Renewable bio-based routes to γ-valerolactone in the presence of hafnium nanocrystalline or hierarchical microcrystalline zeotype catalysts

Antunes, Margarida M.; Silva, Andreia F.; Fernandes, Auguste; Pillinger, Martyn; Ribeiro, M.F.; Valente, Anabela A.

doi:10.1016/j.jcat.2021.12.022

Cited by 13 publications

(13 citation statements)

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“…On the other hand, the introduction of Hf in HL gave 0.28Hf-HL possessing higher amounts of B and L acid sites (L increased from 82 to 128 μmol g −1 , and B increased from 45 to 71 μmol g −1 , respectively (Supplementary Table S3)). These results parallel those reported in the literature for Beta zeolites with and without hafnium (Antunes et al, 2022a).…”

Section: Characterization Of the Catalystssupporting

confidence: 92%

“…The zirconium catalyst 0.28Zr-D-HL(0.15) was less effective than its counterpart 0.28Hf-D-HL(0.15); the former led to less than half the GVL yield reached in the presence of 0.28Hf-D-HL(0.15) (9 and 22% GVL yield, at 200 °C/24 h) (Figure 7A). Hence, hafnium catalysts seem more promising for the target reaction, which parallels literature studies for Hfversus Zr-Beta (Antunes et al, 2022a), and Hf-versus Zr-and Sn-USY (Tang et al, 2019).…”

Section: General Considerationssupporting

confidence: 79%

“…Both AnL and LA may be converted to alkyl levulinates (LE) and γ-valerolactone (GVL) (Manzer, 2005;Liguori et al, 2015;Zhang, 2016;Lima et al, 2018;Yu et al, 2019;Dutta and Bhat, 2021;Antunes et al, 2022a). LE and GVL are attractive oxygenated fuel additives (Morone et al, 2015); e.g., butyl levulinate blends can improve fuel properties such as conductivity, combustion emission, freezing point (Di Bucchianico et al, 2022).…”

Section: Introductionmentioning

confidence: 99%

“…Both AnL and LA may be converted to alkyl levulinates (LE) and γ-valerolactone (GVL) ( Manzer, 2005 ; Liguori et al, 2015 ; Zhang, 2016 ; Lima et al, 2018 ; Yu et al, 2019 ; Dutta and Bhat, 2021 ; Antunes et al, 2022a ). LE and GVL are attractive oxygenated fuel additives ( Morone et al, 2015 ); e.g.…”

Section: Introductionmentioning

confidence: 99%

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Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics

Antunes

Silva²,

Fernandes³

et al. 2022

Front. Chem.

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The biomass-derived platform chemicals furfural and 5-(hydroxymethyl)furfural (HMF) may be converted to α-angelica lactone (AnL) and levulinic acid (LA). Presently, LA (synthesized from carbohydrates) has several multinational market players. Attractive biobased oxygenated fuel additives, solvents, etc., may be produced from AnL and LA via acid and reduction chemistry, namely alkyl levulinates and γ-valerolactone (GVL). In this work, hierarchical hafnium-containing multifunctional Linde type L (LTL) related zeotypes were prepared via top-down strategies, for the chemical valorization of LA, AnL and HMF via integrated catalytic transfer hydrogenation (CTH) and acid reactions in alcohol medium. This is the first report of CTH applications (in general) of LTL related materials. The influence of the post-synthesis treatments/conditions (desilication, dealumination, solid-state impregnation of Hf or Zr) on the material properties and catalytic performances was studied. AnL and LA were converted to 2-butyl levulinate (2BL) and GVL in high total yields of up to ca. 100%, at 200°C, and GVL/2BL molar ratios up to 10. HMF conversion gave mainly the furanic ethers 5-(sec-butoxymethyl)furfural and 2,5-bis(sec-butoxymethyl)furan (up to 63% total yield, in 2-butanol at 200°C/24 h). Mechanistic, reaction kinetics and material characterization studies indicated that the catalytic results depend on a complex interplay of different factors (material properties, type of substrate). The recovered-reused solids performed steadily.

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Section: Characterization Of the Catalystssupporting

confidence: 92%

Section: General Considerationssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

“…Both AnL and LA may be converted to alkyl levulinates (LE) and γ-valerolactone (GVL) ( Manzer, 2005 ; Liguori et al, 2015 ; Zhang, 2016 ; Lima et al, 2018 ; Yu et al, 2019 ; Dutta and Bhat, 2021 ; Antunes et al, 2022a ). LE and GVL are attractive oxygenated fuel additives ( Morone et al, 2015 ); e.g.…”

Section: Introductionmentioning

confidence: 99%

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Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics

Antunes

Silva²,

Fernandes³

et al. 2022

Front. Chem.

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“…Regarding the hydrogenation process for γ-valerolactone synthesis, metal catalysts such as Ru, Pt, and Ni ( Nemanashi et al, 2018 ; Wang Y et al, 2020 ; Maumela et al, 2021 ) are efficient for direct hydrogenation using gaseous H 2 as an H-donor in FAL hydrogenation and LA/levulinate ester lactonization. Compared with the use of H 2 reduction, reaction systems using alcohol as an H-donor for one-pot production of GVL from FAL via a Meerwein–Ponndorf–Verley (MPV) reduction can be effectively catalyzed by acid catalysts ( He et al, 2020 ; Antunes et al, 2022 ). As the ring-opening reaction of furfuryl alcohol (FOL) is also an acidic catalytic reaction, bifunctional catalysts with Brönsted/Lewis acid active sites have been greatly developed for the GVL synthesis via a MPV reaction ( Osatiashtiani et al, 2017 ).…”

Section: Introductionmentioning

confidence: 99%

Recent advances on bifunctional catalysts for one-pot conversion of furfural to γ-valerolactone

et al. 2022

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γ-Valerolactone (GVL) is one of the most valuable compounds derived from furfural (FAL), which has been industrially produced from agricultural byproducts like corn cobs. It is extremely challenging to synthesize GVL from FAL efficiently via a one-pot cascade reaction due to the need for multiple active sites in a single pot. By focusing on the aspects of one-pot synthesis of GVL from FAL, the authors aim to shed light on the rational design and utilization of environmentally friendly bifunctional catalysts with high efficiency in this reaction. Perspectives regarding future research opportunities in bi- or multi-functional catalysts for one-pot GVL synthesis are also discussed.

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Isolated Hf‐Isomorphously Substituted Zeolites for One‐Pot HMF Synthesis from Glucose

Srisuwanno

Saenluang

Prasertsab

et al. 2022

Advanced Sustainable Systems

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The direct conversion of glucose to 5‐hydroxymethylfurfural (HMF) is a crucial process in biorefinery. However, it still suffers from the rational design of highly efficient catalysts for one‐pot HMF production. Herein, the pioneering design of bifunctional hafnium (Hf)‐incorporated zeolites with fine‐tuned Brønsted/Lewis acidity and hierarchical features has been illustrated via one‐pot hydrothermally prepared protocols. Most importantly, the rationally designed catalyst presents the highly dispersed isolated Hf species located at the zeolite framework, which is close to the Brønsted acid site. The designed catalysts eventually reveal superb catalytic performances in glucose conversion (95.4 ± 1.1%) and HMF yield (63.2 ± 2.0%), as well as excellent catalytic stability, which are significantly improved compared to the well‐known tin‐beta zeolite. In addition, the catalytic activity and mechanistic studies of the Hf‐beta zeolite are confirmed by the density functional theory calculations.

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Renewable bio-based routes to γ-valerolactone in the presence of hafnium nanocrystalline or hierarchical microcrystalline zeotype catalysts

Cited by 13 publications

References 126 publications

Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics

Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics

Recent advances on bifunctional catalysts for one-pot conversion of furfural to γ-valerolactone

Isolated Hf‐Isomorphously Substituted Zeolites for One‐Pot HMF Synthesis from Glucose

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