Adsorption and dissociation of NH3 on clean and hydroxylated TiO2 rutile (110) surfaces: A computational study

The adsorption and dissociation of NH3 on the clean and hydroxylated TiO2 rutile (110) surfaces have been investigated by the first‐principles calculations. The monodentate adsorbates such as H3NTi(a), H2NTi(a), NTi(a), H2NO(a), HNO(a), NO(a) and HO(a), as well as the bidentate adsorbate, TiNTi(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five‐fold‐coordinated Ti atoms (5c‐Ti), namely H2NTi(a), HNTi(a), NTi(a) and TiNTi(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two‐fold‐coordinated O atoms (2c‐O). The enhanced adsorption of NHx (x = 1 − 2) on the 5c‐Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NHx (x = 1 − 2) on the two‐fold‐coordinated O atoms (2c‐O) decreasing its basicity. According to potential energy profile, the NH3 dissociation on the TiO2 surface is endothermic and the hydroxyl group is found to lower the energetics of H2NTi(a)+HO(a) and HNTi(a)+2{HO(a)}, but slightly raise the energetic of TiNTi(a)+3{HO(a)} compare to those on the clean surface. However, the dissociation of NH3 is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH3 on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011.

[1]  Y. Hitomi,et al.  Visible Light Absorbed NH2 Species Derived from NH3 Adsorbed on TiO2 for Photoassisted Selective Catalytic Reduction , 2007 .

[2]  J. Lennard-jones,et al.  Molecular Spectra and Molecular Structure , 1929, Nature.

[3]  Michael A. Henderson,et al.  An HREELS and TPD study of water on TiO2(110): the extent of molecular versus dissociative adsorption , 1996 .

[4]  A. Morawski,et al.  The preparation of TiO2–nitrogen doped by calcination of TiO2·xH2O under ammonia atmosphere for visible light photocatalysis , 2005 .

[5]  Jenghan Wang,et al.  Low-pressure organometallic chemical vapor deposition of indium nitride on titanium dioxide nanoparticles. , 2004, ChemPhysChem.

[6]  Ulrike Diebold,et al.  The surface science of titanium dioxide , 2003 .

[7]  Hafner,et al.  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. , 1994, Physical review. B, Condensed matter.

[8]  Siegfried Schmauder,et al.  Comput. Mater. Sci. , 1998 .

[9]  G. Thornton,et al.  Imaging Water Dissociation on TiO(2)(110). , 2001, Physical review letters.

[10]  P. Raghunath,et al.  Adsorption Configurations and Decomposition Pathways of Boric Acid on TiO2 Rutile (110) Surface: A Computational Study , 2009 .

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

[12]  J. Nørskov,et al.  Oxygen vacancies as active sites for water dissociation on rutile TiO(2)(110). , 2001, Physical review letters.

[13]  M. Grätzel,et al.  A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films , 1991, Nature.

[14]  Michael A. Henderson,et al.  Structural Sensitivity in the Dissociation of Water on TiO2 Single-Crystal Surfaces , 1996 .

[15]  L. Gao,et al.  New Method to Prepare Nitrogen‐Doped Titanium Dioxide and Its Photocatalytic Activities Irradiated by Visible Light , 2004 .

[16]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[17]  Jee-Gong Chang,et al.  A Computational Study on Adsorption Configurations and Dissociative Reactions of the HN3 Molecule on the TiO2 Anatase (101) Surface , 2008 .

[18]  C. Minot,et al.  Diffusion versus desorption: complex behavior of H atoms on an oxide surface. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[19]  P. Raghunath,et al.  Adsorption configurations and reactions of boric acid on a TiO2 anatase (101) surface , 2008 .

[20]  Hsin‐Tsung Chen,et al.  Density Functional Theory Study of the Adsorption and Reaction of H2S on TiO2 Rutile (110) and Anatase (101) Surfaces , 2009 .

[21]  C. Minot,et al.  A theoretical analysis of NH3 adsorption on TiO2 , 1996 .

[22]  Richard L. Kurtz,et al.  Synchrotron radiation studies of H2O adsorption on TiO2(110) , 1989 .

[23]  M. J. Gillan,et al.  Mixed Dissociative and Molecular Adsorption of Water on the Rutile (110) Surface , 1998 .

[24]  P Hu,et al.  Identifying an O2 supply pathway in CO oxidation on Au/TiO2(110): a density functional theory study on the intrinsic role of water. , 2006, Journal of the American Chemical Society.

[25]  J. Gole,et al.  Enhanced Nitrogen Doping in TiO2 Nanoparticles , 2003 .

[26]  M. Ruckenbauer,et al.  Multilayer adsorption of water at a rutile TiO2)(110) surface: towards a realistic modeling by molecular dynamics. , 2004, The Journal of chemical physics.

[27]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

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

[29]  島内 みどり,et al.  G. Herzberg: Molecular Spectra and Molecular Structure. III. Electronic Spectra and Electronic Structure of Polyatomic Molecules, D. Van Nostrand, Prinston 1966, 745頁, 16.5×24cm, 8,000円. , 1968 .

[30]  G. Herzberg.  Molecular Spectra and Molecular Structure IV. Constants of Diatomic Molecules , 1939 .

[31]  O. Kitao,et al.  Theoretical studies on the absorption spectra of heteroleptic ruthenium polypyridyl dyes for nanocrystalline TiO2 solar cells: Revisited with transition-component analysis , 2008 .

[32]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[33]  C. Minot,et al.  Electron-count control on adsorption upon reducible and irreducible clean metal-oxide surfaces , 2004 .

[34]  Y. Hitomi,et al.  Mechanism of Photo-Oxidation of NH3 over TiO2: Fourier Transform Infrared Study of the Intermediate Species , 2007 .

[35]  M. Grätzel.  Photoelectrochemical cells : Materials for clean energy , 2001 .

[36]  Xiaobo Chen,et al.  Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. , 2007, Chemical reviews.

[37]  Christian Minot,et al.  Adsorption on perfect and reduced surfaces of metal oxides , 2003 .

[38]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[39]  B. Hammer,et al.  Oxygen vacancies on TiO2(110) and their interaction with H2O and O2: A combined high-resolution STM and DFT study , 2005 .

[40]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[41]  Michael A. Henderson,et al.  The Interaction of Water with Solid Surfaces: Fundamental Aspects Revisited , 2002 .

[42]  P. Liska,et al.  Engineering of efficient panchromatic sensitizers for nanocrystalline TiO(2)-based solar cells. , 2001, Journal of the American Chemical Society.

[43]  Yuka Watanabe,et al.  Nitrogen-Concentration Dependence on Photocatalytic Activity of TiO2-xNx Powders , 2003 .

[44]  Role of hydroxyl groups for the O2 adsorption on CeO2 surface: A DFT + U study , 2010 .

[45]  Oliver Diwald,et al.  Photochemical Activity of Nitrogen-Doped Rutile TiO2(110) in Visible Light , 2004 .

[46]  A. Quong,et al.  Molecular chemisorption as the theoretically preferred pathway for water adsorption on ideal rutile TiO2(110). , 2004, Physical review letters.

[47]  B. Delley.  An all‐electron numerical method for solving the local density functional for polyatomic molecules , 1990 .

[48]  G. Henkelman,et al.  A climbing image nudged elastic band method for finding saddle points and minimum energy paths , 2000 .

[49]  Hsin‐Tsung Chen,et al.  Adsorption Configurations and Reactions of Nitric Acid on TiO2 Rutile (110) and Anatase (101) surfaces , 2009 .

[50]  B. Delley.  From molecules to solids with the DMol3 approach , 2000 .

[51]  G. Herzberg,et al.  Molecular spectra and molecular structure. Vol.3: Electronic spectra and electronic structure of polyatomic molecules , 1966 .

[52]  M. J. Gillan,et al.  The adsorption of H2O on TiO2 and SnO2(110) studied by first-principles calculations , 1996 .

[53]  Ulrike Diebold,et al.  Structure and properties of TiO2 surfaces: a brief review , 2003 .

[54]  G. Henkelman,et al.  Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points , 2000 .

[55]  R. Rosenfeld.  Nature , 2009, Otolaryngology--head and neck surgery : official journal of American Academy of Otolaryngology-Head and Neck Surgery.