Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over zirconium phosphates with adjustable Lewis and Brønsted acid sites

Li, Fukun; Cai, Zhenping; Li, Yingwen; Liu, Sijie; Li, Hongming; Long, Jinxing; Li, Xuehui

doi:10.1016/j.apcatb.2017.05.013

Cited by 230 publications

(114 citation statements)

References 60 publications

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“…Albeit that, the newly formed alkyl levulinate could also be converted to GVL in the presence of hydrogen donor solvent with longer reaction time. The above results clearly showed that primary alcohol was not efficient for the transfer hydrogenation reaction at mild condition, as also revealed by reported literatures . When using the commonly used isopropanol as hydrogen donor, the reaction provided 79% yield of GVL, at 89% EL conversion (Table , entry 14).…”

Section: Resultssupporting

confidence: 75%

“…Several systems showed high efficiency in the conversion of levulinate esters to GVL, which based on metal catalysts such as Ru, Pd, Zr, and others . Among these metals, Zr exhibits an outstanding reactivity in MPV reaction in different forms, such as ZrO 2 , ZrO(OH) 2 and ZrPO . However, the low surface area and non‐mesoporous structures of these oxides greatly prohibited the full utilization of Zr sites by limiting the full access of substrate to all the metal particles.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced Transfer Hydrogenation Activity of Zr‐Doped Mesoporous Silica through Sol‐Gel Method for the Reduction of Biomass‐Derived Unsaturated Carbon‐Oxygen Bonds

et al. 2018

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Efficient reduction of unsaturated functionalities of biomass derived molecules enables the production of new value‐added chemical. Herein, we reported a highly efficient and robust mesoporous silica catalyst (SBA‐15) doped with Zr metal sites for the reduction of biomass derived unsaturated molecules through transfer hydrogenation reaction. Specifically, ethyl levulinate was selected as model compound to investigate the reduction activities of the as‐prepared catalysts. An almost quantitative γ‐valerolactone (GVL) yield of 99%, through the ketone reduction and intramolecular cyclisation, was obtained at 160 °C for 18 h in the presence of hydrogenation donor 2‐Butanol (2‐BuOH). Comparative experiments among different type of Zr catalysts showed that the mesoporous structure of SBA‐15 was beneficial for maximizing the activity and the stability of the Zr sites though highly metal dispersion and metal‐chelation effect, respectively. Detailed studies on the catalyst characterization and optimization revealed the ratio of Si/Zr also affected the above reactivity. Mechanistic studies revealed that the interaction between polar C=O group was key to the reaction efficiency and poisoning experiments confirmed the existence of acid‐base sites for transfer hydrogenation process. The catalyst was also successfully recycled without much loss in reactivity. Finally, the catalyst was also applied to the reduction of a variety of unsaturated molecules with high yields.

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Section: Resultssupporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

Enhanced Transfer Hydrogenation Activity of Zr‐Doped Mesoporous Silica through Sol‐Gel Method for the Reduction of Biomass‐Derived Unsaturated Carbon‐Oxygen Bonds

et al. 2018

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“…ALs can be converted to a variety of high value‐added chemicals. For example, ALs can not only be further converted to γ‐Valerolactone, but also hydrolyzed to levulinate acid …”

Section: Introductionmentioning

confidence: 99%

Efficient Production of Ethyl Levulinate from Furfuryl Alcohol Catalyzed by Modified Zirconium Phosphate

et al. 2019

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The catalytic activities of various solid acid catalysts were investigated via the reaction of the direct alcoholysis from furfuryl alcohol to ethyl levulinate. The modified zirconium phosphate with sulfuric acid, prepared via a sol-gel method, exhibited excellent catalytic performance. By controlling the S/ Zr mole ratio of 0.5 at the catalyst preparation, the modified zirconium phosphate catalyst obtained catalytic activity of 97.8% EL yield and 100% FA conversion. The mechanism of enhancing catalytic activity of modified zirconium phosphate was investigated. Owing to the higher specific surface area and more Lewis and Brønsted acid sites, the modified zirconium phosphate catalyst displayed higher catalytic activity in comparison to unmodified zirconium phosphate. In addition, the modified zirconium phosphate catalyst was suitable for a broad temperature range. This modification method can provide a new way to enhance Lewis and Brønsted acidity of zirconium phosphate by adjusting S/Zr ratio rather than the P/ Zr ratio.

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“…The synergistic effect of Lewis acid‐base pair sites is verified to be responsible for achieving the high efficiency in the production of GVL from alkyl levulinates in alcohol via cascade Meerwein‐Ponndorf‐Verley (MPV) reduction and lactonization ,. Actually, the presence of weak Brønsted acid species is inevitable during reaction and the catalyst preparation process, which can be formed by the interaction of water with Lewis acidic centers on the catalyst surface or intrinsic hydroxy group ,. Moreover, the chemical stability and recyclability of the solid catalysts may be decreased by the formation of extra acidic species especially for metal oxides .…”

Section: Introductionmentioning

confidence: 99%

Porous Zr‐Bibenzyldiphosphonate Nanohybrid with Extra Hydroxy Species for Enhancive Upgrading of Biomass‐Based Levulinates

Yang¹,

Zhao²,

Li³

et al. 2018

ChemistrySelect

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Lewis acidic and/or basic sites are typically clarified to play a positive role in the cascade hydrogen transfer and lactonization process, while the influence of Brønsted acid species on the catalyst activity and stability is rarely studied. In this work, a new acid‐base bifunctional hybrid BPhZr with augmented average pore diameter was prepared from the assembly of ([1, 1’‐biphenyl]‐4,4’‐diylbis(methylene))diphosphonic acid with zirconium via a facile solvothermal method. The effects of reaction parameters, substrate scope, and metal ion type were investigated. Besides the promotional effect of moderate Lewis acid/base sites and improved texture properties, the presence of Brønsted acidic species (e. g., –OH) in BPhZr was demonstrated to positively promote the synthesis of γ‐valerolactone (GVL; ca. 95% yield) from levulinates via cascade transfer hydrogenation and lactonization. In comparison with previously reported catalysts, the BPhZr hybrid exhibited a superior activity in terms of TOF (3.2 h−1) and activation energy (21 kJ/mol) for the reaction. Moreover, BPhZr was found to be highly stable and recyclable in five consecutive cycles, showing no significant decrease in GVL yield and selectivity.

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Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over zirconium phosphates with adjustable Lewis and Brønsted acid sites

Cited by 230 publications

References 60 publications

Enhanced Transfer Hydrogenation Activity of Zr‐Doped Mesoporous Silica through Sol‐Gel Method for the Reduction of Biomass‐Derived Unsaturated Carbon‐Oxygen Bonds

Enhanced Transfer Hydrogenation Activity of Zr‐Doped Mesoporous Silica through Sol‐Gel Method for the Reduction of Biomass‐Derived Unsaturated Carbon‐Oxygen Bonds

Efficient Production of Ethyl Levulinate from Furfuryl Alcohol Catalyzed by Modified Zirconium Phosphate

Porous Zr‐Bibenzyldiphosphonate Nanohybrid with Extra Hydroxy Species for Enhancive Upgrading of Biomass‐Based Levulinates

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