Corresponding Author

De-yin WU(dywu@xmu.edu.cn)


The gold nanoparticles (GNPs) show special activity toward hydrogen (H2) dissociation, comparing with bulk gold. Such activity is significantly affected by the existence of water. To inspect the influence of water on GNPs catalyzed H2 dissociation, we carried out density functional theory (DFT) calculations along the reaction paths for water clusters (H2O)m (m = 1, 2, 3, 7) assisted H2 dissociation on gold clusters (Aunδ, n = 3 ~ 5; δ = 0, 1). Our calculated results show that water benefits to the H2 dissociation. The dissociation mechanism varies with the size of water clusters, from the homolytic cleavage of the H-H bond to the oxidation dissociation mechanism on the small gold clusters. We also suggest Raman and IR spectroscopies can be used to characterize the products of those two mechanisms.

Graphical Abstract


gold nanoparticles, hydrogen dissociation, water assisted reaction, density functional theory, Raman spectroscopy.

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[1]Hammer B, Norskov J K.Why gold is the noblest of all the metals[J].Nature,1995,376(6537):238-240.
[2]Harris J, Andersson S,Holmberg C,et al.The interaction of H2 with metal-surface[J].Physica Scripta,1986,T13:155-160.
[3] Stobinski L, Zommer L, Dus R. Molecular hydrogen interactions with discontinuous and continuous thin gold films[J]. Applied Surface Science, 1999, 141(3/4): 319-325.
[4] Fujitani T, Nakamura I, Akita T, et al. Hydrogen dissociation by gold clusters[J]. Angewandte Chemie International Edition, 2009, 48(50): 9515-9518.
[5] Mukherjee S, Libisch F, Large N, et al. Hot electrons do the impossible: Plasmon-induced dissociation of H2 on Au[J]. Nano Letter, 2013, 13(1): 240-247.
[6] Mukherjee S, Zhou L, Goodman A M, et al. Hot-electron-induced dissociation of H2 on gold nanoparticles supported on SiO2[J]. Journal of the American Chemical Society, 2014, 136(1): 64-67.
[7] Corma A, Boronat M, Gonzalez S, et al. On the activation of molecular hydrogen by gold: a theoretical approximation to the nature of potential active sites[J]. Chemical Communications, 2007, 32(32): 3371-3373.
[8] Determan J J, Moncho S, Brothers E N, et al. Simulating periodic trends in the structure and catalytic activity of coinage metal nanoribbons [J]. International Journal of Quantum Chemistry, 2015, 115(24): 1718-1725.
[9] Mavrikakis M, Stoltze P, Norskov J K. Making gold less noble[J]. Catalysis Letters, 2000, 64(2/4): 101-106.
[10] Kang G J, Chen Z X, Li Z, et al. A theoretical study of the effects of the charge state and size of gold clusters on the adsorption and dissociation of H2[J]. The Journal of Chemical Physics, 2009, 130(3): 034701.
[11] Zanchet A, Dorta-Urra A, Aguado A, et al. Understanding structure, size, and charge effects for the H2 dissociation mechanism on planar gold clusters[J]. Journal of Physical Chemistry C, 2011, 115(1): 47-57.
[12] Kuang X J, Wang X Q, Liu G B. A comparative study between all-electron scalar relativistic calculation and all-electron calculation on the adsorption of hydrogen molecule onto small gold clusters[J]. Journal of Chemistry Sciences, 2013, 125(2): 401-411.
[13] Fang Z, Kuang X. Hydrogen molecule adsorption on AunPt (n = 1-12) clusters in comparison with corresponding pure Aun+1 (n = 1-12) clusters[J]. Physica Status Solidi B, 2014, 251(2): 446-454.
[14] Dorta-Urra A, Zanchet A, Roncero O, et al. A comparative study of the Au + H2, Au+ + H2, and Au- + H2 systems: Potential energy surfaces and dynamics of reactive collisions[J]. The Journal of Chemical Physics, 2015, 142(15): 154301.
[15] Gao M, Lyalin A, Takagi M, et al. Reactivity of gold clusters in the regime of structural fluxionality[J]. Journal of Physical Chemistry C, 2015, 119(20): 11120-11130.
[16] Ghebriel H W, Kshirsagar A. Adsorption of molecular hydrogen and hydrogen sulfide on Au clusters[J]. The Journal of Chemical Physics, 2007, 126(24): 244705.
[17] Varganov S A, Olson R M, Gordon M S, et al. A study of the reactions of molecular hydrogen with small gold clusters[J]. The Journal of Chemical Physics, 2004, 120(11): 5169-5175.
[18] Cox D M, Brickman R, Creegan K, et al. Gold clusters-reactions and deuterium uptake[J]. Zeitschrift fürPhysik D Atoms, Molecules and Clusters, 1991, 19(4): 353-355.
[19] Lang S M, Bernhardt T M, Barnett R N, et al. Hydrogen-promoted oxygen activation by free gold cluster cations[J]. Journal of the American Chemical Society, 2009, 131(25): 8939-8951.
[20] Sun K, Kohyama M, Tanaka S, et al. A study on the mechanism for H2 dissociation on Au/TiO2 catalysts[J]. The Journal of Physical Chemistry C, 2014, 118(3): 1611-1617.
[21] Buceta D, Blanco M C, Lopez-Quintela M A, et al. Critical size range of sub-nanometer Au clusters for the catalytic activity in the hydrogen oxidation reaction[J]. Journal of the Electrochemical Society, 2014, 161(7): D3113-D3115.
[22] Santos E, Quaino P, Schmickler W. Theory of electrocatalysis: Hydrogen evolution and more[J]. Physical Chemistry Chemistry Physics, 2012, 14(32): 11224-11233.
[23] Brust M, Gordillo G J. Electrocatalytic hydrogen redox chemistry on gold nanoparticles[J]. Journal of the American Chemical Society, 2012, 134(7): 3318-3321.
[24] Santos E, Hindelang P, Quaino P, et al. Hydrogen electrocatalysis on single crystals and on nanostructured electrodes[J]. ChemPhysChem, 2011, 12(12): 2274-2279.
[25] Boccuzzi F, Chiorino A, Manzoli M, et al. FTIR study of the low-temperature water-gas shift reaction on Au/Fe2O3 and Au/TiO2 catalysts[J]. Journal of Catalysis, 1999, 188(1): 176-185.
[26] Jiang Y X, Li J F, Wu D Y, et al. Characterization of surface water on Au core Pt-group metal shell nanoparticles coated electrodes by surface-enhanced Raman spectroscopy[J]. Chemical Communications, 2007, 44: 4608-4610.
[27] Kuang X J, Wang X Q, Liu G B. All-electron scalar relativistic calculation of water molecule adsorption onto small gold clusters[J]. Journal of Molecular Modeling, 2011, 17(8): 2005-2016.
[28] Sugawara K, Sobott F, Vakhtin A B. Reactions of gold cluster cations Aun+ (n=1-12) with H2S and H2[J]. The Journal of Chemical Physics, 2003, 118(17): 7808-7816.
[29] Gilb S, Weis P, Furche F, et al. Structures of small gold cluster cations (Aun+, n < 14): Ion mobility measurements versus density functional calculations[J]. The Journal of Chemical Physics, 2002, 116(10): 4094-4101.
[30] Becke A D. Density-functional thermochemistry.3. the role of exact echange[J]. The Journal of Chemical Physics, 1993, 98(7): 5648-5652.
[31] Dunning T H. Gaussian basis sets for use in correlated molecular calculations. 1. The atoms boron through neon and hydrogen[J]. The Journal of Chemical Physics, 1989, 90(2): 1007-1023.
[32] Hay P J, Wadt W R. Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms scandium to mercury[J]. The Journal of Chemical Physics, 1985, 82(1): 270-283.
[33] Lee C T, Yang W T, Parr R G. Development of the collesalvetti correlation-energy formula into a functional of the electron-density[J]. Physical review B, 1988, 37(2): 785-789.
[34] Fukui K. The path of chemical reactions - the IRC approach[J]. Accounts of Chemical Research, 1981, 14(12): 363-368.
[35] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09, revision D. 01[M]. Wallingford, CT; Gaussian, Inc., Wallingford CT. 2009.
[36] Pang R, Yu L J, Zhang M, et al. DFT study of hydrogen-bonding interaction, solvation effect, and electric-field effect on raman spectra of hydrated proton[J]. Journal of Physical Chemistry A, 2016, 120(42): 8273-8284.



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