6 Catalysis with MNPs on N-Doped Carbon
213
N
H
N
N
1.5 mol% catalyst
CHO
120
o
C, mesitylen, 8h
H 2
1.5 mol%
catalyst
formic acid
toluene
120
o C, 1.5 h
Hydrolysis
NaOH
H 2 O/EtOH
3 mol% catalyst
1.5 MPa H 2 , toluene
120
o C, 12h
Scheme 6.16 SAS-Co/OPNC catalyzed reversible system for hydrogen storage and release
Nitrogen-based MOF
Pyrolysis
Metal nanoparticles
supported on N-doped carbon
Nitrogen-based MOF
Immobilization
or assembled on
heterogeneous supports
MOF-heterogeneous
support template
Pyrolysis Metal nanoparticles
encapsulated in
N-doped carbon
Scheme 6.17 Preparation of N-doped carbon supported nanoparticles by using MOFs as precursors
specific nitrogen containing MOF was transformed into graphitic N-doped carbon
with high-density special basic sites, while the Co
2+ ions were reduced to give Conanoparticles which were dispersed on or embedded in N-doped graphitic structures
[30]. These Co-nanoparticles resulted in reusable catalysts for base-free transfer
hydrogenation of nitriles to primary amines and secondary imines in good to excellent
yields by using isopropanol (i-PrOH) as hydrogen source (Scheme 6.18) [30]. The
progress and selectivity of this nitrile transfer hydrogenation reaction is highly dependent on the amount of isopropanol, which was used as both solvent and hydrogen
R
CN
Co@NC-900 (10 ml%)
Co@NC-900 (10 ml%)
1 mL i-PrOH, 8-120
o C
4 mL i-PrOH, 80
o C
R
NH 2
R
N
R Up to 99% yield
Up to 99% yield
Scheme 6.18 Transfer hydrogenation of nitriles by using Co@NC-900 catalyst