TY - JOUR
T1 - Tailoring Mesoporous γ-Al2O3 Properties by Transition Metal Doping
T2 - A Combined Experimental and Computational Study
AU - Fu, Liangjie
AU - Yang, Huaming
AU - Hu, Yuehua
AU - Wu, Di
AU - Navrotsky, Alexandra
N1 - Funding Information:
This work was supported by the National Science Fund for Distinguished Young Scholars (51225403), the Hunan Provincial Science and Technology Project (2016RS2004), and the Postdoctoral Science Foundation of Central South University (201507). All computations were performed at the High Performance Computing Center of Central South University. D.W. thanks the institutional funds from the Gene and Linda Voiland School of Chemical Engineering and Bioengineering at Washington State University.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/14
Y1 - 2017/2/14
N2 - Well crystallized gamma alumina (γ-Al2O3) with high thermal stability is as an important catalyst support. A series of first row transition metal (TM) doped aluminas with ordered mesoporous structures and homogeneous distribution of TM in the bulk structure has been synthesized by a one-pot method. The structures are studied by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM), while the electronic properties are explored by X-ray photoelectron spectroscopy (XPS), valence band XPS, and UV-vis spectra. To explore the influence of TM dopants on atomistic properties (bond length, charge state, band edge, and redox properties) of γ-Al2O3, the cation distribution of TM dopants is studied in detail by combining experiments and density functional theory (DFT) calculations. The cooperative effect of TM dopants and intrinsic defects in γ-Al2O3 induces a doping mechanism distinct from that in other spinel oxides; the concentration of Al vacancies (VAl) decreases with increasing atomic number of the TM dopant as a result of charge compensation effects. Such variation could be used to tailor the properties and alter the reactivity of γ-Al2O3.
AB - Well crystallized gamma alumina (γ-Al2O3) with high thermal stability is as an important catalyst support. A series of first row transition metal (TM) doped aluminas with ordered mesoporous structures and homogeneous distribution of TM in the bulk structure has been synthesized by a one-pot method. The structures are studied by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM), while the electronic properties are explored by X-ray photoelectron spectroscopy (XPS), valence band XPS, and UV-vis spectra. To explore the influence of TM dopants on atomistic properties (bond length, charge state, band edge, and redox properties) of γ-Al2O3, the cation distribution of TM dopants is studied in detail by combining experiments and density functional theory (DFT) calculations. The cooperative effect of TM dopants and intrinsic defects in γ-Al2O3 induces a doping mechanism distinct from that in other spinel oxides; the concentration of Al vacancies (VAl) decreases with increasing atomic number of the TM dopant as a result of charge compensation effects. Such variation could be used to tailor the properties and alter the reactivity of γ-Al2O3.
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U2 - 10.1021/acs.chemmater.6b05041
DO - 10.1021/acs.chemmater.6b05041
M3 - Article
AN - SCOPUS:85012879130
SN - 0897-4756
VL - 29
SP - 1338
EP - 1349
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 3
ER -