Adsorption of gas molecules on transition metal embedded graphene: a search for high-performance graphene-based catalysts and gas sensors

We report an investigation on the adsorption of small gas molecules (O(2), CO, NO(2) and NH(3)) on pristine and various transition metal embedded graphene samples using a first-principles approach based on density-functional theory (DFT). The most stable adsorption geometry, energy, charge transfer, and magnetic moment of these molecules on graphene embedded with different transition metal elements are thoroughly discussed. Our calculations found that embedded transition metal elements in general can significantly enhance the interactions between gas molecules and graphene, and for applications of graphene-based catalysis, Ti and Au may be the best choices among all transition metal elements. We also expect a detailed analysis of the electronic structures and magnetic properties of these systems to shed light on future applications of graphene-based gas sensing and spintronics.

[1]  K. Novoselov,et al.  Detection of individual gas molecules adsorbed on graphene. , 2006, Nature materials.

[2]  E. Williams,et al.  Printed Graphene Circuits , 2007, 0809.1634.

[3]  Hannu Häkkinen,et al.  Charging Effects on Bonding and Catalyzed Oxidation of CO on Au8 Clusters on MgO , 2005, Science.

[4]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[5]  B. Wees,et al.  Electronic spin transport and spin precession in single graphene layers at room temperature , 2007, Nature.

[6]  G. Eda,et al.  Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material. , 2008, Nature nanotechnology.

[7]  Yunhao Lu,et al.  Metal-Embedded Graphene: A Possible Catalyst with High Activity , 2009 .

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

[9]  R. Mülhaupt,et al.  Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction. , 2009, Journal of the American Chemical Society.

[10]  Hoonkyung Lee,et al.  Calcium-decorated graphene-based nanostructures for hydrogen storage. , 2010, Nano letters.

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

[12]  B. H. Weiller,et al.  Practical chemical sensors from chemically derived graphene. , 2009, ACS nano.

[13]  F. Guinea,et al.  The electronic properties of graphene , 2007, Reviews of Modern Physics.

[14]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[15]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[16]  Itaru Honma,et al.  Enhanced electrocatalytic activity of Pt subnanoclusters on graphene nanosheet surface. , 2009, Nano letters.

[17]  Chun Zhang,et al.  Strain-Enhanced Stabilization and Catalytic Activity of Metal Nanoclusters on Graphene , 2010 .

[18]  M I Katsnelson,et al.  Magnetic correlations at graphene edges: basis for novel spintronics devices. , 2007, Physical review letters.

[19]  G. Babcock,et al.  Oxygen activation and the conservation of energy in cell respiration , 1992, Nature.

[20]  F. M. Peeters,et al.  Adsorption of H 2 O , N H 3 , CO, N O 2 , and NO on graphene: A first-principles study , 2007, 0710.1757.

[21]  R. Ruoff,et al.  Graphene-based ultracapacitors. , 2008, Nano letters.

[22]  G. Kresse,et al.  Ab initio molecular dynamics for liquid metals. , 1993 .

[23]  A. Hellman,et al.  First-Principles Studies of NOx Chemistry on Agn/α-Al2O3 , 2009 .

[24]  R. Bader.  Atoms in molecules : a quantum theory , 1990 .

[25]  Prashant V. Kamat,et al.  Graphene-Based Nanoarchitectures. Anchoring Semiconductor and Metal Nanoparticles on a Two-Dimensional Carbon Support , 2010 .

[26]  B. Lundqvist,et al.  Trends in sticking and adsorption of diatomic molecules on the Al(111) surface , 2005 .

[27]  Chun Zhang,et al.  Greatly enhanced adsorption and catalytic activity of Au and Pt clusters on defective graphene. , 2010, The Journal of chemical physics.

[28]  Cai-Hong Liu,et al.  Improving gas sensing properties of graphene by introducing dopants and defects: a first-principles study , 2009, Nanotechnology.

[29]  Zhongfang Chen,et al.  CO Catalytic Oxidation on Iron-Embedded Graphene: Computational Quest for Low-Cost Nanocatalysts , 2010 .

[30]  Tomoaki Ikegami,et al.  Development of carbon nanotube-based gas sensors for NOx gas detection working at low temperature , 2008 .

[31]  A. Krasheninnikov,et al.  Embedding transition-metal atoms in graphene: structure, bonding, and magnetism. , 2009, Physical review letters.

[32]  M. E. Casida,et al.  Comparison of local‐density and Hartree–Fock calculations of molecular polarizabilities and hyperpolarizabilities , 1993 .