Electronic effect of Na promotion for selective mono-N-alkylation of aniline with di-iso-propylamine by Pt/SiO 2 catalysts

Ken Ichi Shimizu, Katsuya Shimura, Kazuo Kato, Naoko Tamagawa, Masazumi Tamura, Atsushi Satsuma

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)


Sodium promoted 5 wt.% Pt/SiO 2 catalysts with similar Pt particle size (2.9-3.5 nm) but with different Na loadings (Na/Pt ratio of 0-10) were prepared by a sequential impregnation method. The catalysts were well characterized by Pt L 3-edge XAFS (X-ray absorption fine structure), X-ray photoelectron spectroscopy (XPS), infrared (IR) study of CO adsorption. Their catalytic activity for mono-N-alkylation of aniline with iPr 2NH, as a test reaction for cross-coupling reaction of different amines, showed a volcano type dependence on the Na/Pt ratio. The catalyst with Na/Pt ratio of 2 showed the highest intrinsic activity. The Na/Pt ratio also affected the electronic states of the support oxide and Pt; the electron densities of Pt and surface oxygen atoms of support oxides increased with the Na/Pt ratio. From the structure-activity relationship, it is shown that the moderate electron densities of Pt and support oxygen atoms lead to the high catalytic activity. Kinetic studies suggest that the present reaction proceeds through a hydrogen-borrowing mechanism that begins with dehydrogenation of iPr 2NH as the rate-limiting step. Based on the mechanistic and structural results, origin of the promotional effect of Na on the catalytic activity of Pt/SiO 2 is discussed.

Original languageEnglish
Pages (from-to)171-177
Number of pages7
JournalJournal of Molecular Catalysis A: Chemical
Publication statusPublished - 2012 Feb


  • Amines
  • Cross-coupling
  • Electronic effect
  • Platinum
  • Sodium

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry


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