TY - JOUR
T1 - Size- and support-dependent selective amine cross-coupling with platinum nanocluster catalysts
AU - Shimizu, Ken Ichi
AU - Ohshima, Keiichiro
AU - Tai, Yutaka
AU - Tamura, Masazumi
AU - Satsuma, Atsushi
PY - 2012/4
Y1 - 2012/4
N2 - γ-Alumina-supported Pt nanoclusters with an average particle size of 0.8 nm, Pt/Al 2O 3-0.8, act as an effective heterogeneous catalyst for mono-N-alkylation of amines with different amines. To establish a catalyst design concept, systematic studies on the structure-activity relationship are carried out, combined with characterization by Pt L 3-edge XAFS (X-ray absorption fine structure), X-ray photoelectron spectroscopy (XPS), and infrared (IR) study of CO adsorption. By changing the particle size of Pt over the size range of 0.8-24 nm, it is demonstrated that the present reaction is a structure-sensitive reaction, demanding coordinatively unsaturated Pt atoms on metallic nanoclusters. The support also affects the activity and electronic state of Pt. The electron density of Pt increases with basicity of the support oxide, and the support with moderate basicity (Al 2O 3) gives the highest activity probably due to a moderate electron density of Pt. Kinetic studies suggest that the present reaction proceeds through a "hydrogen-borrowing" mechanism.
AB - γ-Alumina-supported Pt nanoclusters with an average particle size of 0.8 nm, Pt/Al 2O 3-0.8, act as an effective heterogeneous catalyst for mono-N-alkylation of amines with different amines. To establish a catalyst design concept, systematic studies on the structure-activity relationship are carried out, combined with characterization by Pt L 3-edge XAFS (X-ray absorption fine structure), X-ray photoelectron spectroscopy (XPS), and infrared (IR) study of CO adsorption. By changing the particle size of Pt over the size range of 0.8-24 nm, it is demonstrated that the present reaction is a structure-sensitive reaction, demanding coordinatively unsaturated Pt atoms on metallic nanoclusters. The support also affects the activity and electronic state of Pt. The electron density of Pt increases with basicity of the support oxide, and the support with moderate basicity (Al 2O 3) gives the highest activity probably due to a moderate electron density of Pt. Kinetic studies suggest that the present reaction proceeds through a "hydrogen-borrowing" mechanism.
UR - http://www.scopus.com/inward/record.url?scp=84859372945&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84859372945&partnerID=8YFLogxK
U2 - 10.1039/c2cy00476c
DO - 10.1039/c2cy00476c
M3 - Article
AN - SCOPUS:84859372945
VL - 2
SP - 730
EP - 738
JO - Catalysis Science and Technology
JF - Catalysis Science and Technology
SN - 2044-4753
IS - 4
ER -