Chemistry - A European Journal
10.1002/chem.202003857
FULL PAPER
The reaction was carried out at 110 oC and the conversions and yields
were monitored by GC. After the separation, the catalyst was reused
without extra treatment after washing under the same condition.
would conform to the proposed six-membered ring transition state
during our selective transfer hydrogenation according to
experimental verification and literature exploration.[24]
Acknowledgements ((optional))
This work was financially supported by National Natural Science
Foundation of China (Nos. 21872020, 81872835, 21621003,
Conclusion
2
1805029). Fundamental Research Funds for the Central
In summary, we have successfully designed and synthesized an
armour-type composite catalyst of metal organic framework-
Universities (N180705004, N180504007).
capsulated magnetic CoCu nanoparticles (Fe
CoCu@UiO-66) by the novel half-way injection method for the
selective transfer hydrogenation. Remarkably, part of
nitrobenzaldehydes can be selectively hydrogenated into
corresponding nitrobenzyl alcohols in extremely high conversion
3 4 2 2
O @SiO -NH -
Keywords: MOF-capsulated composite • Half-way Injection
Method • Selective transfer hydrogenation • Metal nanoparticles
a
•
Nitrobenzaldehydes
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99%) and selectivity (99%) rather than the hydrogenation of nitro
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group. Probably, the acid sites of the catalyst could preferentially
bind with the carbonyl group and form a crucial six-membered ring
transition state with isopropanol, and metal nanoparticles could
adsorb and preserve the nitro group. In addition, this armoured
catalyst can be recycled under the same conditions for 9 cycles
without the loss of activity. The armoured UiO-66 armour can
serve as the active component for this catalytic reaction, not only
stabilize CoCu nanoparticles, improve the recycling of the catalyst,
but also cooperate with metal nanoparticles to accelerate the
hydrogen transfer reaction rate, which achieves this
synergistically catalytic and controllable reaction in a “1+1>2”
manner.
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Experimental Section
2
Preparation of Fe
and activated with 50 mL HCl solution (0.125 mol/L). After ultrasonic
treatment for 20 min, pre-treated activated Fe was dispersed in the
3 4 2 2
3 4
O @SiO -NH : Typically, Fe O (0.2 g) was dispersed
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3
O
4
1477-1504.
mixture containing ethanol (170 mL) water (30 mL) and ammonium
hydroxide (4 mL, 25%). Tetraethyl orthosilicate (TEOS, 1 mL) was injected
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the solid components were separated by magnetic collection in the above
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o
mL) at 90 C for 3 hours in order to synthesize Fe
3
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@SiO
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-NH
2
. At last,
the product was gathered by the magnet and washed with ethanol for three
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and washed for three times with ethanol.
3
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@SiO
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-NH
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-CoCu NPs: Fe
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@SiO
2 2
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Preparation of Fe
3
O
4
@SiO
2
-NH
2
-CoCu@UiO-66: Equal molar amounts
BDC) were dissolved in 100 mL
of ZrCl and 1, 4-benzenedicarboxylate (H
4
2
DMF solution. Then, acetic acid (10 mL) was added in the mixture with
vigorously stirring. During the budding period of UiO-66 growth,
Fe O @SiO -NH -CoCu was injected into MOF precursors solution. The
3 4 2 2
final UiO-66-capsulated was washed with ethanol for three times.
Catalytic transfer hydrogenation reaction of nitroaldehydes:
Nitroaldehydes (1 mmol) and catalyst (30 wt%) were mixed into a sealed
tube. The isopropanol (10 mL) was added as solvent and hydrogen source.
6
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