Selective Oxidation of Glycerol with 3% H2O2 Catalyzed by LDH-Hosted Cr(III) Complex

Wu, Gongde; Wang, Xiaoli; Jiang, Taineng; Lin, Qibo

doi:10.3390/catal5042039

Cited by 11 publications

(8 citation statements)

References 26 publications

(33 reference statements)

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“…Some efforts have been dedicated to finding active materials for glycerol oxidation based on CuNi-Al layered double hydroxides and Mg–Al layered double hydroxides (LDHs) in combination with various transition metals (Cr, Mn, Fe, Co, Cu). − Zhou et al incorporated various metals (Ni, Zn, Cu, Co, etc.) into Mg–Al LDHs and investigated the effect of the material composition on the catalytic performance for glycerol oxidation .…”

Section: Glycerol Oxidation Over Nonprecious Metalsmentioning

confidence: 99%

“…Wang et al reported in a series of studies the employment of sulphonato-salen-Cr 3+ complexes intercalated into Mg–Al LDHs (CrAlMg) as catalysts for the selective oxidation of glycerol under neutral or basic conditions. − In the first study in 2012, the authors demonstrated that a selectivity toward dihydroxyacetone of 44% at a glycerol conversion of 73% was achieved over CrAlMg catalysts with 3% H 2 O 2 as oxidant under base-free conditions (60 °C, 4 h reaction time, atmospheric pressure) . It is noteworthy to mention that the best performance of the catalyst was observed to be at neutral pH with a decrease in conversion and selectivity toward dihydroxyacetone with lower or higher pH value.…”

Section: Glycerol Oxidation Over Nonprecious Metalsmentioning

confidence: 99%

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Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation

2018

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Glycerol is a highly versatile molecule because of its three hydroxyl groups and can be transformed to a plethora of different value-added fine chemicals and products. It is an important byproduct in biodiesel production and, hence, produced in high amounts, which resulted in a high surplus flooding the market over the last decades. Thus, glycerol is regarded as a potential platform chemical, and many research efforts were devoted to find active catalysts to transform glycerol to various products via different catalytic processes. The selective oxidation reaction is one of the most promising reaction pathways to produce valuable fine chemicals used in the chemical and pharmaceutical industry. This Review describes the recent developments in selective glycerol oxidation to value-added products over heterogeneous catalysts. Particular emphasis is placed not only on newly developed catalysts based on supported noble-metal nanoparticles but also on catalysts containing nonprecious metals. The idea of using cost-efficient non-noble metals for glycerol oxidation is appealing from an economic point of view. Numerous parameters can influence the catalytic performance of the materials, which can be tuned by various synthetic approaches. The reasons for enhancements in activity are critically examined and put into perspective among the various studies. Moreover, during the past decade, many research groups also reported photocatalytic and, more scarcely, electrocatalytic pathways for glycerol oxidation, which are also described in detail herein and have otherwise found little attention in other reviews.

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Section: Glycerol Oxidation Over Nonprecious Metalsmentioning

confidence: 99%

Section: Glycerol Oxidation Over Nonprecious Metalsmentioning

confidence: 99%

Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation

2018

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“…The plot of the selectivity over the reaction time (Fig. 5) shows that the selectivity towards the C 3 products glyceric acid and tartronic acid increases within the first 1 to 1.5 h. At longer reaction times, increasing C-C cleavage into the C 2 and C 1 products oxalic acid, glycolic acid, and formic acid sets in, as it is also observed in the use of other non-noble 42,49 and noble 73 metal catalysts.…”

Section: View Article Onlinementioning

confidence: 66%

“…[37][38][39][40][41] However, there are only few reports on selective oxidation of glycerol in basic media with non-noble metal catalysts, such as with the toxic and carcinogenic cobalt, [42][43][44] layered double hydroxide supported transition metals, [45][46][47] or using hydrogen peroxide instead of molecular oxygen as an oxidizing agent. 48,49 Key factors for the fabrication of efficient supported catalysts are firstly a high dispersion of the active component on the support material; secondly, high surface areas of the support; and thirdly, large porosity to allow efficient diffusion of reactants to the active centers. A particularly intriguing support for Cu based catalysts is γ-Al 2 O 3 , in which Cu cations are atomically dispersed by occupying the tetrahedral and octahedral sites of Al 2 O 3 .…”

Section: Introductionmentioning

confidence: 99%

Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalysts

Schünemann

Tüysüz

2017

Catal. Sci. Technol.

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Glycerol is a major by-product of the biodiesel production and is therefore produced in high quantities. While currently there are limited possible applications for this highly functionalized molecule, glycerol can be a cheap and abundant feedstock for value-added products that are accessible by selective oxidation.Usually, the selective oxidation of glycerol utilizes expensive noble metal catalysts, such as Au, Pt, and Pd. Here we report the selective oxidation of glycerol in basic media, using ordered mesoporous Cu-Al 2 O 3 catalysts with various Cu loadings prepared by a facile soft-templating method. The materials were characterized in detail by nitrogen physisorption, vis-NIR spectroscopy, EDX, low-and wide-angle XRD, XPS, and TEM. Subsequently the reaction conditions for glycerol oxidation were optimized. The catalytic oxidation of glycerol yields C 3 products, such as glyceric acid and tartronic acid, and also C 2 and C 1 products, such as glycolic acid, oxalic acid, and formic acid. Moreover, the role of the solvent on the catalytic reaction was investigated, and the addition of various co-solvents to the aqueous reaction mixture was found to increase the initial reaction rate up to a factor of three. The trends of the initial reaction rates correlate well with the polarity of the water/co-solvent mixtures. The prepared Cu-Al 2 O 3 catalysts are a more costefficient and environmentally viable alternative to the reported noble metal catalysts.

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“…An interesting area of research for selective oxidation has seen a focus on lower temperature approaches in the liquid phase, as opposed to gas phase approaches at higher temperature [6]. In particular, the use of supported metal nanoparticles demonstrates great promise.…”

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confidence: 99%

Reflections on Catalytic Selective Oxidation: Opportunities and Challenges

Taylor

2017

Catalysts

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Currently, and looking forward, there is an ever increasing demand to perform chemical transformations with optimized atom and energy efficiency. In parallel, there is also growing interest in diversification of chemical feedstocks from more traditional ones. For example, effective and economic transformation of biorenewable chemical feedstocks and shale-gas, are just two that can be highlighted. These targets are demanding and challenging, and the required shift in industrial production of energy and chemicals will not be possible without advances in catalysis.This Special Issue focuses on selective catalytic oxidation, as it offers significant potential as an approach to achieving green and efficient chemical transformations of a broad range of substrates. Selective oxidation offers many challenges, not least of which is the control of product selectivity to the required products. Control of selectivity can be particularly challenging, as the desired products are less thermodynamically favoured compared to carbon oxides. This can be a particular problem if high temperatures are required to activate stable molecules, as these conditions can result in significant sequential over-oxidation of the desired products. A number of strategies have been developed to minimise such affects, and perhaps one of the most common is to utilise oxidants which are more active than molecular oxygen. A number of oxidants can be employed for selective catalytic oxidation, and depending on scale, reaction efficiency and relative cost of the oxidant and product, specific oxidants can be economic to use (e.g., hydrogen peroxide). However, the use of molecular oxygen, preferably directly from air, to achieve high yields of target products selectively must be the ultimate aim.There are some large scale selective catalytic oxidation processes that operate commercially. Formaldehyde is a bulk commodity chemical with a large worldwide market, it has many important uses, with major applications for thermosetting resins, manufacture of polyurethane foam, thermoplastics and adhesives. The two major industrial processes for production of formaldehyde are from the catalytic oxidation of methanol. One method is via an oxidation-dehydrogenation reaction using a silver-based catalyst. The alternative is direct oxidation of methanol to formaldehyde by oxygen using a mixed metal oxide iron molybdate catalyst [1]. The iron molybdate catalysed process is becoming increasingly prevalent, since it operates at a lower temperature than the silver catalysed process, and the catalyst is more robust. These advantages mean that the cost per tonne of formaldehyde production using iron molybdate catalysts is lower and yields a higher return on capital investment [2]. The industrial iron molybdate catalyst consists of a mixed metal oxide phase, Fe 2 (MoO 4 ) 3 , together with excess MoO 3 . Fe 2 (MoO 4 ) 3 is considered to be the active/selective phase, with MoO 3 being selective but with low activity, and Fe 2 O 3 unselective forming CO 2 . It has been reported...

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Selective Oxidation of Glycerol with 3% H2O2 Catalyzed by LDH-Hosted Cr(III) Complex

Cited by 11 publications

References 26 publications

Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation

Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation

Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalysts

Reflections on Catalytic Selective Oxidation: Opportunities and Challenges

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