One-step upgrading of bio-based furfural to γ-valerolactone <i>via</i> HfCl<sub>4</sub>-mediated bifunctional catalysis

Li, Mingrui; Liu, Yixuan; Lin, Xialing; Tan, Jinyu; Yang, Song; Li, Hu

doi:10.1039/d1ra05637a

Cited by 13 publications

(5 citation statements)

References 51 publications

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“…This may be because the process of FUR to FE was very fast over the Zr-SBA-15_25 catalyst at a so high temperature (190 °C). Based on the above discussion and the report of the literature, , a possible reaction mechanism for the cascade conversion of FUR to GVL was proposed, as depicted in Scheme . In the CTH reaction (FUR to FAL and IPL to 4-HPE processes), the LAS and Lewis base site (LBS) play a synergistic role. , The Zr 4+ and O 2– in the Zr-SBA-15_ x catalyst provide the LAS and LBS, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…Based on the above discussion and the report of the literature, , a possible reaction mechanism for the cascade conversion of FUR to GVL was proposed, as depicted in Scheme . In the CTH reaction (FUR to FAL and IPL to 4-HPE processes), the LAS and Lewis base site (LBS) play a synergistic role. , The Zr 4+ and O 2– in the Zr-SBA-15_ x catalyst provide the LAS and LBS, respectively. At the beginning of the reaction process, the oxygen atom and hydrogen of the 2-propanol hydroxyl group are adsorbed on the LAS (Zr 4+ ) and LBS (O 2– ) of the catalyst, and the C=O bond of FUR is adsorbed on the LAS (Zr 4+ ).…”

Section: Resultsmentioning

confidence: 99%

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One-Pot Conversion of Furfural to Gamma-Valerolactone over Zr-SBA-15: Cooperation of Lewis and Brønsted Acidic Sites

Liu

Zhang

et al. 2023

ACS Appl. Nano Mater.

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A series of bifunctional Zr-SBA-15_x of varying molar Si/ Zr ratio x (15−730) with isolated Lewis and Brønsted acid sites were prepared by an in situ synthesis procedure and applied to the one-pot conversion of furfural (FUR) to gamma-valerolactone (GVL). These catalysts were detailed and characterized by XRF, XRD, N 2 physisorption, FTIR, SEM, TEM, NH 3 -TPD, and pyridine-DRIFT techniques. On all these Zr-SBA-15_x catalysts, the conversion of FUR was higher than 99%, while the GVL selectivity first increased and then decreased with decreasing x. A Zr-SBA-15_25 was identified as the best-performing catalyst, offering a 93.3% selectivity of GVL under optimized reaction conditions. The effects of reaction temperature, time, and solvent on catalytic performance were also investigated. Correlating the catalyst performance with the Brønsted acid site (BAS)/Lewis acid site (LAS) ratio uncovers that the balance between the LAS and the BAS would be the key to the higher catalytic performance. The possible reaction mechanism for the cascade conversion of FUR to GVL was proposed. Moreover, basic (lutidine and pyridine) additives were added, respectively, to the reaction solution to investigate their effects on catalytic performance, which provide a piece of evidence in support of the cooperative LAS−BAS bifunctional catalytic mechanism.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

One-Pot Conversion of Furfural to Gamma-Valerolactone over Zr-SBA-15: Cooperation of Lewis and Brønsted Acidic Sites

Liu

Zhang

et al. 2023

ACS Appl. Nano Mater.

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“…It is used as a green solvent, biofuel additive, and biopolymer precursor. 125 The Zrbased catalyst was used for the transformation of FA to GVL but allied with its own disadvantage of involving complex steps or a longer synthesis route as explained by Li et al 126 HfCl 4mediated bifunctional catalyst developed by Li et al, for the upgrade of FA to GVL. The synergistic effect of the catalyst, Lewis base species, promoted catalytic transfer hydrogenation process, whereas Bronsted acid catalysts assisted in the furan ring opening.…”

Section: Catalytic Hydrogenation Of Fa To Other Value-added Chemicalsmentioning

confidence: 99%

Review on Catalytic Hydrogenation of Biomass-Derived Furfural to Furfuryl Alcohol: Recent Advances and Future Trends

Racha,

Samanta,

Sreekantan

et al. 2023

Energy Fuels

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Biomass is one of the highly abundant renewable resources available that can be converted into several high-value-added products, including chemicals, biofuels, and advanced materials. To achieve net-zero emissions and improve biomass application, researchers around the world have recently focused on expanding biomass processing techniques to value-added products with the eventual goal of industrializing some of the products. In this review, we summarize lignocellulosic biomass derived furfural (FA) and its subsequent hydrogenation to furfuryl alcohol (FAL). This work reviews the various types of hydrogenation catalysts and their utility in the production of value-added products from FA. There will be an increase in the demand for selective catalysts and process technologies, as well as an increase in the challenges during valorization, as the usage of biomass to achieve carbon neutrality increases. The review aims to provide a concise overview of the advancements in this field and the potential for sustainable FAL production. In this paper, we present a simple strategy for selecting catalyst systems and associated process parameters that facilitate the highly efficient and selective valorization of FA to chemicals or fuel (bioadditives) for industrial use.

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“…In general, the β-H of secondary alcohols is easier to be removed from the transition state, so the hydrogen supply capacity of secondary alcohols is stronger than that of primary alcohols ( Elsayed et al, 2020 ; Li J. et al, 2021 ). However, the steric hindrance of secondary alcohols will gradually increase with the extension of the carbon chain, and excessive steric hindrance is not conducive to the formation of stable transition states, thereby reducing the hydrogen supply capacity ( Li M. et al, 2021 ; Li W. et al, 2021 ). Therefore, due to the small steric hindrance, 2-propanol was used as the H-donor to prepare GVL in most cases.…”

Section: Effect Of Reaction Parametersmentioning

confidence: 99%

Cascade Upgrading of Biomass-Derived Furfural to γ-Valerolactone Over Zr/Hf-Based Catalysts

Sun

Wang

et al. 2022

Front. Chem.

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Biomass feedstocks are promising candidates of renewable clean energy. The development and utilization of biological energy is in line with the concept of sustainable development and circular economy. As an important platform chemical, γ-valerolactone (GVL) is often used as green solvent and biofuel additive. Regarding this, the efficient synthesis of GVL from biomass derivative furfural (FF) has attracted wide attention recently, However, suitable catalyst with appropriate acid-base sites is required due to the complex reaction progress. In this Mini Review, the research progress of catalytic synthesis of GVL from furfural by Zr/Hf-based catalysts was reviewed. The different effects of Lewis acid-base and Brønsted acid sites in the catalysts on each steps in the reaction process were discussed firstly. Then the effects of regulation of acid-base sites in the catalysts was also studied. Finally, the advantages and challenges of Zr/Hf-based catalysts in FF converted to GVL system were proposed.

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One-step upgrading of bio-based furfural to γ-valerolactone via HfCl₄-mediated bifunctional catalysis

Abstract: The one-pot multi-step conversion of biomass-derived furfural to γ-valerolactone (GVL) with 64.5% yield is achieved via acid–base bifunctional catalysis enabled by HfCl4 in 2-propanol, and the recovered solid is active for transfer hydrogenation.

Cited by 13 publications

References 51 publications

One-Pot Conversion of Furfural to Gamma-Valerolactone over Zr-SBA-15: Cooperation of Lewis and Brønsted Acidic Sites

One-Pot Conversion of Furfural to Gamma-Valerolactone over Zr-SBA-15: Cooperation of Lewis and Brønsted Acidic Sites

Review on Catalytic Hydrogenation of Biomass-Derived Furfural to Furfuryl Alcohol: Recent Advances and Future Trends

Cascade Upgrading of Biomass-Derived Furfural to γ-Valerolactone Over Zr/Hf-Based Catalysts

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One-step upgrading of bio-based furfural to γ-valerolactone via HfCl4-mediated bifunctional catalysis

Abstract: The one-pot multi-step conversion of biomass-derived furfural to γ-valerolactone (GVL) with 64.5% yield is achieved via acid–base bifunctional catalysis enabled by HfCl4 in 2-propanol, and the recovered solid is active for transfer hydrogenation.

Cited by 13 publications

References 51 publications

One-Pot Conversion of Furfural to Gamma-Valerolactone over Zr-SBA-15: Cooperation of Lewis and Brønsted Acidic Sites

One-Pot Conversion of Furfural to Gamma-Valerolactone over Zr-SBA-15: Cooperation of Lewis and Brønsted Acidic Sites

Review on Catalytic Hydrogenation of Biomass-Derived Furfural to Furfuryl Alcohol: Recent Advances and Future Trends

Cascade Upgrading of Biomass-Derived Furfural to γ-Valerolactone Over Zr/Hf-Based Catalysts

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One-step upgrading of bio-based furfural to γ-valerolactone via HfCl₄-mediated bifunctional catalysis