Facile synthesis of triangular shaped palladium nanoparticles decorated nitrogen doped graphene and their catalytic study for renewable energy applications

Abstract We report a novel method for the synthesis of triangular shaped palladium nanoparticles (Pd NPs) decorated nitrogen doped graphene. Nitrogen doped graphene (N-G) is synthesized by uniform coating of polyelectrolyte modified graphene surface with a nitrogen containing polymer followed by their pyrolysis. The triangular shaped Pd NPs are decorated over nitrogen doped graphene (Pd/N-G) by kinetically controlling the polyol reduction process. The kinetic control of the growth of the nanoparticles and nitrogen doping of the supporting material leads to the formation of highly dispersed anisotropic nanoparticles over the graphene support. Hydrogen storage study of N-G and Pd/N-G give a storage capacity of 1.1 wt% and 1.9 wt%, respectively at 25 °C and 2 MPa hydrogen equilibrium pressure. Electrocatalytic study of Pd/N-G shows that it is a very good electrocatalyst for oxygen reduction reaction and highly stable in acidic media due to the strong binding between Pd NPs and graphene support as a result of nitrogen doping besides has high methanol tolerance in acidic media. The present synthesis procedure highlights a new pathway for the highly dispersed and different morphological metal nanoparticles decorated graphene composites for energy related applications.

[1]  G. Shi,et al.  Graphene based new energy materials , 2011 .

[2]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[3]  W. Schuhmann,et al.  Metal-free and electrocatalytically active nitrogen-doped carbon nanotubes synthesized by coating with polyaniline. , 2010, Nanoscale.

[4]  Philip N. Ross,et al.  Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability , 2007, Science.

[5]  T. Nejat Veziroglu,et al.  Storage of hydrogen in nanostructured carbon materials , 2009 .

[6]  Yawen Tang,et al.  Carbon supported Palladium–Iron nanoparticles with uniform alloy structure as methanol-tolerant electrocatalyst for oxygen reduction reaction , 2012 .

[7]  George E. Froudakis,et al.  Fundamental studies and perceptions on the spillover mechanism for hydrogen storage. , 2011, Chemical communications.

[8]  R. Li,et al.  High oxygen-reduction activity and durability of nitrogen-doped graphene , 2011 .

[9]  M. Hasik,et al.  XPS studies of nitrogen-containing conjugated polymers–palladium systems , 2002 .

[10]  R. Piner,et al.  Synthesis of graphene-like nanosheets and their hydrogen adsorption capacity , 2010 .

[11]  F. Stavale,et al.  Measuring disorder in graphene with the G and D bands , 2010 .

[12]  Michael Hirscher,et al.  Hydrogen storage properties of Pd nanoparticle/carbon template composites , 2008 .

[13]  Chaoyang Wang,et al.  Improved performance of proton exchange membrane fuel cells with p-toluenesulfonic acid-doped co-PPy/C as cathode electrocatalyst. , 2010, Journal of the American Chemical Society.

[14]  S. Ramaprabhu,et al.  Investigation of Spillover Mechanism in Palladium Decorated Hydrogen Exfoliated Functionalized Graphene , 2011 .

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

[16]  G. Seifert,et al.  Packings of Carbon Nanotubes – New Materials for Hydrogen Storage , 2011, Advanced materials.

[17]  Y. Liu,et al.  Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. , 2010, ACS nano.

[18]  Huyen N. Dinh,et al.  Enhancement of Pt and Pt-alloy fuel cell catalyst activity and durability via nitrogen-modified carbon supports , 2010 .

[19]  B. Vinayan,et al.  Novel Platinum–Cobalt Alloy Nanoparticles Dispersed on Nitrogen‐Doped Graphene as a Cathode Electrocatalyst for PEMFC Applications , 2012 .

[20]  Yong Wang,et al.  Nitrogen-doped graphene and its electrochemical applications , 2010 .

[21]  Soojin Park,et al.  Hydrogen storage behaviors of platinum-supported multi-walled carbon nanotubes , 2010 .

[22]  E. Antolini.  Palladium in fuel cell catalysis , 2009 .

[23]  M. De Francesco,et al.  Comparison of high surface Pt/C catalysts by cyclic voltammetry , 2002 .

[24]  S. Ramaprabhu,et al.  Effect of nitrogen doping on hydrogen storage capacity of palladium decorated graphene. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[25]  S. Citalán-Cigarroa,et al.  Kinetics of oxygen reduction reaction on nanosized Pd electrocatalyst in acid media , 2007 .

[26]  Fan Yang,et al.  Carbon Nanotubes Decorated with Pt Nanocubes by a Noncovalent Functionalization Method and Their Role in Oxygen Reduction , 2008 .

[27]  B. Vinayan,et al.  Catalytic activity of platinum–cobalt alloy nanoparticles decorated functionalized multiwalled carbon nanotubes for oxygen reduction reaction in PEMFC , 2012 .

[28]  Y. Son,et al.  Oxygen reduction reactions on pure and nitrogen-doped graphene: a first-principles modeling. , 2011, Nanoscale.

[29]  G. Cui,et al.  Nitrogen-doped graphene nanosheets with excellent lithium storage properties , 2011 .

[30]  Huamin Zhang,et al.  A facile synthesis of Pd/C cathode electrocatalyst for proton exchange membrane fuel cells , 2011 .

[31]  Gui Yu,et al.  Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. , 2009, Nano letters.

[32]  S. Ordóñez,et al.  Hydrogen adsorption on Pd-modified carbon nanofibres: Influence of CNF surface chemistry and impregnation procedure , 2010 .

[33]  B. Liu,et al.  Nitrogen and boron doped monolayer graphene by chemical vapor deposition using polystyrene, urea and boric acid , 2012 .

[34]  Lipeng Zhang,et al.  Mechanisms of Oxygen Reduction Reaction on Nitrogen-Doped Graphene for Fuel Cells , 2011 .

[35]  Claude R. Henry,et al.  Morphology of supported nanoparticles , 2005 .

[36]  Licheng Liu,et al.  Shape-dependent catalytic activity of palladium nanocrystals for the oxidation of carbon monoxide , 2012 .

[37]  C. M. Li,et al.  Surface functionalization-enhanced spillover effect on hydrogen storage of Ni–B nanoalloy-doped activated carbon , 2011 .

[38]  P. J. Sebastian,et al.  Synthesis, characterization and application of a Pd/Vulcan and Pd/C catalyst in a PEM fuel cell , 2004 .

[39]  F. Švec,et al.  Nanoporous polymers for hydrogen storage. , 2009, Small.

[40]  Younan Xia,et al.  A water-based synthesis of octahedral, decahedral, and icosahedral Pd nanocrystals. , 2007, Angewandte Chemie.

[41]  Kee Suk Nahm,et al.  Enhancement of hydrogen storage capacity of carbon nanotubes via spill-over from vanadium and palladium nanoparticles , 2005 .

[42]  I. Jain,et al.  Hydrogen the fuel for 21st century , 2009 .

[43]  Lin Shao,et al.  Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. , 2011, ACS nano.

[44]  S. Ramaprabhu,et al.  Graphene synthesis via hydrogen induced low temperature exfoliation of graphite oxide , 2010 .

[45]  S. Choi,et al.  Synthesis, characterization, and electrocatalytic properties of a polypyrrole-composited Pd/C catalyst , 2011 .

[46]  S. Rowshanzamir,et al.  Review of the proton exchange membranes for fuel cell applications , 2010 .

[47]  Joseph M. McLellan,et al.  Kinetically controlled synthesis of triangular and hexagonal nanoplates of palladium and their SPR/SERS properties. , 2005, Journal of the American Chemical Society.

[48]  Ling Zhang,et al.  Shape-controlled synthesis of single-crystalline palladium nanocrystals. , 2010, ACS nano.