Selective synthesis of γ-valerolactone from levulinic and formic acid over ZnAl mixed oxide

Belguendouz, Meriem N.E.H.; Gancedo, Juan Carlos Bada; Rapado, Paula; Ursueguía, David; Patiño, Yolanda; Faba, Laura; Bahmani, Abdellah; Dı́az, Eva; Ordóñez, Salvador

doi:10.1016/j.cej.2021.128902

Cited by 15 publications

(10 citation statements)

References 47 publications

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“…Surprisingly, the Fe-based MOFs performed comparably to the Pd catalyst but did not possess comparable material stability. For all materials, the conversion and subsequent turnover frequency (TOF) is low, especially when compared to like MOFs such as UiO-66(Zr) ( Valekar et al, 2016 ), likely a result of low reaction temperature ( Belguendouz et al, 2021 ).…”

Section: Resultsmentioning

confidence: 99%

Product selectivity and mass transport in levulinic acid transfer hydrogenation by monolithic MIL-100, MIL-88B and ZIF-8@Pd MOFs

McIntyre

Sáenz-Cavazos²,

Hunter‐Sellars³

2023

Front. Chem.

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The diffusion processes between adsorbent and adsorbate naturally play a significant role in the efficiency and selectivity of the heterogenous catalytic process. This paper considers the importance of diffusion processes in the transfer hydrogenation reaction of levulinic acid to γ-valerolactone by MIL-88B, MIL-100, and ZIF8@Pd monolithic catalysts. Over a period of five catalytic cycles, it was shown that the Fe-based catalysts can achieve similar conversions to the ZIF-8 supported Pd, with the only current limitation being the lower aqueous stability of these MOFs. Diffusion constants were calculated using the ZLC method, with micropore diffusion limitation found for ZIF-8 and MIL-100 monolithic frameworks at 2.7 x 10−8 and 4.6 x 10−8 cm2 s−1 respectively. This diffusion limitation was also confirmed by IR spectroscopy with an increasing concentration of C—H bands on the MOF substrate post-reaction. Mass transfer coefficients, also calculated by ZLC, revealed increased mass transport for the hydrophobic ZIF-8 framework, which perhaps aids in the γ-valerolactone selectivity over side products that are produced in the absence of catalytic material, as seen for MIL-88B and MIL-100 after multiple uses.

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Section: Resultsmentioning

confidence: 99%

Product selectivity and mass transport in levulinic acid transfer hydrogenation by monolithic MIL-100, MIL-88B and ZIF-8@Pd MOFs

McIntyre

Sáenz-Cavazos²,

Hunter‐Sellars³

2023

Front. Chem.

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“…It is well known that the conversion of LA to GVL is a temperature sensitive reaction. [33,34] It can also be found from Table 3 that the conversion of LA increases gradually with the increase of temperature. When the temperature reaches 160 °C, the conversion of LA reaches 100 %.…”

Section: Chemcatchemmentioning

confidence: 93%

Design of N‐Doped Carbon Materials Assisted Co−CoOx Anchoring on Mesoporous Silica Spheres Catalyst for Levulinic Acid Valorization

et al. 2022

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The design of robust catalyst was of great significance for the valorization of biomass platforms. Herein, an efficient Co@mSiO2−CN catalyst was constructed via a simple impregnation‐mixing‐pyrolysis strategy, which could give 100 % yield of γ‐valerolactone from levulinic acid for no less than five cycles under a relatively mild reaction conditions (160 °C, 1.5 MPa H2,3 h).The results of catalyst characterizations and comparative experiments showed that the introduction of nitrogen‐doped carbon materials promoted the dispersion of Co and enhanced the Lewis acidity of the catalyst, thereby promoting the dissociation of H2 and the activation of C−O, respectively. The synergistic effect between the hydrogenation metal sites and the Lewis acidic site ensures excellent activity of the catalyst.

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“…Very recently, Ordònez and coworkers prepared and tested different hydrotalcite‐like mixed oxides in the liquid phase GVL production. [ 185 ] By using Zn‐Al mixed oxide, a GVL yield of 90% of was achieved at 140 °C, with a 1:5 LA:FA. The mechanism proceeded through an acid catalyzed dehydration of LA to AL, and subsequent reduction to GVL.…”

Section: Lohcs In γ‐Valerolactone Productionmentioning

confidence: 99%

Liquid Organic Hydrogen Carriers (LOHCs) as H‐Source for Bio‐Derived Fuels and Additives Production

Valentini

Marrocchi

Vaccaro

2022

Advanced Energy Materials

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consumption combined with a resource efficient circular economy approach, with the final goal of minimizing the impact of health, safety, security and environment.In the design of a greener future, the replacement of depleting sources with renewable ones is at the center of a sustainable development. [2] Biomass is a natural, abundant, renewable, carbon-neutral source; its use represents a promising strategy to address the need for substituting fossil feedstock in the preparation of chemicals, fuels, and materials, besides energy production. [3][4][5][6][7][8][9][10][11][12][13][14] The major issues that limit the large-scale utilization of biomass in fuel production are the differences in cost and process efficiencies compared to those for fossil fuels. [15] After the Covid-19 crisis, this aspect has become even more evident, as reported by the International Agency of Energy, ultimately causing the first contraction in biofuel production over the past two decades. [16] The reduced transport fuel demand and the decreased petroleum-based fuel prices have transitorily lowered the economic interest for biofuel production. In this pandemic and emergency scenario, therefore, has emerged even more clearly the importance of developing efficient strategies for biomass conversion into fuels, making economically attractive the use of environmentally friendly renewable energy systems (Figure 1). [17] Among the plethora of biomass transformations, hydrogenation and hydrodeoxygenation reactions are widely used for decreasing the oxygen content of biomass-derived platforms to increase their potential as fuels. [18][19][20] In this context, as well as in the challenging goal of creating a decarbonized energy system, hydrogen plays a prominent role in the chemical industry. [21][22][23][24] It is important to notice that the vast majority of the worldwide hydrogen production (45-65 Mt/year) features a significant CO 2 footprint as a consequence of different hydrocarbon reforming processes (i.e., steam-reforming of fossil fuels, thermal cracking of natural gas, solar-thermal reforming of methane) or of coal gasification. [25] Several efforts have been directed during the past years toward the definition of possible effective approaches to a green H 2 production by water splitting. [26][27][28][29][30][31] To date, however, both water electrolysis and photo-driven water splitting are economically and energetically unfavorable, with a long way ahead to hold the promise of a zero-carbon energy system. Indeed, the associated energy demand as well as the low market prices of oxygen, inevitably co-produced from water electrolysis, hinder the shaping of a large-scale employment of this technology.Liquid organic hydrogen carriers (LOHCs) are attractive materials for their ability to generate in situ hydrogen that may be directly used to produce target biofuel precursors, fuels or fuel additives. Indeed, the replacement of fossil feedstock is an urgent necessity for shifting toward a carbon neutral energy economy. Several desired chemica...

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Selective synthesis of γ-valerolactone from levulinic and formic acid over ZnAl mixed oxide

Cited by 15 publications

References 47 publications

Product selectivity and mass transport in levulinic acid transfer hydrogenation by monolithic MIL-100, MIL-88B and ZIF-8@Pd MOFs

Product selectivity and mass transport in levulinic acid transfer hydrogenation by monolithic MIL-100, MIL-88B and ZIF-8@Pd MOFs

Design of N‐Doped Carbon Materials Assisted Co−CoOx Anchoring on Mesoporous Silica Spheres Catalyst for Levulinic Acid Valorization

Liquid Organic Hydrogen Carriers (LOHCs) as H‐Source for Bio‐Derived Fuels and Additives Production

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