Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution.

Molybdenum disulfide (MoS2) has emerged as a promising electrocatalyst for catalyzing protons to hydrogen via the so-called hydrogen evolution reaction (HER). In order to enhance the HER activity, tremendous effort has been made to engineer MoS2 catalysts with either more active sites or higher conductivity. However, at present, synergistically structural and electronic modulations for HER still remain challenging. In this work, we demonstrate the successfully synergistic regulations of both structural and electronic benefits by controllable disorder engineering and simultaneous oxygen incorporation in MoS2 catalysts, leading to the dramatically enhanced HER activity. The disordered structure can offer abundant unsaturated sulfur atoms as active sites for HER, while the oxygen incorporation can effectively regulate the electronic structure and further improve the intrinsic conductivity. By means of controllable disorder engineering and oxygen incorporation, an optimized catalyst with a moderate degree of disorder was developed, exhibiting superior activity for electrocatalytic hydrogen evolution. In general, the optimized catalyst exhibits onset overpotential as low as 120 mV, accompanied by extremely large cathodic current density and excellent stability. This work will pave a new pathway for improving the electrocatalytic activity by synergistically structural and electronic modulations.

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

[2]  Yi Xie,et al.  Recent advances in free-standing two-dimensional crystals with atomic thickness: design, assembly and transfer strategies. , 2013, Chemical Society reviews.

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

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

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

[6]  Jiangtian Li,et al.  Solar hydrogen generation by nanoscale p-n junction of p-type molybdenum disulfide/n-type nitrogen-doped reduced graphene oxide. , 2013, Journal of the American Chemical Society.

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

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

[9]  Thomas E Mallouk,et al.  Water electrolysis: Divide and conquer. , 2013, Nature chemistry.

[10]  Jian‐Hao Chen,et al.  Atomic resolution imaging of grain boundary defects in monolayer chemical vapor deposition-grown hexagonal boron nitride. , 2013, Journal of the American Chemical Society.

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

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

[13]  Jinlong Yang,et al.  Hydrogen-incorporated TiS2 ultrathin nanosheets with ultrahigh conductivity for stamp-transferrable electrodes. , 2013, Journal of the American Chemical Society.

[14]  Yongsheng Zhu,et al.  Layered nanojunctions for hydrogen-evolution catalysis. , 2013, Angewandte Chemie.

[15]  Yimei Zhu,et al.  Highly active and durable nanostructured molybdenum carbide electrocatalysts for hydrogen production , 2013 .

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

[17]  Zhiyuan Zeng,et al.  Metal dichalcogenide nanosheets: preparation, properties and applications. , 2013, Chemical Society reviews.

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

[19]  Hailiang Wang,et al.  Strongly coupled inorganic/nanocarbon hybrid materials for advanced electrocatalysis. , 2013, Journal of the American Chemical Society.

[20]  Jun Lou,et al.  Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers. , 2013, Nature materials.

[21]  Hongzheng Chen,et al.  Graphene-like two-dimensional materials. , 2013, Chemical reviews.

[22]  H. Vrubel,et al.  Molybdenum boride and carbide catalyze hydrogen evolution in both acidic and basic solutions. , 2012, Angewandte Chemie.

[23]  G. Eda,et al.  Enhanced catalytic activity in strained chemically exfoliated WS₂ nanosheets for hydrogen evolution. , 2012, Nature materials.

[24]  T. Jaramillo,et al.  Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. , 2012, Nature materials.

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

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

[27]  Taotao Zhuang,et al.  Mixed-solution synthesis of sea urchin-like NiSe nanofiber assemblies as economical Pt-free catalysts for electrochemical H2 production , 2012 .

[28]  A. Frenkel,et al.  Hydrogen-evolution catalysts based on non-noble metal nickel-molybdenum nitride nanosheets. , 2012, Angewandte Chemie.

[29]  K. Müllen,et al.  3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction. , 2012, Journal of the American Chemical Society.

[30]  Jinlong Yang,et al.  Ambient rutile VO2(R) hollow hierarchitectures with rich grain boundaries from new-state nsutite-type VO2, displaying enhanced hydrogen adsorption behavior. , 2012, Physical chemistry chemical physics : PCCP.

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

[32]  J. Long,et al.  A Molecular MoS2 Edge Site Mimic for Catalytic Hydrogen Generation , 2012, Science.

[33]  Jinlong Yang,et al.  Metallic few-layered VS2 ultrathin nanosheets: high two-dimensional conductivity for in-plane supercapacitors. , 2011, Journal of the American Chemical Society.

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

[35]  T. Jaramillo,et al.  Core-shell MoO3-MoS2 nanowires for hydrogen evolution: a functional design for electrocatalytic materials. , 2011, Nano letters.

[36]  Wei Luo,et al.  Self-assembled hierarchical MoO2/graphene nanoarchitectures and their application as a high-performance anode material for lithium-ion batteries. , 2011, ACS nano.

[37]  H. Vrubel,et al.  Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water , 2011 .

[38]  Ziyu Wu,et al.  Hydrogen-incorporation stabilization of metallic VO2(R) phase to room temperature, displaying promising low-temperature thermoelectric effect. , 2011, Journal of the American Chemical Society.

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

[40]  E. Rabani,et al.  Heavily Doped Semiconductor Nanocrystal Quantum Dots , 2011, Science.

[41]  Carl W. Magnuson,et al.  Domain (grain) boundaries and evidence of "twinlike" structures in chemically vapor deposited grown graphene. , 2011, ACS nano.

[42]  W. Regan,et al.  Grain boundary mapping in polycrystalline graphene. , 2011, ACS nano.

[43]  Pinshane Y. Huang,et al.  Grains and grain boundaries in single-layer graphene atomic patchwork quilts , 2010, Nature.

[44]  M. Fontecave,et al.  Cobalt and nickel diimine-dioxime complexes as molecular electrocatalysts for hydrogen evolution with low overvoltages , 2009, Proceedings of the National Academy of Sciences.

[45]  L. Mai,et al.  From MoO3 nanobelts to MoO2 nanorods: structure transformation and electrical transport. , 2009, ACS nano.

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

[47]  B. Brunschwig,et al.  Electrocatalytic hydrogen evolution at low overpotentials by cobalt macrocyclic glyoxime and tetraimine complexes. , 2007, Journal of the American Chemical Society.

[48]  J. Nørskov,et al.  Computational high-throughput screening of electrocatalytic materials for hydrogen evolution , 2006, Nature materials.

[49]  Claus H. Christensen,et al.  Toward Efficient Hydrogen Production at Surfaces , 2006, Science.

[50]  T. Schulthess,et al.  Electronic structure and exchange coupling of Mn impurities in III–V semiconductors , 2005 .

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

[52]  John A. Turner,et al.  Sustainable Hydrogen Production , 2004, Science.

[53]  H. Abruña,et al.  Electrocatalytic activity of ordered intermetallic phases for fuel cell applications. , 2004, Journal of the American Chemical Society.

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

[55]  H. V. Swygenhoven,et al.  Grain Boundaries and Dislocations , 2002 .

[56]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[57]  K. Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[58]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[59]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[60]  J. Bockris,et al.  Hydrogen Evolution Reaction on Copper, Gold, Molybdenum, Palladium, Rhodium, and Iron Mechanism and Measurement Technique under High Purity Conditions , 1957 .

[61]  Ning Zhang,et al.  Layer-by-layer β-Ni(OH)2/graphene nanohybrids for ultraflexible all-solid-state thin-film supercapacitors with high electrochemical performance , 2013 .

[62]  M. Matheron,et al.  Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H₂ evolution under fully aqueous conditions. , 2013, Nature chemistry.