Oxidation of Glycerol to Dicarboxylic Acids Using Cobalt Catalysts

Jin, Xin; Zhao, Meng; Zeng, Chun; Yan, Wenjuan; Song, Ziwei; Thapa, Prem; Subramaniam, Bala; Chaudhari, Raghunath V.

doi:10.1021/acscatal.6b00961

Cited by 73 publications

(55 citation statements)

References 30 publications

(60 reference statements)

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“…Little is known on glycerol oxidation in the presence of non‐noble metal catalysts . In another work, we reported lattice incorporated Co catalysts prepared by conventional co‐precipitation and modified sol‐gel methods . Co species can be atomically incorporated into hydrotalcite network during co‐precipitation, while in modified sol‐gel method, Co hydroxide species are immobilized on the surface of layered double hydroxide surface (Figure ).…”

Section: Figurementioning

confidence: 99%

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Jin

Fang

Wang

et al. 2018

The Chemical Record

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Conversion of biomass to chemicals provides essential products to human society from renewable resources. In this context, achieving atom‐economical and energy‐efficient conversion with high selectivity towards target products remains a key challenge. Recent developments in nanostructured catalysts address this challenge reporting remarkable performances in shape and morphology dependent catalysis by metals on nano scale in energy and environmental applications. In this review, most recent advances in synthesis of heterogeneous nanomaterials, surface characterization and catalytic performances for hydrogenation and oxidation for biorenewables with plausible mechanism have been discussed. The perspectives obtained from this review paper will provide insights into rational design of active, selective and stable catalytic materials for sustainable production of value‐added chemicals from biomass resources.

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Section: Figurementioning

confidence: 99%

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Jin

Fang

Wang

et al. 2018

The Chemical Record

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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: 55%

“…An attractive alternative to noble metals in selective oxidation reactions is copper, which was demonstrated to be active for the selective oxidation of various alcohols and polyols. [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.…”

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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“…60 % and 30 % for glyceric and tartronic acids, respectively 68) . Recently, Jin et al reported Co/Mg _ Al catalyst prepared by sol-gel method was found to be active for aqueous glycerol oxidation at 343 K with 0.1 MPa O2 and NaOH, forming tartronic acid with 64 % selectivity at 100 % glycerol conversion 69) . The Co species concentrated on the Mg3AlOx surface were proposed to catalyze this deep glycerol oxidation.…”

Section: Oxidative Transformations Of Glycerolmentioning

confidence: 99%

金属担持触媒を用いたバイオマス由来アルコールの選択的酸化反応

Nishimura

Ebitani

2017

J. Jpn. Petrol. Inst.

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Simple transformation of sustainable biomass-resources to value-added chemicals and fuels has become important to diminish our heavy reliance on decreasing petroleum resources. Biomass-derived materials with hydroxyl groups such as 5-hydroxymethylfurfural (HMF) and glycerol can be obtained from sugars directly and transesterification of triglycerides with methanol as by-products, respectively. These chemicals are versatile starting materials because hydroxyl groups can be easily converted to afford value-added chemicals and fuels under oxidative/reductive conditions using supported metal catalysts. This review overviews recent studies on supported metal catalyzed oxidation reactions of HMF, glycerol and biomass-derived aliphatic a,w-diols together with our research to develop highly efficient catalytic systems for bio-refining, based on petroleum conversion and nanotechnologies. Especially, role of external bases in the selective oxidation of biomass-derived alcohols will be discussed. We found that external base-free oxidation of HMF and glycerol is possible if basic supports are used. The activity of alloyed metal nanoparticles for selective oxidation of aliphatic a,w-diols to w-hydroxycarboxylic acids in basic aqueous media at high-pH value is also demonstrated. Keywords5-Hydroxymethylfurfural, Glycerol, Aliphatic a,w-diols, Selective oxidation, Supported metal catalyst, Bimetallic nanoparticle DOI: doi.org/10.1627/jpi.60.72 To whom correspondence should be addressed. E-mail: ebitani@jaist.ac.jp using molecular oxygen as the oxidant 18) . For example, Sahu and Dhepe compared the catalytic performance of various metal-oxide supported Pt catalysts with 0.1 MPa O2 in the presence of NaOH (1 equiv.) at 348 K for 12 h 19) . Under the same reaction conditions, Pt/ γ-A12O3, Pt/ZrO2, and Pt/C showed high catalytic activity with FDCA yields of 96, 94, and 89 %, respectively. In contrast, Pt supported on reducible TiO2 and CeO2 produced little FDCA (2 % and 8 % yields) even with ca. 100 % HMF conversion. Cai et al. reported superior catalytic performance of Au nanoparticles (1 nm size) encapsulated in the supercage of HY zeolite for selective HMF oxidation into FDCA with 99 % FDCA yield in water under 0.3 MPa O2 in the presence of NaOH at 333 K 20) . It has been reported the structures of Au nanoparticles and HY zeolite are stable under these conditions, and the Au/HY catalyst is reusable for several catalytic cycles. Negatively-charged Au nanoparticles may be responsible for this excellent catalytic performance.Pasini et al. reported AuCu bimetallic alloy catalyst (4.4 nm diameter) supported on TiO2 for HMF oxidation to FDCA under 1 MPa O2 in the presence of NaOH at 368 K to afford 99 % FDCA yield with complete HMF conversion 21) . A strong synergistic effect is evident with the addition of Cu to Au, especially for catalyst reusability without significant leaching of metal nanoparticles. However, stability test experiments showed the final product is mainly 5-hydroxymethyl-2-furancaoboxylic acid (HMFCA) instead...

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Oxidation of Glycerol to Dicarboxylic Acids Using Cobalt Catalysts

Cited by 73 publications

References 30 publications

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalysts

金属担持触媒を用いたバイオマス由来アルコールの選択的酸化反応

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