Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction.

Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non-noble-metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed-metal alloy catalysts are well-known, MoP|S represents a more uncommon mixed-anion catalyst where synergistic effects between sulfur and phosphorus produce a high-surface-area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water-splitting cells.

[1]  Nathan S Lewis,et al.  Highly active electrocatalysis of the hydrogen evolution reaction by cobalt phosphide nanoparticles. , 2014, Angewandte Chemie.

[2]  T. Jaramillo,et al.  Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2- clusters. , 2014, Nature chemistry.

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

[4]  R. Prins,et al.  Different role of H2S and dibenzothiophene in the incorporation of sulfur in the surface of bulk MoP during hydrodesulfurization , 2013 .

[5]  S. Oyama,et al.  Synthesis, characterization, and hydrotreating activity of carbon-supported transition metal phosphides , 2005 .

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

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

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

[9]  S. Rundqvist,et al.  X-RAY STUDIES OF MOLYBDENUM AND TUNGSTEN PHOSPHIDES , 1963 .

[10]  Qian Liu,et al.  Closely Interconnected Network of Molybdenum Phosphide Nanoparticles: A Highly Efficient Electrocatalyst for Generating Hydrogen from Water , 2014, Advanced materials.

[11]  Timothy R. Cook,et al.  Solar energy supply and storage for the legacy and nonlegacy worlds. , 2010, Chemical reviews.

[12]  Jens K. Nørskov,et al.  The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions: A density functional study , 2007 .

[13]  Xiaoming Ge,et al.  Molybdenum phosphide as an efficient electrocatalyst for the hydrogen evolution reaction , 2014 .

[14]  N. Lewis,et al.  Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution , 2014 .

[15]  R. Prins,et al.  Metal Phosphides: Preparation, Characterization and Catalytic Reactivity , 2012, Catalysis Letters.

[16]  A. Lasia,et al.  Investigation of hydrogen evolution on Raney-Nickel composite-coated electrodes , 1990 .

[17]  Xile Hu,et al.  Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. , 2014, Chemical Society reviews.

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

[19]  Thomas F. Jaramillo,et al.  Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols , 2010 .

[20]  M. Boudart,et al.  Turnover Rates in Heterogeneous Catalysis , 1995 .

[21]  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.

[22]  Kevin J. Smith,et al.  The effect of cobalt addition to bulk MoP and Ni2P catalysts for the hydrodesulfurization of 4,6-dimethyldibenzothiophene , 2006 .

[23]  Ping Liu,et al.  Catalysts for hydrogen evolution from the [NiFe] hydrogenase to the Ni2P(001) surface: the importance of ensemble effect. , 2005, Journal of the American Chemical Society.

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

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

[26]  James R. McKone,et al.  Ni–Mo Nanopowders for Efficient Electrochemical Hydrogen Evolution , 2013 .

[27]  D. Phillips,et al.  Synthesis, Characterization, and Hydrodesulfurization Properties of Silica-Supported Molybdenum Phosphide Catalysts , 2002 .

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

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

[30]  Dong Sung Choi,et al.  Molybdenum sulfide/N-doped CNT forest hybrid catalysts for high-performance hydrogen evolution reaction. , 2014, Nano letters.

[31]  James R. McKone,et al.  Solar water splitting cells. , 2010, Chemical reviews.