Magnetron Sputter-Coated Nanoparticle MoS2 Supported on Nanocarbon: A Highly Efficient Electrocatalyst toward the Hydrogen Evolution Reaction

The design and fabrication of inexpensive highly efficient electrocatalysts for the production of hydrogen via the hydrogen evolution reaction (HER) underpin a plethora of emerging clean energy technologies. Herein, we report the fabrication of highly efficient electrocatalysts for the HER based on magnetron-sputtered MoS2 onto a nanocarbon support, termed MoS2/C. Magnetron sputtering time is explored as a function of its physiochemical composition and HER performance; increased sputtering times give rise to materials with differing compositions, i.e., Mo4+ to Mo6+ and associated S anions (sulfide, elemental, and sulfate), and improved HER outputs. An optimized sputtering time of 45 min was used to fabricate the MoS2/C material. This gave rise to an optimal HER performance with regard to its HER onset potential, achievable current, and Tafel value, which were −0.44 (vs saturated calomel electrode (SCE)), −1.45 mV s–1, and 43 mV dec–1, respectively, which has the highest composition of Mo4+ and sulfide (MoS2). Electrochemical testing toward the HER via drop casting MoS2/C upon screen-printed electrodes (SPEs) to electrically wire the nanomaterial is found to be mass coverage dependent, where the current density increases up to a critical mass (ca. 50 μg cm–2), after which a plateau is observed. To allow for a translation of the bespoke fabricated MoS2/C from laboratory to new industrial applications, MoS2/C was incorporated into the bulk ink utilized in the fabrication of SPEs (denoted as MoS2/C-SPE), thus allowing for improved electrical wiring to the MoS2/C and resulting in the production of scalable and reproducible electrocatalytic platforms. The MoS2/C-SPEs displayed far greater HER catalysis with a 450 mV reduction in the HER onset potential and a 1.70 mA cm–2 increase in the achievable current density (recorded at −0.75 V (vs SCE)), compared to a bare/unmodified graphitic SPE. The approach of using magnetron sputtering to modify carbon with MoS2 facilitates the production of mass-producible, stable, and effective electrode materials for possible use in electrolyzers, which are cost competitive to Pt and mitigate the need to use time-consuming and low-yield exfoliation techniques typically used to fabricate pristine MoS2.

[1]  Craig E Banks,et al.  Mass-Producible 2D-MoS2-Impregnated Screen-Printed Electrodes That Demonstrate Efficient Electrocatalysis toward the Oxygen Reduction Reaction. , 2017, ACS applied materials & interfaces.

[2]  Rou Jun Toh,et al.  Ultrapure Molybdenum Disulfide Shows Enhanced Catalysis for Hydrogen Evolution over Impurities‐Doped Counterpart , 2017 .

[3]  Christopher W. Foster,et al.  Mass-producible 2D-MoSe2 bulk modified screen-printed electrodes provide significant electrocatalytic performances towards the hydrogen evolution reaction , 2017 .

[4]  P. Kelly,et al.  Reactive magnetron sputtering deposition of bismuth tungstate onto titania nanoparticles for enhancing visible light photocatalytic activity , 2017 .

[5]  Weitao Yang,et al.  All The Catalytic Active Sites of MoS2 for Hydrogen Evolution. , 2016, Journal of the American Chemical Society.

[6]  Carmen C. Mayorga-Martinez,et al.  Valence and oxide impurities in MoS2 and WS2 dramatically change their electrocatalytic activity towards proton reduction. , 2016, Nanoscale.

[7]  D. Yaron,et al.  In-Situ Platinum Deposition on Nitrogen-Doped Carbon Films as a Source of Catalytic Activity in a Hydrogen Evolution Reaction. , 2016, ACS applied materials & interfaces.

[8]  N. V. Rees,et al.  Enhancement of the Hydrogen Evolution Reaction from Ni-MoS2 Hybrid Nanoclusters , 2016, ACS catalysis.

[9]  P. Kelly,et al.  A Novel Technique for the Deposition of Bismuth Tungstate onto Titania Nanoparticulates for Enhancing the Visible Light Photocatalytic Activity , 2016 .

[10]  Angelina F. Ambrose,et al.  Hydrogen fuel and transport system: A sustainable and environmental future , 2016 .

[11]  Peiyi Wu,et al.  Ultra-thin and porous MoSe2 nanosheets: facile preparation and enhanced electrocatalytic activity towards the hydrogen evolution reaction. , 2016, Physical chemistry chemical physics : PCCP.

[12]  D. A. Brownson,et al.  2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction. , 2015, Nanoscale.

[13]  M. Pumera,et al.  Electrochemistry of Nanostructured Layered Transition-Metal Dichalcogenides. , 2015, Chemical reviews.

[14]  G. Lacconi,et al.  Kinetics of the hydrogen evolution on nickel in alkaline solution: new insight from rotating disk electrode and impedance spectroscopy analysis , 2015 .

[15]  Craig E. Banks,et al.  Exploring the electrical wiring of screen-printed configurations utilised in electroanalysis , 2015 .

[16]  Jonathan N. Coleman,et al.  Large-Scale Production of Size-Controlled MoS2 Nanosheets by Shear Exfoliation , 2015 .

[17]  M. P. Kumar,et al.  On the large capacitance of nitrogen doped graphene derived by a facile route , 2014 .

[18]  Z. Yin,et al.  Preparation and applications of mechanically exfoliated single-layer and multilayer MoS₂ and WSe₂ nanosheets. , 2014, Accounts of chemical research.

[19]  M. Naebe,et al.  Mechanical Property and Structure of Covalent Functionalised Graphene/Epoxy Nanocomposites , 2014, Scientific Reports.

[20]  G. Eda,et al.  Conducting MoS₂ nanosheets as catalysts for hydrogen evolution reaction. , 2013, Nano letters.

[21]  C. Zhang,et al.  Exfoliated MoS2 nanosheets as efficient catalysts for electrochemical hydrogen evolution , 2013 .

[22]  J. Mun,et al.  Chemical Vapor Deposition of MoS2 Films , 2013 .

[23]  Haotian Wang,et al.  MoSe2 and WSe2 nanofilms with vertically aligned molecular layers on curved and rough surfaces. , 2013, Nano letters.

[24]  A. Abbaspour,et al.  Electrocatalytic hydrogen evolution reaction on carbon paste electrode modified with Ni ferrite nanoparticles , 2013 .

[25]  Jakob Kibsgaard,et al.  Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. , 2012, Nature materials.

[26]  Thomas F. Jaramillo,et al.  Amorphous Molybdenum Sulfide Catalysts for Electrochemical Hydrogen Production: Insights into the Origin of their Catalytic Activity , 2012 .

[27]  Jing Kong,et al.  van der Waals epitaxy of MoS₂ layers using graphene as growth templates. , 2012, Nano letters.

[28]  Dominique Baillargeat,et al.  From Bulk to Monolayer MoS2: Evolution of Raman Scattering , 2012 .

[29]  Jacob Bonde,et al.  Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. , 2005, Journal of the American Chemical Society.

[30]  Thomas Diehl,et al.  Air Pollution and Climate-Forcing Impacts of a Global Hydrogen Economy , 2003, Science.

[31]  P. Kelly,et al.  Magnetron sputtering: a review of recent developments and applications , 2000 .

[32]  E. D. Crozier,et al.  A study of single-layer and restacked MoS2 by X-ray diffraction and X-ray absorption spectroscopy , 1987 .

[33]  Changming Mao,et al.  MoS2/nitrogen-doped carbon hybrid nanorods with expanded interlayer spacing as an advanced anode material for lithium ion batteries , 2018 .

[34]  M. Otyepka,et al.  Role of the Edge Properties in the Hydrogen Evolution Reaction on MoS2. , 2017, Chemistry.

[35]  J. Coleman,et al.  Production of Two-Dimensional Nanomaterials via Liquid-Based Direct Exfoliation. , 2016, Small.

[36]  W. Marsden.  I and J , 2012 .

[37]  W. Stickle,et al.  Handbook of X-Ray Photoelectron Spectroscopy , 1992 .

[38]  M. Seah,et al.  Auger and x-ray photoelectron spectroscopy , 1990 .