Negative Electrocatalytic Effects of p-Doping Niobium and Tantalum on MoS2 and WS2 for the Hydrogen Evolution Reaction and Oxygen Reduction Reaction

Transition-metal dichalcogenides (TMDs) are at the forefront of research for their promising catalytic abilities and unique materials properties. With great interest in the study of mono- or few-layered TMDs, we seek to fundamentally explore the effects of doping on bulk TMDs, particularly MoS2 and WS2 for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) with p-dopants Nb and Ta. Despite promises reported in the computational studies of doped TMDs on the HER, our results show otherwise. Doped bulk TMDs display less catalytic activity in comparison to their undoped counterparts for the HER. A similar effect is observed for ORR catalysis. Characterization was done to shed light on its surface elemental composition, properties, and morphologies. It was found that doped WS2 has a high percentage of 1T phase but this does not correlate with a lower overpotential for the HER at −10 mA cm–2, which contradicts the general consensus. We therefore show that p-dopants have a negative electro...

[1]  M. Pumera,et al.  Aromatic-Exfoliated Transition Metal Dichalcogenides: Implications for Inherent Electrochemistry and Hydrogen Evolution , 2016 .

[2]  W. Que,et al.  Molybdenum disulfide nanomaterials: Structures, properties, synthesis and recent progress on hydrogen evolution reaction , 2016 .

[3]  Aleksander A. Tedstone,et al.  Synthesis, Properties, and Applications of Transition Metal-Doped Layered Transition Metal Dichalcogenides , 2016 .

[4]  Rui Wang,et al.  Additive Effects on Asymmetric Catalysis. , 2016, Chemical reviews.

[5]  L. Wirtz,et al.  Vibrational and optical properties of MoS2: From monolayer to bulk , 2015, 1606.03017.

[6]  C. Xia,et al.  Effect of structural defects on electronic and magnetic properties of pristine and Mn-doped MoS2 monolayer , 2015 .

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

[8]  S. Dillon,et al.  Mechanical Properties of Molybdenum Disulfide and the Effect of Doping: An in Situ TEM Study. , 2015, ACS applied materials & interfaces.

[9]  L. Chu,et al.  Halide-Assisted Atmospheric Pressure Growth of Large WSe2 and WS2 Monolayer Crystals , 2015, 1509.00555.

[10]  Luigi Colombo,et al.  Impurities and Electronic Property Variations of Natural MoS2 Crystal Surfaces. , 2015, ACS nano.

[11]  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.

[12]  M. Pumera,et al.  Pristine Basal- and Edge-Plane-Oriented Molybdenite MoS2 Exhibiting Highly Anisotropic Properties. , 2015, Chemistry.

[13]  M. Pumera,et al.  Catalytic and charge transfer properties of transition metal dichalcogenides arising from electrochemical pretreatment. , 2015, ACS nano.

[14]  Martin Pumera,et al.  Lithium intercalation compound dramatically influences the electrochemical properties of exfoliated MoS2. , 2015, Small.

[15]  Lu Wang,et al.  Photothermoelectric and photovoltaic effects both present in MoS2 , 2015, Scientific Reports.

[16]  M. Pumera,et al.  Precise tuning of the charge transfer kinetics and catalytic properties of MoS2 materials via electrochemical methods. , 2014, Chemistry.

[17]  M. Pumera,et al.  Electrochemistry of transition metal dichalcogenides: strong dependence on the metal-to-chalcogen composition and exfoliation method. , 2014, ACS nano.

[18]  Sefaattin Tongay,et al.  Doping against the native propensity of MoS2: degenerate hole doping by cation substitution. , 2014, Nano letters.

[19]  Sohail Ahmad,et al.  A Comparative Study of Electronic Properties of Bulk MoS2 and Its Monolayer Using DFT Technique: Application of Mechanical Strain on MoS2 Monolayer , 2014 .

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

[21]  G. Ozin,et al.  Colloidal synthesis of 1T-WS2 and 2H-WS2 nanosheets: applications for photocatalytic hydrogen evolution. , 2014, Journal of the American Chemical Society.

[22]  Yi Xie,et al.  Semimetallic molybdenum disulfide ultrathin nanosheets as an efficient electrocatalyst for hydrogen evolution. , 2014, Nanoscale.

[23]  Charlie Tsai,et al.  Active edge sites in MoSe2 and WSe2 catalysts for the hydrogen evolution reaction: a density functional study. , 2014, Physical chemistry chemical physics : PCCP.

[24]  Martin Pumera,et al.  Layered transition metal dichalcogenides for electrochemical energy generation and storage , 2014 .

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

[26]  Thomas F. Kent,et al.  p-type doping of MoS2 thin films using Nb , 2014 .

[27]  Weitao Yang,et al.  Layer-dependent electrocatalysis of MoS2 for hydrogen evolution. , 2013, Nano letters.

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

[29]  J. Kong,et al.  Integrated circuits based on bilayer MoS₂ transistors. , 2012, Nano letters.

[30]  L. David,et al.  Synthesis of Surface-Functionalized WS2 Nanosheets and Performance as Li-Ion Battery Anodes. , 2012, The journal of physical chemistry letters.

[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]  Zhong Chen,et al.  Tribological properties of Cr- and Ti-doped MoS2 composite coatings under different humidity atmosphere , 2010 .

[33]  Rong Zeng,et al.  Synthesis of molybdenum disulfide (MoS2) for lithium ion battery applications , 2009 .

[34]  C. Colliex,et al.  Ab initio study of bilateral doping within the MoS2-NbS2 system , 2008, 0806.1411.

[35]  Sidney R. Cohen,et al.  Fullerene-Like (IF) NbxMo1-xS2 Nanoparticles , 2007 .

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

[37]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

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

[39]  C. Haas,et al.  An X-ray photoemission spectroscopy study of interlayer charge transfer in some misfit layer compounds , 1993 .

[40]  A. Sobczyński.  Molybdenum disulfide as a hydrogen evolution catalyst for water photodecomposition on semiconductors , 1991 .

[41]  N. H. Turner,et al.  Determination of peak positions and areas from wide‐scan XPS spectra , 1990 .

[42]  S. Contarini,et al.  Ion-beam-induced chemical changes in the oxyanions (Moyn-) and oxides (Mox) where M = chromium, molybdenum, tungsten, vanadium, niobium and tantalum , 1987 .

[43]  Hsieng-Ming Wu,et al.  Dopant-polymer interaction: WCl6-doped polyacetylene , 1987 .

[44]  W. Kautek,et al.  Anisotropic photocorrosion of n-type MoS2, MoSe2, and WSe2 single crystal surfaces: The role of cleavage steps, line and screw dislocations , 1982 .

[45]  Richard S. Nicholson,et al.  Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. , 1965 .

[46]  Katsuhiko Ariga,et al.  Catalytic nanoarchitectonics for environmentally compatible energy generation , 2016 .

[47]  Charlie Tsai,et al.  Rational design of MoS2 catalysts: tuning the structure and activity via transition metal doping , 2015 .

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

[49]  Greg M. Swain,et al.  Solid Electrode Materials: Pretreatment and Activation , 2007 .

[50]  Helmut Tributsch,et al.  Interfacial properties of semiconducting transition metal chalcogenides , 1988 .

[51]  W. Jaegermann,et al.  Reactivity of layer type transition metal chalcogenides towards oxidation , 1986 .