Unraveling the mechanism of the oxidation of glycerol to dicarboxylic acids over a sonochemically synthesized copper oxide catalyst

Amaniampong, Prince Nana; Trịnh, Quang Thang; Varghese, Jithin John; Behling, Ronan; Valange, Sabine; Mushrif, Samir H.; Jérôme, François

doi:10.1039/c8gc00961a

Cited by 111 publications

(58 citation statements)

References 79 publications

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“…The author also mentioned that if there is the presence of OH radical within the conversion of the aldehyde species, the barriers could be even lower. And surface OH can activate the primary OH group of glycerol with the lower barriers . In our work, the water molecule is similar to the OH radical in the above literature because the OH group in water closely resembles the function of the OH radical, accepting and transferring protons.…”

Section: Resultssupporting

confidence: 57%

Theoretical study on the formation mechanisms, dynamics and the effective catalysis of the nitrophenols

Jia

Bai

et al. 2018

ChemistrySelect

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The hydrogen abstraction reactions of mono‐substituted phenols and nitrogen dioxide may be the sources of HONO and phenoxy radical. Further addition reaction of NO2 and phenoxy radical can form 2‐nitrophenol (2‐NP) and 4‐nitrophenol (4‐NP). The specific formation mechanisms and dynamics of NPs have drawn significant attention in recent days. The promoted reaction mechanisms by water, phenol and intermediate have also been studied. Compared with the naked reaction, the catalytic pathways can reduce the energy barrier from 48.40 kcal/mol to 18.23, 23.03 and 18.87 kcal/mol to form 2‐NP, respectively. Water molecules are the most effective catalysts, and the energy barrier could be further reduced to 8.20 kcal/mol when three water molecules are participating in the reaction. Water molecules can not only promote the formation of 4‐NP, but also simplify the reaction steps. In general, the water molecules serve as catalysts in the formation of NPs. The rate constants of 2‐NP and its hydrates have been predicted. The results are listed as follows: k2‐NP =3.82×10−13; k2‐NP‐1W =2.43×10−7; k2‐NP‐2W =3.39×10−4 cm3molecule−1s−1. The rate constants of mono‐substituted phenols (methylamino phenol, aminophenol and hydroquinone) and NO2 are also predicted by the traditional transitional state theory and variational transition state theory using the B3LYP/6‐311++G(3df,3pd)//6‐311++G(d). For the most dominant path, the rate constants for o/m/p‐methylaminophenol are 1.91×10−14, 4.28×10−20 and 8.78×10−15 cm3molecule−1s−1, respectively.

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Section: Resultssupporting

confidence: 57%

Theoretical study on the formation mechanisms, dynamics and the effective catalysis of the nitrophenols

Jia

Bai

et al. 2018

ChemistrySelect

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“…The sonochemically synthesized materials also possess greater amounts of surface defects and have shown excellent catalytic activity in the selective oxidation of benzyl alcohol to benzyl aldehyde compared to conventionally prepared OMS-2 catalysts. Highly pure and crystalline 2D CuO nanoleaves have been synthesized at 25°C under low frequency ultrasound (19.95 kHz, 8.2 W electric power) and further used in the base-free aqueous oxidation of glycerol to dicarboxylic acids in the presence of hydrogen peroxide under mild reaction conditions [63]. The significant advantages of this ultrasonic route over conventional methods include a direct synthesis, incredibly fast experiments (5 min), non-thermal activation and in situ pseudo-calcination.…”

Section: Unconventional Activation Methods For the Synthesis Of Selecmentioning

confidence: 99%

General and Prospective Views on Oxidation Reactions in Heterogeneous Catalysis

Valange¹,

Védrine²

2018

Preprint

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In this short review paper we have assembled the main characteristics of partial oxidation reactions (oxidative dehydrogenation and selective oxidation to olefins or oxygenates, as aldehydes and carboxylic acids and nitriles), as well as total oxidation, particularly for depollution, environmental issues and wastewater treatments. Both gas-solid and liquid-solid media have been considered with recent and representative examples within these fields. We have also discussed about their potential and prospective industrial applications. Particular attention has been brought to new raw materials stemming from biomass and to liquid-solid catalysts cases. This review paper also summarizes the progresses made in the use of unconventional activation methods for performing oxidation reactions, highlighting the synergy of these technologies with heterogeneous catalysis. Focus has been centered on usual catalysts activation methods but also on less usual ones, such as the use of ultrasounds, microwaves, grinding (mechanochemistry) and photo-activated processes, as well as their combined use.

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“…The sonochemically synthesized materials also possess greater amounts of surface defects and have shown enhanced catalytic activity in the selective oxidation of benzyl alcohol to benzaldehyde (TON of 8.32) compared to conventionally prepared OMS-2 catalysts (TON of 3.36). Highly pure and crystalline 2D CuO nanoleaves have been synthesized at 25 • C under low frequency ultrasound (19.95 kHz, 8.2 W electric power) and further used in the base-free aqueous oxidation of glycerol to dicarboxylic acids in the presence of hydrogen peroxide under mild reaction conditions [63]. The significant advantages of this sonochemical preparation route over conventional methods include a direct synthesis, incredibly fast experiments (5 min), non-thermal activation and in situ pseudo-calcination.…”

Section: Figurementioning

confidence: 99%

General and Prospective Views on Oxidation Reactions in Heterogeneous Catalysis

Valange

Védrine

2018

Catalysts

Self Cite

View full text Add to dashboard Cite

In this review paper, we have assembled the main characteristics of partial oxidation reactions (oxidative dehydrogenation and selective oxidation to olefins or oxygenates, as aldehydes and carboxylic acids and nitriles), as well as total oxidation, particularly for depollution, environmental issues and wastewater treatments. Both gas–solid and liquid–solid media have been considered with recent and representative examples within these fields. We have also discussed about their potential and prospective industrial applications. Particular attention has been brought to new raw materials stemming from biomass, as well as to liquid–solid catalysts cases. This review paper also summarizes the progresses made in the use of unconventional activation methods for performing oxidation reactions, highlighting the synergy of these technologies with heterogeneous catalysis. Focus has been centered on both usual catalysts activation methods and less usual ones, such as the use of ultrasounds, microwaves, grinding (mechanochemistry) and photo-activated processes, as well as their combined use.

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Unraveling the mechanism of the oxidation of glycerol to dicarboxylic acids over a sonochemically synthesized copper oxide catalyst

Abstract: Glycerol was oxidized selectively to oxalic and tartronic acids in 78% yield over a highly crystalline CuO catalyst prepared within a few minutes by a sonochemical synthesis.

Cited by 111 publications

References 79 publications

Theoretical study on the formation mechanisms, dynamics and the effective catalysis of the nitrophenols

Theoretical study on the formation mechanisms, dynamics and the effective catalysis of the nitrophenols

General and Prospective Views on Oxidation Reactions in Heterogeneous Catalysis

General and Prospective Views on Oxidation Reactions in Heterogeneous Catalysis

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