The interaction of H2S with the ZnO(1010) surface. 2013

Jakub Goclon, and Bernd Meyer
Interdisziplinäres Zentrum für Molekulare Materialien (ICMM) and Computer-Chemie-Centrum (CCC), Universität Erlangen-Nürnberg, 91052 Erlangen, Germany. jakub.goclon@chemie.uni-erlangen.de

Using density functional theory with and without Hubbard-U correction we have calculated the geometric structure and the binding energy of H2S molecules adsorbed on the main cleavage plane of ZnO. We find that H2S molecules preferentially dissociate upon adsorption, with a negligible barrier for the first and an activation energy of about 0.5 eV for the second SH bond dissociation. In the low coverage limit of individual molecules single and double dissociation are energetically almost degenerate. At higher coverage double dissociation is favored because of attractive adsorbate-adsorbate interactions. Thermodynamic analysis shows that the double-dissociated state at full saturation with a coverage of 1/2 monolayer is the most stable adsorbate structure for a wide range of temperatures and partial pressures. However, at high H2S chemical potential a full monolayer of single-dissociated H2S becomes thermodynamically more favorable. In addition, at low temperature this structure may exist as a metastable configuration due to the activation barrier for the second SH bond cleavage. Finally we show that it is thermodynamically favorable for adsorbed H2S to react with the first ZnO surface layer to form ZnS and water.

UI MeSH Term Description Entries
D008958 Models, Molecular Models used experimentally or theoretically to study molecular shape, electronic properties, or interactions; includes analogous molecules, computer-generated graphics, and mechanical structures. Molecular Models,Model, Molecular,Molecular Model
D000327 Adsorption The adhesion of gases, liquids, or dissolved solids onto a surface. It includes adsorptive phenomena of bacteria and viruses onto surfaces as well. ABSORPTION into the substance may follow but not necessarily. Adsorptions
D001665 Binding Sites The parts of a macromolecule that directly participate in its specific combination with another molecule. Combining Site,Binding Site,Combining Sites,Site, Binding,Site, Combining,Sites, Binding,Sites, Combining
D013447 Sulfites Inorganic salts of sulfurous acid. Sulfite,Sulfites, Inorganic,Inorganic Sulfites
D013499 Surface Properties Characteristics or attributes of the outer boundaries of objects, including molecules. Properties, Surface,Property, Surface,Surface Property
D013816 Thermodynamics A rigorously mathematical analysis of energy relationships (heat, work, temperature, and equilibrium). It describes systems whose states are determined by thermal parameters, such as temperature, in addition to mechanical and electromagnetic parameters. (From Hawley's Condensed Chemical Dictionary, 12th ed) Thermodynamic
D015034 Zinc Oxide A mild astringent and topical protectant with some antiseptic action. It is also used in bandages, pastes, ointments, dental cements, and as a sunblock. Lassar's Paste,Lassar Paste,Lassars Paste,Oxide, Zinc,Paste, Lassar's

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