Comparison of liquid exfoliated transition metal dichalcogenides reveals MoSe2 to be the most effective hydrogen evolution catalyst.

While 2D transition metal dichalcogenides are known to be promising materials for electrocatalysis of hydrogen production, it is not clear which member of this family of materials is the most effective catalyst. Here we perform a comprehensive study, comparing the catalytic performance of electrodes consisting of porous arrays of liquid exfoliated MX2 nanosheets (M = Mo, W; X = S, Se, Te). We find a clear hierarchy with selenides > sulphides > tellurides with MoSe2 clearly out-performing the other materials. In all cases the performance, as characterised by current density at a given potential, can be improved by increasing the number of active sites (via control of the electrode thickness) and/or by adding carbon nanotubes to the electrode (i.e. increasing the electrode conductivity). While all materials formed reasonably stable electrodes, addition of nanotubes tended to improve mechanical cohesion. In an attempt to maximise performance, we prepared thick (∼15 μm), free standing MoSe2/SWNT composite electrodes which displayed Tafel slopes of ∼77 mV per decade and exchange current densities of ∼0.1 mA cm(-2). These electrodes had low onset potentials, reaching -2 mA cm(-2) at -41 mV (vs. RHE) and generated high current densities of -35 mA cm(-2) at -200 mV (vs. RHE).

[1]  James R. McKone,et al.  Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction. , 2013, Journal of the American Chemical Society.

[2]  Fei Meng,et al.  Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. , 2013, Journal of the American Chemical Society.

[3]  Hao‐Li Zhang,et al.  A mixed-solvent strategy for efficient exfoliation of inorganic graphene analogues. , 2011, Angewandte Chemie.

[4]  Yan Li,et al.  Size-Dependent Enhancement of Electrocatalytic Oxygen-Reduction and Hydrogen-Evolution Performance of MoS2 Particles. , 2013, Chemistry.

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

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

[7]  Xile Hu,et al.  Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts , 2011 .

[8]  H. Vrubel,et al.  Hydrogen evolution catalyzed by MoS3 and MoS2 particles , 2012 .

[9]  Xitian Zhang,et al.  Ultrathin MoSe2 Nanosheets Decorated on Carbon Fiber Cloth as Binder-Free and High-Performance Electrocatalyst for Hydrogen Evolution. , 2015, ACS applied materials & interfaces.

[10]  Hisato Yamaguchi,et al.  Enhanced catalytic activity in strained chemically exfoliated WS₂ nanosheets for hydrogen evolution. , 2012, Nature Materials.

[11]  J. S. Lee,et al.  Highly active and stable hydrogen evolution electrocatalysts based on molybdenum compounds on carbon nanotube-graphene hybrid support. , 2014, ACS nano.

[12]  Lain-Jong Li,et al.  Highly Efficient Electrocatalytic Hydrogen Production by MoSx Grown on Graphene‐Protected 3D Ni Foams , 2013, Advanced materials.

[13]  Jonathan N. Coleman,et al.  Approaching the theoretical limit for reinforcing polymers with graphene , 2012 .

[14]  D. Smirnov,et al.  New First Order Raman-active Modes in Few Layered Transition Metal Dichalcogenides , 2014, Scientific Reports.

[15]  Ib Chorkendorff,et al.  Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation. , 2015, The journal of physical chemistry letters.

[16]  J. Coleman,et al.  High-yield production of graphene by liquid-phase exfoliation of graphite. , 2008, Nature nanotechnology.

[17]  Benjamin J. Carey,et al.  Investigation of Two-Solvent Grinding-Assisted Liquid Phase Exfoliation of Layered MoS2 , 2015 .

[18]  J. Coleman,et al.  Percolation scaling in composites of exfoliated MoS2 filled with nanotubes and graphene. , 2012, Nanoscale.

[19]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[20]  H. Fei,et al.  Edge‐Oriented MoS2 Nanoporous Films as Flexible Electrodes for Hydrogen Evolution Reactions and Supercapacitor Devices , 2014, Advanced materials.

[21]  Mohammad Asadi,et al.  High‐Quality Black Phosphorus Atomic Layers by Liquid‐Phase Exfoliation , 2015, Advanced materials.

[22]  Guosong Hong,et al.  MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. , 2011, Journal of the American Chemical Society.

[23]  J. Coleman,et al.  Liquid Exfoliation of Layered Materials , 2013, Science.

[24]  Ying Yang,et al.  Enhanced hydrogen evolution reaction on few–layer MoS2 nanosheets–coated functionalized carbon nanotubes , 2015 .

[25]  C. Zhi,et al.  Large‐Scale Fabrication of Boron Nitride Nanosheets and Their Utilization in Polymeric Composites with Improved Thermal and Mechanical Properties , 2009 .

[26]  M. Grätzel,et al.  Revealing and accelerating slow electron transport in amorphous molybdenum sulphide particles for hydrogen evolution reaction. , 2013, Chemical communications.

[27]  B. V. Tilak,et al.  Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H , 2002 .

[28]  Dongke Zhang,et al.  Recent progress in alkaline water electrolysis for hydrogen production and applications , 2010 .

[29]  J. Coleman,et al.  High-concentration solvent exfoliation of graphene. , 2010, Small.

[30]  Electrocatalytic Hydrogen Evolution Reaction on Edges of a Few Layer Molybdenum Disulfide Nanodots. , 2015, ACS applied materials & interfaces.

[31]  I. Chorkendorff,et al.  A high-porosity carbon molybdenum sulphide composite with enhanced electrochemical hydrogen evolution and stability. , 2013, Chemical communications.

[32]  Kevin Barraclough,et al.  I and i , 2001, BMJ : British Medical Journal.

[33]  J. Coleman,et al.  Photoconductivity of solution-processed MoS2 films , 2013 .

[34]  Yi Cui,et al.  Electrochemical tuning of MoS2 nanoparticles on three-dimensional substrate for efficient hydrogen evolution. , 2014, ACS nano.

[35]  Jingbo Hu,et al.  Enhanced electrocatalytic activity for hydrogen evolution reaction from self-assembled monodispersed molybdenum sulfide nanoparticles on an Au electrode , 2013 .

[36]  Yongfeng Hu,et al.  Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis , 2014, Nature Communications.

[37]  Thomas F. Jaramillo,et al.  Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials , 2014 .

[38]  Niall McEvoy,et al.  Edge and confinement effects allow in situ measurement of size and thickness of liquid-exfoliated nanosheets , 2014, Nature Communications.

[39]  S. Gul,et al.  Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst , 2014, Journal of the American Chemical Society.

[40]  Chunming Wang,et al.  A Novel MoSe2–Reduced Graphene Oxide/Polyimide Composite Film for Applications in Electrocatalysis and Photoelectrocatalysis Hydrogen Evolution , 2015 .

[41]  Shun Mao,et al.  Perpendicularly oriented MoSe2 /graphene nanosheets as advanced electrocatalysts for hydrogen evolution. , 2015, Small.

[42]  B. Guo,et al.  Design of two-dimensional, ultrathin MoS₂ nanoplates fabricated within one-dimensional carbon nanofibers with thermosensitive morphology: high-performance electrocatalysts for the hydrogen evolution reaction. , 2014, ACS applied materials & interfaces.

[43]  Qing Hua Wang,et al.  Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. , 2012, Nature nanotechnology.

[44]  J. Coleman,et al.  Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials , 2011, Science.

[45]  X. Lou,et al.  Defect‐Rich MoS2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution , 2013, Advanced materials.

[46]  A. Lasia,et al.  Study of the hydrogen evolution reaction on nickel-based composite coatings containing molybdenum powder , 2007 .

[47]  J. Coleman,et al.  Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions , 2008, 0809.2690.

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

[49]  Philip N. Ross,et al.  TEMPERATURE-DEPENDENT HYDROGEN ELECTROCHEMISTRY ON PLATINUM LOW-INDEX SINGLE-CRYSTAL SURFACES IN ACID SOLUTIONS , 1997 .

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

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

[52]  Yanguang Li,et al.  Ultrathin WS2Nanoflakes as a High-Performance Electrocatalyst for the Hydrogen Evolution Reaction , 2014 .

[53]  J. Wilson,et al.  The transition metal dichalcogenides discussion and interpretation of the observed optical, electrical and structural properties , 1969 .

[54]  Xin Wang,et al.  Recent Development of Molybdenum Sulfides as Advanced Electrocatalysts for Hydrogen Evolution Reaction , 2014 .

[55]  J. Nørskov,et al.  Hydrogen evolution on nano-particulate transition metal sulfides. , 2008, Faraday discussions.

[56]  Jonathan N. Coleman,et al.  Preparation of Gallium Sulfide Nanosheets by Liquid Exfoliation and Their Application As Hydrogen Evolution Catalysts , 2015 .

[57]  H. Tributsch,et al.  Electrochemistry and photochemistry of MoS2 layer crystals. I , 1977 .

[58]  Jin Yu,et al.  Enhanced Electrocatalytic Properties of Transition-Metal Dichalcogenides Sheets by Spontaneous Gold Nanoparticle Decoration. , 2013, The journal of physical chemistry letters.

[59]  Thomas M. Higgins,et al.  Avoiding Resistance Limitations in High-Performance Transparent Supercapacitor Electrodes Based on Large-Area, High-Conductivity PEDOT:PSS Films. , 2015, ACS applied materials & interfaces.

[60]  B. Pan,et al.  Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. , 2013, Journal of the American Chemical Society.

[61]  Niall McEvoy,et al.  Large variations in both dark- and photoconductivity in nanosheet networks as nanomaterial is varied from MoS2 to WTe2. , 2015, Nanoscale.

[62]  Seungho Yu,et al.  Edge-exposed MoS2 nano-assembled structures as efficient electrocatalysts for hydrogen evolution reaction. , 2014, Nanoscale.

[63]  Desheng Kong,et al.  Synthesis of MoS2 and MoSe2 films with vertically aligned layers. , 2013, Nano letters.

[64]  J. Coleman,et al.  Thickness Dependence and Percolation Scaling of Hydrogen Production Rate in MoS2 Nanosheet and Nanosheet-Carbon Nanotube Composite Catalytic Electrodes. , 2016, ACS nano.

[65]  M. Pumera,et al.  2H → 1T phase transition and hydrogen evolution activity of MoS2, MoSe2, WS2 and WSe2 strongly depends on the MX2 composition. , 2015, Chemical communications.

[66]  A. Bourlinos,et al.  Liquid-phase exfoliation of graphite towards solubilized graphenes. , 2009, Small.

[67]  Mustafa Lotya,et al.  Solvent Exfoliation of Transition Metal Dichalcogenides: Dispersability of Exfoliated Nanosheets Varies Only Weakly between Compounds /v Sol (mol/ml) Characterisation of Dispersions , 2022 .

[68]  Thomas F. Jaramillo,et al.  Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts , 2007, Science.

[69]  Hua Zhang,et al.  The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. , 2013, Nature chemistry.

[70]  Shihe Yang,et al.  Space-Confined Growth of MoS2 Nanosheets within Graphite: The Layered Hybrid of MoS2 and Graphene as an Active Catalyst for Hydrogen Evolution Reaction , 2014 .

[71]  Thomas M. Higgins,et al.  Production of Molybdenum Trioxide Nanosheets by Liquid Exfoliation and Their Application in High-Performance Supercapacitors , 2014 .

[72]  Jonathan N. Coleman,et al.  Development of stiff, strong, yet tough composites by the addition of solvent exfoliated graphene to polyurethane , 2010 .

[73]  H. Shin,et al.  Recent advances in layered transition metal dichalcogenides for hydrogen evolution reaction , 2014 .

[74]  Jun Jin,et al.  Synthesis of Cu-MoS2/rGO hybrid as non-noble metal electrocatalysts for the hydrogen evolution reaction , 2015 .

[75]  Sasha Omanovic,et al.  Characterization of Ni, NiMo, NiW and NiFe electroactive coatings as electrocatalysts for hydrogen evolution in an acidic medium , 2005 .

[76]  Thomas M. Higgins,et al.  Effect of percolation on the capacitance of supercapacitor electrodes prepared from composites of manganese dioxide nanoplatelets and carbon nanotubes. , 2014, ACS nano.

[77]  Andrea Kellenberger,et al.  Kinetics of hydrogen evolution reaction on skeleton nickel and nickel–titanium electrodes obtained by thermal arc spraying technique , 2007 .

[78]  Christoph Gadermaier,et al.  Production of Highly Monolayer Enriched Dispersions of Liquid-Exfoliated Nanosheets by Liquid Cascade Centrifugation. , 2016, ACS nano.

[79]  Z. Yin,et al.  MoS2 nanoflower-decorated reduced graphene oxide paper for high-performance hydrogen evolution reaction. , 2014, Nanoscale.

[80]  Haotian Wang,et al.  Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction , 2013, Proceedings of the National Academy of Sciences.

[81]  Micheál D. Scanlon,et al.  MoS2 Formed on Mesoporous Graphene as a Highly Active Catalyst for Hydrogen Evolution , 2013 .