Enhancement of Pt and Pt-alloy fuel cell catalyst activity and durability via nitrogen-modified carbon supports

Insufficient catalytic activity and durability are key barriers to the commercial deployment of low temperature polymer electrolyte membrane (PEM) and direct-methanol fuel cells (DMFCs). Recent observations suggest that carbon-based catalyst support materials can be systematically doped with nitrogen to create strong, beneficial catalyst-support interactions which substantially enhance catalyst activity and stability. Data suggest that nitrogen functional groups introduced into a carbon support appear to influence at least three aspects of the catalyst/support system: 1) modified nucleation and growth kinetics during catalyst nanoparticle deposition, which results in smaller catalyst particle size and increased catalyst particle dispersion, 2) increased support/catalyst chemical binding (or “tethering”), which results in enhanced durability, and 3) catalyst nanoparticle electronic structure modification, which enhances intrinsic catalytic activity. This review highlights recent studies that provide broad-based evidence for these nitrogen-modification effects as well as insights into the underlying fundamental mechanisms.

[1]  Yingke Zhou,et al.  First principles study of doped carbon supports for enhanced platinum catalysts. , 2010, Physical chemistry chemical physics : PCCP.

[2]  Zhaolin Liu,et al.  Pt Nanoparticles Supported on Nitrogen-Doped Porous Carbon Nanospheres as an Electrocatalyst for Fuel Cells , 2010 .

[3]  B. Popov,et al.  Highly stable Pt and PtPd hybrid catalysts supported on a nitrogen-modified carbon composite for fuel cell application ☆ , 2010 .

[4]  R. O’Hayre,et al.  Dopant-Induced Electronic Structure Modification of HOPG Surfaces: Implications for High Activity Fuel Cell Catalysts , 2010 .

[5]  Drew C. Higgins,et al.  Highly Active Nitrogen-Doped Carbon Nanotubes for Oxygen Reduction Reaction in Fuel Cell Applications , 2009 .

[6]  R. Li,et al.  Ultrathin single crystal Pt nanowires grown on N-doped carbon nanotubes. , 2009, Chemical communications.

[7]  M. Groves,et al.  Improving platinum catalyst binding energy to graphene through nitrogen doping , 2009 .

[8]  R. O’Hayre,et al.  Improving PEM fuel cell catalyst activity and durability using nitrogen-doped carbon supports: observations from model Pt/HOPG systems , 2009 .

[9]  Keith J. Stevenson,et al.  Effect of Nitrogen Concentration on Capacitance, Density of States, Electronic Conductivity, and Morphology of N-Doped Carbon Nanotube Electrodes , 2009 .

[10]  C. Bock,et al.  Ternary PtRuNi Nanocatalysts Supported on N-Doped Carbon Nanotubes: Deposition Process, Material Characterization, and Electrochemistry , 2009 .

[11]  R. Li,et al.  Enhanced stability of Pt electrocatalysts by nitrogen doping in CNTs for PEM fuel cells , 2009 .

[12]  Z. Lei,et al.  Structural evolution and electrocatalytic application of nitrogen-doped carbon shells synthesized by pyrolysis of near-monodisperse polyaniline nanospheres , 2009 .

[13]  Thorsten Schilling,et al.  Towards nitrogen-containing CNTs for fuel cell electrodes , 2009 .

[14]  W. Schuhmann,et al.  Electrocatalytic Activity and Stability of Nitrogen-Containing Carbon Nanotubes in the Oxygen Reduction Reaction , 2009 .

[15]  W. Schuhmann,et al.  PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation , 2009 .

[16]  E. Antolini Carbon supports for low-temperature fuel cell catalysts , 2009 .

[17]  T. Fujigaya,et al.  Design of an assembly of poly(benzimidazole), carbon nanotubes, and Pt nanoparticles for a fuel-cell electrocatalyst with an ideal interfacial nanostructure. , 2009, Small.

[18]  Z. Lei,et al.  Highly dispersed platinum supported on nitrogen-containing ordered mesoporous carbon for methanol electrochemical oxidation , 2009 .

[19]  Chun-Wei Chen,et al.  A first-principles study of nitrogen- and boron-assisted platinum adsorption on carbon nanotubes , 2009 .

[20]  R. Li,et al.  3-D composite electrodes for high performance PEM fuel cells composed of Pt supported on nitrogen-doped carbon nanotubes grown on carbon paper , 2009 .

[21]  Jae-Hyun Park,et al.  Effects of electrospun polyacrylonitrile-based carbon nanofibers as catalyst support in PEMFC , 2009 .

[22]  Svitlana Pylypenko,et al.  Non-platinum oxygen reduction electrocatalysts based on pyrolyzed transition metal macrocycles , 2008 .

[23]  Deyu Li,et al.  Enhanced methanol electro-oxidation activity of PtRu catalysts supported on heteroatom-doped carbon , 2008 .

[24]  M. Terrones,et al.  Efficient anchorage of Pt clusters on N-doped carbon nanotubes and their catalytic activity , 2008 .

[25]  C. Bittencourt,et al.  Platinum-carbon nanotube interaction , 2008 .

[26]  Hansung Kim,et al.  Synthesis and characterization of PtNx/C as methanol-tolerant oxygen reduction electrocatalysts for a direct methanol fuel cell , 2008 .

[27]  Edmar P. Marques,et al.  A review of Fe-N/C and Co-N/C catalysts for the oxygen reduction reaction , 2008 .

[28]  A. Striolo,et al.  Platinum nanoparticles on carbonaceous materials: the effect of support geometry on nanoparticle mobility, morphology, and melting , 2008, Nanotechnology.

[29]  T. Maiyalagan Synthesis and electro catalytic activity of methanol oxidation on nitrogen containing carbon nanotubes supported Pt electrodes , 2008 .

[30]  S. Yen,et al.  Controlled platinum nanoparticles uniformly dispersed on nitrogen-doped carbon nanotubes for methanol oxidation , 2008 .

[31]  Xizhang Wang,et al.  CNx nanotubes as catalyst support to immobilize platinum nanoparticles for methanol oxidation , 2008 .

[32]  Deyu Li,et al.  Well-dispersed high-loading pt nanoparticles supported by shell-core nanostructured carbon for methanol electrooxidation. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[33]  Yuyan Shao,et al.  Nitrogen-doped carbon nanostructures and their composites as catalytic materials for proton exchange membrane fuel cell , 2008 .

[34]  J. Jang,et al.  Highly dispersed Pt nanoparticles on nitrogen-doped magnetic carbon nanoparticles and their enhanced activity for methanol oxidation , 2007 .

[35]  Siyu Ye,et al.  Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC: Part II: Degradation mechanism and durability enhancement of carbon supported platinum catalyst , 2007 .

[36]  Siyu Ye,et al.  Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC: Part I. Physico-chemical and electronic interaction between Pt and carbon support, and activity enhancement of Pt/C catalyst , 2007 .

[37]  R. Penner,et al.  Physical vapor deposition of one-dimensional nanoparticle arrays on graphite: seeding the electrodeposition of gold nanowires. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[38]  Jong‐Sung Yu,et al.  Novel ordered nanoporous graphitic C3N4 as a support for Pt–Ru anode catalyst in direct methanol fuel cell , 2007 .

[39]  Keith J Stevenson,et al.  Synergistic assembly of dendrimer-templated platinum catalysts on nitrogen-doped carbon nanotube electrodes for oxygen reduction. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[40]  Kuei-Hsien Chen,et al.  High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth , 2006 .

[41]  A. Ōya,et al.  Simultaneous doping of boron and nitrogen into a carbon to enhance its oxygen reduction activity in proton exchange membrane fuel cells , 2006 .

[42]  I. Hsing,et al.  Surfactant-stabilized PtRu colloidal catalysts with good control of composition and size for methanol oxidation , 2006 .

[43]  Hubert A. Gasteiger,et al.  Determination of Catalyst Unique Parameters for the Oxygen Reduction Reaction in a PEMFC , 2006 .

[44]  Elizabeth J. Biddinger,et al.  Oxygen reduction reaction catalysts prepared from acetonitrile pyrolysis over alumina-supported metal particles. , 2006, The journal of physical chemistry. B.

[45]  Stephen A. Morin,et al.  Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping , 2006 .

[46]  Kuei-Hsien Chen,et al.  Atomic-scale deformation in N-doped carbon nanotubes. , 2006, Journal of the American Chemical Society.

[47]  Gang Yu,et al.  Fabrication of Pd–Ni alloy nanowire arrays on HOPG surface by electrodeposition , 2006 .

[48]  P. Kuo,et al.  Enhanced stabilization and deposition of Pt nanocrystals on carbon by dumbbell-like polyethyleniminated poly(oxypropylene)diamine. , 2006, The journal of physical chemistry. B.

[49]  Jens K Nørskov,et al.  Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. , 2006, Angewandte Chemie.

[50]  Umit S. Ozkan,et al.  The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction , 2006 .

[51]  Ermete Antolini,et al.  The methanol oxidation reaction on platinum alloys with the first row transition metals The case of Pt-Co and -Ni alloy electrocatalysts for DMFCs: A short review , 2006 .

[52]  Alfred B. Anderson,et al.  O2 reduction on graphite and nitrogen-doped graphite: experiment and theory. , 2006, The journal of physical chemistry. B.

[53]  M. Arenz,et al.  CO surface electrochemistry on Pt-nanoparticles: A selective review , 2005 .

[54]  U. V. Varadaraju,et al.  Nitrogen containing carbon nanotubes as supports for Pt – Alternate anodes for fuel cell applications , 2005 .

[55]  D. Carroll,et al.  Temperature and flow rate of NH3 effects on nitrogen content and doping environments of carbon nanotubes grown by injection CVD method. , 2005, The journal of physical chemistry. B.

[56]  P N Ross,et al.  The impact of geometric and surface electronic properties of pt-catalysts on the particle size effect in electrocatalysis. , 2005, The journal of physical chemistry. B.

[57]  Kuei-Hsien Chen,et al.  Ultrafine Platinum Nanoparticles Uniformly Dispersed on Arrayed CNx Nanotubes with High Electrochemical Activity , 2005 .

[58]  H. Gasteiger,et al.  Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs , 2005 .

[59]  K. Stevenson,et al.  Influence of nitrogen doping on oxygen reduction electrocatalysis at carbon nanofiber electrodes. , 2005, The journal of physical chemistry. B.

[60]  Stephen Maldonado,et al.  Direct preparation of carbon nanofiber electrodes via pyrolysis of iron(II) phthalocyanine: Electrocatalytic aspects for oxygen reduction , 2004 .

[61]  T. Grzybek,et al.  Influence of nitrogen surface functionalities on the catalytic activity of activated carbon in low temperature SCR of NOx with NH3 , 2004 .

[62]  C. Wen,et al.  Controlling steps during early stages of the aligned growth of carbon nanotubes using microwave plasma enhanced chemical vapor deposition , 2002 .

[63]  Z. Deng,et al.  Synthesis and thermal decomposition of carbon nitride films prepared by nitrogen ion implantation into graphite , 2002 .

[64]  T. Ando,et al.  XPS study of nitridation of diamond and graphite with a nitrogen ion beam , 2001 .

[65]  Shimshon Gottesfeld,et al.  Electrocatalysis in direct methanol fuel cells: in-situ probing of PtRu anode catalyst surfaces , 2000 .

[66]  B. Rambabu,et al.  A study of methanol electro-oxidation reactions in carbon membrane electrodes and structural properties of Pt alloy electro-catalysts by EXAFS , 2000 .

[67]  N. Grobert,et al.  Carbon Nitride Nanocomposites: Formation of Aligned CxNy Nanofibers , 1999 .

[68]  Daniel Guay,et al.  Effect of the Pre-Treatment of Carbon Black Supports on the Activity of Fe-Based Electrocatalysts for the Reduction of Oxygen , 1999 .

[69]  I. Gouzman,et al.  Electron spectroscopic study of C–N bond formation by low-energy nitrogen ion implantation of graphite and diamond surfaces , 1999 .

[70]  W. Sigle,et al.  Transport and structural modification during nitrogen implantation of hard amorphous carbon films , 1998 .

[71]  Sudipta Roy,et al.  Spectroelectrochemical Study of the Role Played by Carbon Functionality in Fuel Cell Electrodes , 1997 .

[72]  P. Christensen,et al.  Direct Methanol Fuel Cell Cathodes with Sulfur and Nitrogen‐Based Carbon Functionality , 1996 .

[73]  D. Chu,et al.  Methanol Electro‐oxidation on Unsupported Pt‐Ru Alloys at Different Temperatures , 1996 .

[74]  A. Shukla,et al.  Electro‐oxidation of Methanol in Sulfuric Acid Electrolyte on Platinized‐Carbon Electrodes with Several Functional‐Group Characteristics , 1994 .

[75]  Hubert A. Gasteiger,et al.  Methanol electrooxidation on well-characterized Pt-Ru alloys , 1993 .

[76]  T. Kuwana,et al.  Scanning electron microscopic and x-ray photoelectron spectroscopic examination of Tokai glassy carbon surfaces subjected to radio frequency plasmas , 1981 .

[77]  T. Kuwana,et al.  Introduction of functional groups onto carbon electrodes via treatment with radio-frequency plasmas , 1979 .

[78]  R. Murray,et al.  CHEMICALLY MODIFIED ELECTRODES , 1977 .

[79]  C. M. Elliott,et al.  Chemically modified carbon electrodes , 1976 .

[80]  Svitlana Pylypenko,et al.  Bifunctional Oxygen Reduction Reaction Mechanism on Non-Platinum Catalysts Derived from Pyrolyzed Porphyrins , 2010 .

[81]  Yong Wang,et al.  Novel catalyst support materials for PEM fuel cells : current status and future prospects , 2009 .

[82]  Yuan Juan,et al.  Pd-Ni Nanowires Prepared by Electrochemical Step-edge Decoration , 2005 .

[83]  I. Dukhno,et al.  Mechanism of reductive oxygen adsorption on active carbons with various surface chemistry , 2004 .

[84]  P. A. Thrower,et al.  On the mechanism of possible influence of heteroatoms of nitrogen, boron and phosphorus in a carbon matrix on the catalytic activity of carbons in electron transfer reactions , 2000 .

[85]  H. Gasteiger,et al.  Methanol electrooxidation on a colloidal PtRu-alloy fuel-cell catalyst , 1999 .

[86]  L. Dao,et al.  A New Fuel Cell Electrocatalyst Based on Carbonized Polyacrylonitrile Foam The Nature of Platinum‐Support Interactions , 1997 .

[87]  H. Gasteiger,et al.  On the reaction pathway for methanol and carbon monoxide electrooxidation on Pt-Sn alloy versus Pt-Ru alloy surfaces , 1996 .

[88]  L. Dao,et al.  A New Fuel Cell Electrocatalyst Based on Highly Porous Carbonized Polyacrylonitrile Foam with Very Low Platinum Loading , 1996 .

[89]  Freek Kapteijn,et al.  Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis , 1995 .

[90]  R. Spontak,et al.  Preparation of Nanoscale Platinum(0) Clusters in Glassy Carbon and Their Catalytic Activity , 1993 .

[91]  H. Marsh,et al.  Inhibiting effect of incorporated nitrogen on the oxidation of microcrystalline carbons , 1992 .

[92]  R. McCreery,et al.  Feature articls. Doped glassy carbon: a new material for electrocatalysis , 1992 .

[93]  Robert Schlögl,et al.  Enhancement of the catalytic activity of activated carbons in oxidation reactions by thermal treatment with ammonia or hydrogen cyanide and observation of a superoxide species as a possible intermediate , 1991 .