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Photocatalytic Selective Oxidation of 5-(Hydroxymethyl)-2-furaldehyde to 2,5-Furandicarbaldehyde in Water by Using Anatase, Rutile, and Brookite TiO2 Nanoparticles
5-(Hydroxymethyl)-2-furaldehyde (HMF) was selectively oxidized to 2,5-furandicarbaldehyde (FDC) in; aqueous medium by using home prepared (HP) anatase, rutile, and brookite TiO2 nanoparticles. HP samples were prepared via a sol-gel method by using TiCl4 as the TiO2 precursor. Commercial TiO2 catalysts were also used for, comparison. All samples were characterized by BET specific surface area, XRD, TGA, and SEM, and the reactivity results showed that HP catalysts are predominantly amorphous and give rise to selectivities toward FDC more than twice that of commercial and well crystallized catalysts.
Selective photooxidation of ortho-substituted benzyl alcohols and the catalytic role of ortho-methoxybenzaldehyde
It has been recently reported by Palmisano et al. (2015) [1] that the oxidation of 2-methoxybenzyl alcohol (2-MBA) to 2-methoxybenzaldehyde (2-MBAD) proceeds in water under near-UV light with an unexpected catalytic effect of 2-MBAD. In order to investigate the catalytic role of aldehyde in photolytic oxidation of ortho-substituted benzyl alcohols (OSBAs), reactivity runs were carried out with 2-methylbenzyl alcohol (2-MeBA), 2-nitrobenzyl alcohol (2-NBA), 2-hydroxybenzyl alcohol (2-HBA) and 2-chlorobenzyl alcohol (2-CIBA) in the absence and in the presence of their corresponding aldehyde. None of those alcohols showed a measurable oxidation rate even in the presence of their aldehydes but …
Tuning The Selectivity To Aldehyde Via Ph Regulation In The Photocatalytic Oxidation Of 4-Methoxybenzyl Alcohol And Vanillyl Alcohol By Tio2 Catalysts
Abstract The influence of pH on the photocatalytic partial oxidation of 4-methoxybenzyl alcohol (MBA) and vanillyl alcohol (VA) to their corresponding aldehydes in aqueous suspension under UVA irradiation was investigated by using poorly crystalline home-prepared and crystalline commercial TiO2 (BDH, Merck and Degussa P25) photocatalysts. The results clearly show as tuning pH can strongly impart selectivity and activity to photocatalytic processes which are often quite unselective in aqueous suspensions. It was found that pH effect on reaction rate and product selectivity strongly depended on TiO2 crystallinity and substrate type. In the case of MBA oxidation, photoreactivity and selectivit…
Unexpectedly ambivalent O-2 role in the autocatalytic photooxidation of 2-methoxybenzyl alcohol in water
An unusual autocatalytic photooxidation of 2-methoxybenzyl alcohol has been observed under UV irradiation in aqueous medium. The homogeneous oxidation is catalyzed by the corresponding aldehyde that is also the main oxidation product. The trend of alcohol disappearance rate matches the typical shape of an autocatalytic process, where a crucial and ambivalent role is played by the presence of molecular oxygen. Low oxygen concentrations give rise to a zero-order reaction since the beginning of irradiation, while higher amounts of oxygen reduce the alcohol oxidation rate until the aldehyde reaches a concentration high enough to speed up the alcohol's conversion. Experiments performed by varyin…