title: Binding mechanism of arsenate on rutile (110) and (001) planes studied using grazing-incidence EXAFS measurement and DFT calculation.
abstract: Characterization of contaminant molecules on different exposed crystal planes is required to conclusively describe its behavior on mineral surfaces. Here, the structural properties and relative stability of arsenate adsorbed on rutile TiO2 (110) and (001) surfaces were investigated using grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) spectra and periodic density functional theory (DFT) calculation. The combined results indicated that arsenate mainly formed inner-sphere bidentate binuclear (BB) and monodentate mononuclear (MM) complexes on both surfaces, but the orientational polar angles of arsenate on the (110) surface were commonly smaller than that on the (001) surface for the two adsorption modes. The DFT calculation showed that the (110) plane had a higher affinity toward arsenate than the (001) plane, suggesting that, for a given adsorption mode (i.e., MM or BB structure), a small polar angle was more favorable for arsenate stabilized on the rutile surfaces.
authors.affiliation: Department of Environmental Nano-materials, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China. Electronic address: myzhang@rcees.ac.cn.
authors.forename: Meiyi
authors.initials: M
authors.lastname: Zhang
authors.affiliation: Department of Environmental Nano-materials, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China. Electronic address: gzhhe@rcees.ac.cn.
authors.forename: Guangzhi
authors.initials: G
authors.lastname: He
authors.affiliation: Department of Environmental Nano-materials, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China. Electronic address: gpan@rcees.ac.cn.
authors.forename: Gang
authors.initials: G
authors.lastname: Pan
mesh_terms: D000327:Adsorption; D001149:Arsenates / Q000737:chemistry*; D014025:Titanium / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D001149:Arsenates; C009495:titanium dioxide; D014025:Titanium; C025657:arsenic acid
keywords: Adsorption stability; Density functional theory; GI-EXAFS; Molecular orientation; Surface complex