Phosphorus-modified tungsten nitride/reduced graphene oxide as a high-performance, non-noble-metal electrocatalyst for the hydrogen evolution reaction.

Phosphorus-modified tungsten nitride/reduced graphene oxide (P-WN/rGO) is designed as a high-efficient, low-cost electrocatalyst for the hydrogen evolution reaction (HER). WN (ca. 3 nm in size) on rGO is first synthesized by using the H3[PO4(W3O9)4] cluster as a W source. Followed by phosphorization, the particle size increase slightly to about 4 nm with a P content of 2.52 at %. The interaction of P with rGO and WN results in an obvious increase of work function, being close to Pt metal. The P-WN/rGO exhibits low onset overpotential of 46 mV, Tafel slope of 54 mV dec(-1), and a large exchange current density of 0.35 mA cm(-2) in acid media. It requires overpotential of only 85 mV at current density of 10 mA cm(-2), while remaining good stability in accelerated durability testing. This work shows that the modification with a second anion is powerful way to design new catalysts for HER.

[1]  M. Jaroniec,et al.  Porous C3N4 nanolayers@N-graphene films as catalyst electrodes for highly efficient hydrogen evolution. , 2015, ACS nano.

[2]  Abdullah M. Asiri,et al.  High-Efficiency Electrochemical Hydrogen Evolution Catalyzed by Tungsten Phosphide Submicroparticles , 2015 .

[3]  Shi-Zhang Qiao,et al.  Elektrochemie der Wasserstoffentwicklungsreaktion: Optimierung durch Korrelation von Experiment und Theorie , 2015 .

[4]  Yao Zheng,et al.  Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. , 2015, Angewandte Chemie.

[5]  Liangmin Yu,et al.  Transparent metal selenide alloy counter electrodes for high-efficiency bifacial dye-sensitized solar cells. , 2014, Angewandte Chemie.

[6]  T. Jaramillo,et al.  Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction. , 2014, Angewandte Chemie.

[7]  Abdullah M. Asiri,et al.  A cost-effective 3D hydrogen evolution cathode with high catalytic activity: FeP nanowire array as the active phase. , 2014, Angewandte Chemie.

[8]  S. Ramakrishna,et al.  Cobalt sulfide nanosheet/graphene/carbon nanotube nanocomposites as flexible electrodes for hydrogen evolution. , 2014, Angewandte Chemie.

[9]  Mingsen Deng,et al.  Surface polarization matters: enhancing the hydrogen-evolution reaction by shrinking Pt shells in Pt-Pd-graphene stack structures. , 2014, Angewandte Chemie.

[10]  Shuhong Yu,et al.  Nanowire-directed templating synthesis of metal-organic framework nanofibers and their derived porous doped carbon nanofibers for enhanced electrocatalysis. , 2014, Journal of the American Chemical Society.

[11]  Abdullah M. Asiri,et al.  Self-supported Cu3P nanowire arrays as an integrated high-performance three-dimensional cathode for generating hydrogen from water. , 2014, Angewandte Chemie.

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

[13]  H. Fu,et al.  Small-sized and high-dispersed WN from [SiO4(W3O9)4]4− clusters loading on GO-derived graphene as promising carriers for methanol electro-oxidation , 2014 .

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

[15]  Bingfei Cao,et al.  Mixed close-packed cobalt molybdenum nitrides as non-noble metal electrocatalysts for the hydrogen evolution reaction. , 2013, Journal of the American Chemical Society.

[16]  E. Fujita,et al.  Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. , 2013, Chemical communications.

[17]  H. Fu,et al.  Synergistic effect of tungsten carbide and palladium on graphene for promoted ethanol electrooxidation. , 2013, ACS applied materials & interfaces.

[18]  D. Portehault,et al.  Nanoscaled metal borides and phosphides: recent developments and perspectives. , 2013, Chemical reviews.

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

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

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

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

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

[24]  A. Morpurgo,et al.  Quantitative determination of the band gap of WS2 with ambipolar ionic liquid-gated transistors. , 2012, Nano letters.

[25]  D. Bhattacharjya,et al.  Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media. , 2012, Journal of the American Chemical Society.

[26]  D. Wilkinson,et al.  Nano-architecture and material designs for water splitting photoelectrodes. , 2012, Chemical Society reviews.

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

[28]  H. Fu,et al.  Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells. , 2012, Chemistry.

[29]  H. Fu,et al.  A facile one-pot route for the controllable growth of small sized and well-dispersed ZnO particles on GO-derived graphene , 2012 .

[30]  T. Ma,et al.  Two flexible counter electrodes based on molybdenum and tungsten nitrides for dye-sensitized solar cells , 2011 .

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

[32]  Xiao-ru Wang,et al.  Synthesis of "clean" and well-dispersive Pd nanoparticles with excellent electrocatalytic property on graphene oxide. , 2011, Journal of the American Chemical Society.

[33]  Y. Liu,et al.  Structural and Electrochemical Studies of Pt Clusters Supported on High-Surface-Area Tungsten Carbide for Oxygen Reduction , 2011 .

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

[35]  Jinwoo Lee,et al.  Platinum-free tungsten carbides as an efficient counter electrode for dye sensitized solar cells. , 2010, Chemical communications.

[36]  H. Ju,et al.  Nanostructured FeS as a mimic peroxidase for biocatalysis and biosensing. , 2009, Chemistry.

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

[38]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[39]  S. Reich,et al.  Raman spectroscopy of graphite , 2004, Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

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

[41]  M. Dresselhaus,et al.  Alternative energy technologies , 2001, Nature.

[42]  Jingguang G. Chen Carbide and Nitride Overlayers on Early Transition Metal Surfaces: Preparation, Characterization, and Reactivities. , 1996, Chemical reviews.

[43]  O. Petrii,et al.  Real surface area measurements in electrochemistry , 1991 .

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

[45]  H. Michaelson The work function of the elements and its periodicity , 1977 .

[46]  Angel T. Garcia-Esparza,et al.  Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting. , 2013, ChemSusChem.