Zinc polyoxometalate on activated carbon: an efficient catalyst for selective oxidation of alcohols with hydrogen peroxide

Assady, Elham; Yadollahi, Bahram; Farsani, Mostafa Riahi

doi:10.1002/aoc.3332

Cited by 28 publications

(21 citation statements)

References 54 publications

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“…Furthermore, 1-phenylethanol and its derivatives also afforded complete conversion and more than 99% selectivity in relatively short reaction times (Table 6, entries 1 and 2). Commonly, the oxidation of aliphatic alcohols is much more difficult than aromatic ones [94][95][96]. Indeed, our catalytic protocol was also found to be effective for oxidation of secondary aliphatic alcohols to their corresponding ketones under the similar reaction conditions (Table 6, entries 7-9).…”

Section: Oxidation Of Different Types Of Alcohols Over 1%mentioning

confidence: 64%

Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO₃, –MnO₂, and –Mn₂O₃ Nanocomposites for Aerial Oxidation of Alcohols

Assal

Kuniyil

Shaik

et al. 2017

Journal of Chemistry

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Zinc oxide nanoparticles doped manganese carbonate catalysts [ % ZnO x -MnCO 3 ] (where = 0-7) were prepared via a facile and straightforward coprecipitation procedure, which upon different calcination treatments yields different manganese oxides, that is, [ % ZnO x -MnO 2 ] and [ % ZnO x -Mn 2 O 3 ]. A comparative catalytic study was conducted to evaluate the catalytic efficiency between carbonates and oxides for the selective oxidation of secondary alcohols to corresponding ketones using molecular oxygen as a green oxidizing agent without using any additives or bases. The prepared catalysts were characterized by different techniques such as SEM, EDX, XRD, TEM, TGA, BET, and FTIR spectroscopy. The 1% ZnO x -MnCO 3 calcined at 300 ∘ C exhibited the best catalytic performance and possessed highest surface area, suggesting that the calcination temperature and surface area play a significant role in the alcohol oxidation. The 1% ZnO x -MnCO 3 catalyst exhibited superior catalytic performance and selectivity in the aerial oxidation of 1-phenylethanol, where 100% alcohol conversion and more than 99% product selectivity were obtained in only 5 min with superior specific activity (48 mmol⋅g −1 ⋅h −1 ) and 390.6 turnover frequency (TOF). The specific activity obtained is the highest so far (to the best of our knowledge) compared to the catalysts already reported in the literatures used for the oxidation of 1-phenylethanol. It was found that ZnO x nanoparticles play an essential role in enhancing the catalytic efficiency for the selective oxidation of alcohols. The scope of the oxidation process is extended to different types of alcohols. A variety of primary, benzylic, aliphatic, allylic, and heteroaromatic alcohols were selectively oxidized into their corresponding carbonyls with 100% convertibility without overoxidation to the carboxylic acids under base-free conditions.

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Section: Oxidation Of Different Types Of Alcohols Over 1%mentioning

confidence: 64%

Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO₃, –MnO₂, and –Mn₂O₃ Nanocomposites for Aerial Oxidation of Alcohols

Assal

Kuniyil

Shaik

et al. 2017

Journal of Chemistry

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“…Hence, it can be said that the aerobic oxidation of substituted benzylic alcohols in presence of ZnO x (1%)-MnCO 3 /(1%)HRG nanocomposite is influenced by two factors, electronic density and steric hindrance. Conversely, the oxidation of aliphatic alcohols is much more difficult than that of benzylic alcohols [100,105]. In this regard, the oxidation of citronellol into citronellal occurs in longer time by compared to aromatic ones, may be owing to the absence of conjugation in the β-position of the OH group (Table 7, entry 21).…”

Section: Oxidation Of Wide Range Of Benzylic and Aliphatic Alcoholsmentioning

confidence: 99%

Mixed Zinc/Manganese on Highly Reduced Graphene Oxide: A Highly Active Nanocomposite Catalyst for Aerial Oxidation of Benzylic Alcohols

et al. 2017

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Nanocomposites of highly reduced graphene oxide (HRG) and ZnO x nanoparticles doped manganese carbonate containing different percentages of HRG were prepared via a facile co-precipitation method.The prepared sample calcined at 300 • C yielded i.e., ZnO x (1%)-MnCO 3 /(X%)HRG (where X = 0-7), calcination at 400 • C and 500 • C, yielded different manganese oxides i.e., ZnO x (1%)-MnO 2 /(X%)HRG and ZnO x (1%)-Mn 2 O 3 /(X%)HRG respectively. The prepared catalyst were subjected to catalytic evaluation and a comparative catalytic study between carbonates and oxides for the liquid-phase aerobic oxidation of benzylic alcohols to corresponding aldehydes using molecular oxygen as an eco-friendly oxidant without adding additives or bases. The influence of various parameters such as percentage of HRG, reaction time, catalyst amount, calcination and reaction temperature was systematically examined to optimize reaction conditions using oxidation of benzyl alcohol as a substrate model. It was found that the catalytic performance is remarkably enhanced after using HRG as catalyst co-dopant for the aerobic oxidation of alcohols, possibly owing to the presence of carbon defects and oxygenated functional groups on HRG surface. The as-synthesized catalysts were characterized by SEM, EDX, XRD, Raman, TGA, BET, and FT-IR. Under optimal conditions, the catalyst with composition ZnO x (1%)-MnCO 3 /(1%)HRG calcined at 300 • C exhibited remarkable specific activity (57.1 mmol·g −1 ·h −1 ) with 100% conversion of benzyl alcohol and more than 99% product selectivity within extremely short time (7 min). The as-prepared catalyst was re-used up to five consecutive times without significant decrease in its activity and selectivity. To the best of our knowledge, the achieved specific activity is the highest so far compared to the earlier reported catalysts used for the benzyl alcohol oxidation. A wide range of substituted benzylic and aliphatic alcohols were selectively oxidized into their corresponding aldehydes with complete convertibility and selectivity in short reaction times without over-oxidation to the acids. Due to their significant low cost, superior reproducibility, excellent catalytic efficiency, the ZnO x (1%)-MnCO 3 /(X%)HRG nanocomposites possess several application prospect in other organic chemistry reactions.

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“…Moreover, 1-phenylethanol and its derivatives also exhibited complete conversion and more than 99% selectivity in relatively short reaction times (Table 6, entries 1 and 2). Commonly, the oxidation of aromatic alcohols is much easier than aliphatic counterparts [84][85][86]. Besides, compared to secondary aromatic alcohols the oxidation of secondary aliphatic alcohols to their corresponding ketones exhibited relatively low reactivity towards oxidation process (Table 6, entries 7-9).…”

Section: Oxidation Of a Variety Of Alcohols With Molecular Oxygenmentioning

confidence: 99%

Comparative Catalytic Evaluation of Nano-ZrO_x Promoted Manganese Catalysts: Kinetic Study and the Effect of Dopant on the Aerobic Oxidation of Secondary Alcohols

Assal

Kuniyil

Khan

et al. 2017

Advances in Materials Science and Engineering

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This work reports the zirconia (ZrO x ) nanoparticles doped MnCO 3 catalysts prepared by facile and simple coprecipitation technique and the synthesis of zirconia-manganese carbonate [X% ZrO x -MnCO 3 ] (where % = 0-7%) catalyst which upon calcination at 400 ∘ C is converted to zirconia-manganese dioxide [1% ZrO x -MnO 2 ] and when calcined at 500 ∘ C is converted to zirconiamanganic trioxide [1% ZrO x -Mn 2 O 3 ]. A comparative catalytic study was performed to investigate the catalytic efficiency between carbonate and oxides for the selective oxidation of 1-phenylethanol by using molecular O 2 as a clean oxidant. The influence of several parameters such as w/w% of ZrO x , reaction time, calcination temperature, catalyst amount, and reaction temperature has been thoroughly examined using oxidation of 1-phenylethanol as a model substrate. The 1% ZrO x -MnCO 3 precalcined at 300 ∘ C exhibited the best catalytic efficiency. It was found that ZrO x nanoparticles also play an essential role in enhancing the effectiveness of the catalytic system for the aerobic oxidation of alcohols. Furthermore, the physical and chemical properties of synthesized catalysts were evaluated by microscopic and spectroscopic techniques. An extremely high specific activity of 40 mmol⋅g −1 ⋅h −1 with a 100% conversion of oxidation product and selectivity of >99% was achieved within extremely short reaction time (6 min).

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Zinc polyoxometalate on activated carbon: an efficient catalyst for selective oxidation of alcohols with hydrogen peroxide

Cited by 28 publications

References 54 publications

Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO₃, –MnO₂, and –Mn₂O₃ Nanocomposites for Aerial Oxidation of Alcohols

Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO₃, –MnO₂, and –Mn₂O₃ Nanocomposites for Aerial Oxidation of Alcohols

Mixed Zinc/Manganese on Highly Reduced Graphene Oxide: A Highly Active Nanocomposite Catalyst for Aerial Oxidation of Benzylic Alcohols

Comparative Catalytic Evaluation of Nano-ZrO_x Promoted Manganese Catalysts: Kinetic Study and the Effect of Dopant on the Aerobic Oxidation of Secondary Alcohols

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Zinc polyoxometalate on activated carbon: an efficient catalyst for selective oxidation of alcohols with hydrogen peroxide

Cited by 28 publications

References 54 publications

Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO3, –MnO2, and –Mn2O3 Nanocomposites for Aerial Oxidation of Alcohols

Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO3, –MnO2, and –Mn2O3 Nanocomposites for Aerial Oxidation of Alcohols

Mixed Zinc/Manganese on Highly Reduced Graphene Oxide: A Highly Active Nanocomposite Catalyst for Aerial Oxidation of Benzylic Alcohols

Comparative Catalytic Evaluation of Nano-ZrOx Promoted Manganese Catalysts: Kinetic Study and the Effect of Dopant on the Aerobic Oxidation of Secondary Alcohols

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Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO₃, –MnO₂, and –Mn₂O₃ Nanocomposites for Aerial Oxidation of Alcohols

Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO₃, –MnO₂, and –Mn₂O₃ Nanocomposites for Aerial Oxidation of Alcohols

Comparative Catalytic Evaluation of Nano-ZrO_x Promoted Manganese Catalysts: Kinetic Study and the Effect of Dopant on the Aerobic Oxidation of Secondary Alcohols