Highly selective hydrogenation and hydrogenolysis using a copper-doped porous metal oxide catalyst

Petitjean, L.; Gagne, Raphael; Beach, Evan S.; Xiao, Dequan; Anastas, Paul T.

doi:10.1039/c5gc01464f

Cited by 50 publications

(47 citation statements)

References 37 publications

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“…[17] Co/N-C-600 gave an early quantitative MMP yield after 4h at al ower temperature of 170 8Ca nd 10 bar H 2 .O bviously,t he use of non-noble metal catalysts at lower temperatures showedg reat potential for practical application. [20] Many undetected side reactions took place in the Mo 2 C/AC catalytic system.A lthough hydrotalcite-supported Cu produced MMP with 90 %s electivity at full conversion of vanillin, the reactionw as performed under harsh conditions, at 180 8Ca nd 40 bar H 2 ,w ith al ong reaction time of 18 h. [21] We attributet he high catalytic activity of Co/N-C-600 to the synergistic effect of nitrogen and Co nanoparticles in the activation of H 2 to promote the reduction process (as discussed in our previousw ork). For example, although activatedc arbon-supported molybdenumc arbide( Mo 2 C/AC) nanoparticles produced high vanillin conversion at 20 bar H 2 and 100 8C, the selectivity to MMP andt he total carbon balance weret oo low.…”

Section: Comparison Of the Performance Of Co/n-c-600 With Other Catalmentioning

confidence: 78%

“…Of particular note is that the deoxygenation of vanillin over the Co/N-C-600 catalyst can be performed under atmosphericp ressure of H 2 ,e nabling the use of commong lass reactors, which shows great promise for practical application without need for specialized instruments. [20][21][22] The highest MMP yield was 99.0 % at full vanillinc onversion after 4h at 170 8Ca nd 10 bar pressure. To our knowledge,t he catalytic transformationo fv anillin into MMP under atmospheric pressure has not been reported to date.…”

Section: The Effect Of Hydrogen Pressure On the Deoxygenation Of Vanimentioning

confidence: 97%

“…[11] To overcome the drawbackso f homogeneous catalysts, great efforts have been devoted to the development of heterogeneous catalysts for this reaction. [20,21] Owing to the intrinsic low activity of non-noblem etal catalysts, their use in the reduction of vanillin is restricted by their low resistance to deactivation and low energy efficiency caused by the severe reaction conditions. For example, Wang and co-workers reported that the N-doped-carbon-supported Pd exhibits much higherc atalytic activityi nt he hydrodeoxygenation of vanillin than other Pd catalysts supported on metal oxidesa nd activated carbon.…”

mentioning

confidence: 99%

“…[20,21] Owing to the intrinsic low activity of non-noblem etal catalysts, their use in the reduction of vanillin is restricted by their low resistance to deactivation and low energy efficiency caused by the severe reaction conditions. Af ew non-noble metal catalysts have been reported for the hydrodeoxygenation of vanillini nto MMP.…”

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confidence: 99%

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Cobalt Nanoparticles Supported on Nitrogen‐Doped Carbon: An Effective Non‐Noble Metal Catalyst for the Upgrade of Biofuels

et al. 2018

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A new method has been developed for the deoxygenation of vanillin to produce 2-methoxy-4-methylphenol (MMP) as a promising liquid fuel over a heterogeneous non-noble metal catalyst. Cobalt nanoparticles supported on nitrogen-doped carbon (Co/N-C-600) exhibit high activity and stability for the deoxygenation of vanillin into MMP under mild conditions (150 °C, 10 bar H ). Nearly quantitative MMP yield is obtained in isopropanol after 8 h at 150 °C and 10 bar H pressure. According to the distribution of products with time, the deoxygenation of vanillin into MMP mainly proceeds through the hydrogenation of vanillin into vanillyl alcohol and the subsequent hydrogenolysis of vanillyl alcohol into MMP, of which the latter is the rate-determining step, owing to a much higher activation energy. Moreover, after being recycled several times, the loss of catalytic activity is negligible, which demonstrates that the Co/N-C-600 catalyst shows good resistance to deactivation.

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Section: Comparison Of the Performance Of Co/n-c-600 With Other Catalmentioning

confidence: 78%

Section: The Effect Of Hydrogen Pressure On the Deoxygenation Of Vanimentioning

confidence: 97%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Cobalt Nanoparticles Supported on Nitrogen‐Doped Carbon: An Effective Non‐Noble Metal Catalyst for the Upgrade of Biofuels

et al. 2018

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“…Nagaraja et al reported a highly efficient Cu/MgO catalyst for vapour phase hydrogenation of furfural to furfuryl alcohol, in which high conversion of furfural (98.0%) and high selectivity toward furfuryl alcohol (98.0%) were achieved . Recently, Petitjean et al prepared a Cu‐PMO (PMO: porous metal oxide) catalyst and applied it into HDO of vanillin, which gave a 100% conversion and 90% MMP selectivity under 180 °C and 4.0 MPa H 2 pressure within18 h . Moreover, the corresponding catalyst could be extended to catalytic reduction of other unsaturated compounds.…”

Section: Introductionmentioning

confidence: 99%

Highly Dispersed Copper Nanoparticles Supported on Activated Carbon as an Efficient Catalyst for Selective Reduction of Vanillin

Fan

Chen

Han

et al. 2018

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Highly dispersed copper nanoparticles (Cu NPs) supported on activated carbon (AC) are effectively synthesized by one-pot carbothermal method at temperature range of 400-700 °C. The X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller analysis reveal that Cu NPs with diameters of 20-30 nm are evenly anchored in carbon matrix. The 15 wt%-Cu/AC-600 catalyst (derived at 600 °C) exhibits best bifunctional catalysis of aqueous-phase hydrodeoxygenation (HDO) and organic-phase transfer-hydrogenation reaction (THR) to selectively transform vanillin to 2-methoxy-4-methylphenol (MMP). In HDO of vanillin, the as-prepared catalyst achieves a 99.9% vanillin conversion and 93.2% MMP selectivity under 120 °C, 2.0 MPa H within 5 h. Meanwhile, near-quantitative vanillin conversion and 99.1% MMP selectivity are also obtained under 180 °C within 5 h in THR of vanillin by using 2-propanol as hydrogen donor. The transforming pathways of vanillin are also proposed: vanillin is transformed into MMP via intermediate of 4-hydroxymethyl-2-methoxyphenol in HDO case and by direct hydrogenolysis of vanillin in THR course. More importantly, the activity and the selectivity do not change after 5 cycles, indicating the catalyst has excellent stability. The Cu-based catalyst is relatively cheap and preparation method is facile, green, and easy scale-up, thus achieving a low-cost transformation of biomass to bio-oils and chemicals.

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Copper‐Decorated Iron Carbide Nanoparticles Heated by Magnetic Induction as Adaptive Multifunctional Catalysts for the Selective Hydrodeoxygenation of Aldehydes

Lin

Hetaba

Chaudret

et al. 2022

Advanced Energy Materials

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an important transformation for the fine chemical and pharmaceutical industries, and is also considered an important enabler for chemical energy conversion and especially for the upgrading of biomass feedstock to value-added chemicals. [1] In particular, the selective hydrodeoxygenation of renewable platform chemicals such as furfural, hydroxymethylfurfural and vanillin has attracted tremendous attention in the past years. [2] This requires selectively hydrodeoxygenating aromatic aldehydes, while leaving the aromaticity of the ring untouched. To provide alternatives to stoichiometric methods that involve toxic reagents and hazardous wastes (Wolff-Kishner, [3] Clemmensen [4] ), recent efforts focused on the development of catalytic systems possessing such reactivity. While noble metal catalysts often suffer from low selectivity due to undesired aromatic hydrogenation, [5] promising results for the selective reduction of aromatic carbonyls have been obtained using bimetallic nanoparticles as well as 3d metal catalysts. [6] However, the development of catalytic systems fulfilling the requirements of high yields, selectivity, stability, productivity, safety, and environmental compatibility remains a challenge. [7] In addition, with the rise of alternative renewable energy sources, the permanent evolution of catalysts and catalytic processes is crucial to face the inevitable variations in electricity production. In particular, energy efficiency, benignity of reaction conditions, and adaptivity to intermittent energy supply are parameters of ever-increasing importance. [8] In this context, magnetic induction offers the possibility to heat directly magnetic nanoparticles (e.g., catalysts) in an extremely localized, rapid, and energy efficient manner, saving the need to heat the complete reactor environment (solvent, reactor parts, etc.). [8c,9] In turn, this may result in milder overall process temperatures and lower energy consumption. In addition, the rapid heating and cooling of nanoparticles activated by magnetic induction is of great interest to address the challenges associated to the use of fluctuating renewable energy. Magnetic induction is a mature technology that is used for decades also on industrial scale (e.g., metallurgy), and that can thus offer promising new perspectives for process intensification, in particular of small to medium-size processes requiring constant heating.Copper-decorated iron carbide nanoparticles (Cu@ICNPs) are prepared following an organometallic approach, producing a multifunctional catalytic system that can be heated magnetically. ICNPs act as heating agents, generating thermal energy from the alternating current magnetic field in an extremely localized, rapid, and efficient manner, thereby heating and activating the catalytically active Cu-containing NPs present at their surface. Upon exposure to magnetic induction, the Cu@ICNPs catalyst is capable of selectively hydrodeoxygenating aromatic aldehydes under mild observable conditions (≈100 °C, 3 bar H 2 ), without hydrogenatio...

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Highly selective hydrogenation and hydrogenolysis using a copper-doped porous metal oxide catalyst

Abstract: A copper-doped porous metal oxide catalyst in combination with hydrogen shows selective and quantitative hydrogenolysis of benzyl ketones and aldehydes, and hydrogenation of alkenes.

Cited by 50 publications

References 37 publications

Cobalt Nanoparticles Supported on Nitrogen‐Doped Carbon: An Effective Non‐Noble Metal Catalyst for the Upgrade of Biofuels

Cobalt Nanoparticles Supported on Nitrogen‐Doped Carbon: An Effective Non‐Noble Metal Catalyst for the Upgrade of Biofuels

Highly Dispersed Copper Nanoparticles Supported on Activated Carbon as an Efficient Catalyst for Selective Reduction of Vanillin

Copper‐Decorated Iron Carbide Nanoparticles Heated by Magnetic Induction as Adaptive Multifunctional Catalysts for the Selective Hydrodeoxygenation of Aldehydes

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