| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1306736 | Inorganica Chimica Acta | 2015 | 7 Pages |
•Sieving effect in catalysis of Henry reaction by HKUST-1 was found.•Accessibility of pores to reagents was confirmed by sorption measurements.•Rate of salicylaldehyde sorption is governed by the internal diffusion stage.•Molecular mechanic modeling showed that pores are accessible to salicylaldehyde.•Diffusion of reagents in pores has significant contribution to reaction rate.
Catalytic activity of copper(II) 1,3,5-benzenetricarboxylate, HKUST-1, in reactions of condensation of aromatic aldehydes with nitromethane was studied. It was shown that HKUST-1 catalyzed condensation of salicylaldehyde with nitromethane leading to formation of trans-nitrovinylphenol, while 9-anthracenecarbaldehyde did not react in the same conditions. Catalytic activity of HKUST-1 was consistent with its sorption capacity in respect to the reagents. The difference in catalytic activity of HKUST-1 in reactions with salicylaldehyde and 9-anthracenecarbaldehyde can be caused by sieving effect (molecules discrimination by size). Kinetics of salicylaldehyde condensation with nitromethane, catalyzed by HKUST-1, as well as kinetics of salicylaldehyde sorption by HKUST-1 were studied. Accessibility of pores of HKUST-1 to salicylaldehyde and condensation product (trans-nitrovinylphenol) was evaluated by molecular mechanics. Catalytic activity (reaction rate and salicylaldehyde diffusion rate) of HKUST-1 is compared with FeIII analog, role of diffusion rate is shown.
Graphical abstractHKUST-1 catalyzed condensation of salicylaldehyde with nitromethane leading to formation of trans-nitrovinylphenol, while 9-anthracenecarbaldehyde did not react. Kinetics of salicylaldehyde condensation with nitromethane, as well as kinetics of salicylaldehyde sorption by HKUST-1 were studied. Accessibility of catalyst’s pores to salicylaldehyde and trans-nitrovinylphenol was evaluated by molecular mechanics.Figure optionsDownload full-size imageDownload as PowerPoint slide
