanosheets
journal, March 2016


Role of Magnetism in Catalysis: RuO 2 (110) Surface
journal, March 2013

  • Torun, E.; Fang, C. M.; de Wijs, G. A.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 12
  • DOI: 10.1021/jp4020367