TY - JOUR
T1 - Novel MoO2/carbon hierarchical nano/microcomposites
T2 - Synthesis, characterization, solid state transformations and thiophene HDS activity
AU - Avendaño, Carlos
AU - Briceño, Alexander
AU - Méndez, Franklin J.
AU - Brito, Joaquín L.
AU - González, Gema
AU - Cañizales, Edgar
AU - Atencio, Reinaldo
AU - Dieudonné, Philippe
PY - 2013/2/28
Y1 - 2013/2/28
N2 - Novel MoO2/C nano/microcomposites were prepared via a bottom-up approach by hydrothermal carbonization of a solution of glucose as a carbon precursor in the presence of polyoxometalates (POMs: phosphomolybdic acid [H3PMo12O40] and ammonium heptamolybdate tetrahydrate [(NH4)6Mo7O24] ·4H2O). The structural characterization by FT-IR, XRPD, SEM and TEM analyses revealed the controlled formation of hierarchical MoO 2/C composites with different morphologies: strawberry-like, based on carbon microspheres decorated with MoO2 nanoparticles; MoO 2/C core-shell composites; and irregular aggregates in combination with ring-like microstructures bearing amorphous Mo species. These composites can be fine-tuned by varying reaction time, glucose/POM ratio and type of POM precursor. Subsequent transformations in the solid state through calcinations of MoO2/C core-shell composites in air lead to hollow nanostructured molybdenum trioxide microspheres together with nanorods and plate microcrystals or cauliflower-like composites (MoO2/C). In addition, the MoO 2/C composite undergoes a morphology evolution to urchin-like composites when it is calcined under nitrogen atmosphere (MoO 2/C-N2). The MoO2/C strawberry-like and MoO2/C-N2 composites were transformed into Mo carbide and nitride supported on carbon microspheres (Mo2C/C, MoN/C, and MoN/C-N2). These phases were tested as precursors in thiophene hydrodesulphurization (HDS) at 400°C, observing the following trend in relation to the thiophene steady-state conversion: MoN/C-N2 > MoN/C > Mo2C/C > MoO2/C-N2 > MoO 2/C. According to these conversion values, a direct correlation was observed between higher HDS activity and decreasing crystal size as estimated from the Scherrer equation. These results suggest that such composites represent interesting and promising precursors for HDS catalysts, where the activity and stability can be modified either by chemical or structural changes of the composites under different conditions.
AB - Novel MoO2/C nano/microcomposites were prepared via a bottom-up approach by hydrothermal carbonization of a solution of glucose as a carbon precursor in the presence of polyoxometalates (POMs: phosphomolybdic acid [H3PMo12O40] and ammonium heptamolybdate tetrahydrate [(NH4)6Mo7O24] ·4H2O). The structural characterization by FT-IR, XRPD, SEM and TEM analyses revealed the controlled formation of hierarchical MoO 2/C composites with different morphologies: strawberry-like, based on carbon microspheres decorated with MoO2 nanoparticles; MoO 2/C core-shell composites; and irregular aggregates in combination with ring-like microstructures bearing amorphous Mo species. These composites can be fine-tuned by varying reaction time, glucose/POM ratio and type of POM precursor. Subsequent transformations in the solid state through calcinations of MoO2/C core-shell composites in air lead to hollow nanostructured molybdenum trioxide microspheres together with nanorods and plate microcrystals or cauliflower-like composites (MoO2/C). In addition, the MoO 2/C composite undergoes a morphology evolution to urchin-like composites when it is calcined under nitrogen atmosphere (MoO 2/C-N2). The MoO2/C strawberry-like and MoO2/C-N2 composites were transformed into Mo carbide and nitride supported on carbon microspheres (Mo2C/C, MoN/C, and MoN/C-N2). These phases were tested as precursors in thiophene hydrodesulphurization (HDS) at 400°C, observing the following trend in relation to the thiophene steady-state conversion: MoN/C-N2 > MoN/C > Mo2C/C > MoO2/C-N2 > MoO 2/C. According to these conversion values, a direct correlation was observed between higher HDS activity and decreasing crystal size as estimated from the Scherrer equation. These results suggest that such composites represent interesting and promising precursors for HDS catalysts, where the activity and stability can be modified either by chemical or structural changes of the composites under different conditions.
UR - http://www.scopus.com/inward/record.url?scp=84873310218&partnerID=8YFLogxK
U2 - 10.1039/c2dt31248d
DO - 10.1039/c2dt31248d
M3 - Artículo
C2 - 23243664
AN - SCOPUS:84873310218
SN - 1477-9226
VL - 42
SP - 2822
EP - 2830
JO - Dalton Transactions
JF - Dalton Transactions
IS - 8
ER -