Hydrothermally Stable, Conformal, Sulfated Zirconia Monolayer Catalysts for Glucose Conversion to 5-HMF

Osatiashtiani, Amin; Lee, Adam F.; Granollers, Marta; Brown, David R.; Olivi, Luca; Morales, Gabriel; Melero, Juan A.; Wilson, Karen

doi:10.1021/acscatal.5b00965

Cited by 144 publications

(112 citation statements)

References 55 publications

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“…The obtained results shows that both the Zr-MOFs possess acidic and basic sites; and that moreover, the quantity of these sites was much greater in MOF-808 than UiO-66(Zr). The origin of the acid-base sites was development from Zr-O-Zr or Zr-OH-Zr bonding present in the metal clusters of the Zr-MOFs, similar to the bonding observed in ZrO 2 and Zr(OH) 4 . Considering all the above mentioned points, a plausible reaction mechanism for this reaction was proposed in Scheme 2.…”

Section: Reaction Mechanismmentioning

confidence: 59%

“…5 . After five cycles, the catalyst lost one more BDC linker from its framework (combining BDC anions with two protons from OH of a hexanuclear Zr cluster, and a departure of neutral acid) leaving a material with the formula Zr 6 O 6 (OH) 4 (BDC) 4 . The charge imbalance generated due to linker deficiency was compensated by partial replacement of μ 3 -OH ions by μ 3 -O 2ions.…”

Section: Catalyst Recyclability and Characterizationsmentioning

confidence: 99%

“…For this purpose, two alternative Zr-MOFs (MOF-801 and MOF-808), which possesses metal center (Zr 6 O 4 (OH) 4 ) in their framework like UiO-66(Zr) were selected for this reaction. Table 2 represents the porous properties of the selected Zr-MOFs along with linker and molecular formulas.…”

Section: Evaluation Of Zr-mofs Possessing Different Physico-chemical mentioning

confidence: 99%

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Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium-based metal–organic frameworks

et al. 2016

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A series of highly crystalline, porous, zirconium-based metal-organic frameworks (Zr-MOFs) with different ligand functionality and porosity were applied for catalytic transfer hydrogenation of ethyl levulinate (EL) to form γ-valerolactone (GVL), using isopropanol as a hydrogen donor. The role of ligand functionality and the metal center of the Zr-MOFs were identified and reaction parameters were optimized, for selective production of GVL. Maximum yield of GVL (up to 92.7%) was achieved in 2 h at 200 o C with UiO-66(Zr). Interestingly, zirconium trimesate (MOF-808) emerged as the most suitable candidate, with the highest GVL formation rate (94.4 μmol/g/min) among the catalysts tested at 130 o C. It was also found effective in conversion of EL to GVL in an open system using the solvent refluxing method. Both the catalysts (UiO-66(Zr) and MOF-808) were recycled at least five times under their specified reaction conditions without notable change in catalytic activity and product selectivity. Fresh and recycled catalysts were characterized in detail using X-ray diffraction (XRD), N2 adsorption-desorption, thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) in order to understand the stability and structural changes that occurred in the catalysts. Finally, a plausible reaction mechanism was presented on the basis of active sites present in catalysts confirmed by characterization results.

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Section: Reaction Mechanismmentioning

confidence: 59%

Section: Catalyst Recyclability and Characterizationsmentioning

confidence: 99%

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Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium-based metal–organic frameworks

et al. 2016

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“…Among the heterogeneous acid catalysts developed, superacid catalysts exhibit excellent thermal stability and superior acidity, which have been applied to various types of acid‐catalyzed reactions such as isomerization, alkylation, esterification, and transesterification . Zirconia can retain a higher amount of sulfur than other metal oxides, and thus sulfated zirconia is one important type of superacid catalyst and obtained much attention …”

Section: Introductionmentioning

confidence: 99%

Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural

Shao

Sun

et al. 2019

Energy Tech

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Distinct crystal phases of an oxide affect the configuration of surface atoms, which might further affect coordination with sulfate during sulfonation for the preparation of SO42−/MxOy type of acid catalyst. Herein, such an effect is investigated with zirconia of the tetragonal or monoclinic phase as the model catalysts. The results show that sulfonation inhibits the transformation of zirconia from the tetragonal phase to the monoclinic phase, whereas the varied phase of zirconia also affects the bonding patterns of sulfate species with zirconia in sulfonation. The sulfated zirconia of monoclinic phase contains more abundant acidic sites and more Brønsted acid sites than that of sulfated zirconia of tetragonal phase. Consequently, the sulfated zirconia of monoclinic phase is more active than the sulfated zirconia of tetragonal phase for the conversion of furfuryl alcohol in ethanol and conversion of fructose in dimethyl sulfoxide, achieving the yield of ethyl levulinate of 96.4% and a high yield of 5‐hydroxymethylfurfural. The sulfated zirconia is not stable in protic solvent due to the leaching of sulfur species and the change in configurations of the sulfate species and the zirconium species, but in the aprotic solvent, they show good stability and recyclability.

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“…The support activates carbonyl group of LA, while ruthenium efficiently dissociates H 2 [31,33,34]. Ruthenium is an excellent hydrogenation catalyst, and ZrO 2 is a known support for hydrogenation, [40][41][42] dehydration, [43] esterification [38], and isomerization reactions [44][45][46][47]. The mechanical, thermal and chemical properties of ZrO 2 are favourable for these reactions.…”

Section: Resultsmentioning

confidence: 99%

Highly Selective Hydrogenation of Levulinic Acid to γ-Valerolactone Over Ru/ZrO2 Catalysts

et al. 2017

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We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO 2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrO x (OH) 4−2x and ZrO 2 ). Although the final compositions of the catalysts are the same, the pre-treatments strongly affect catalytic activity. Remarkably, one of the catalysts gave >99% yield of γ-valerolactone under mild conditions. This catalyst was also robust, and could be recycled at least four times without any loss in activity or selectivity. The activity is attributed to the presence of small ruthenium particles together with acidic sites on the catalyst.Graphical Abstract Pre-treatment changes the performance for ruthenium nanoparticles on zirconia supports, giving TONs over 3500 in the hydrogenation of levulinic acid to γ-valerolactone with over 99% yield. Electronic supplementary materialThe online version of this article

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Hydrothermally Stable, Conformal, Sulfated Zirconia Monolayer Catalysts for Glucose Conversion to 5-HMF

Cited by 144 publications

References 55 publications

Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium-based metal–organic frameworks

Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium-based metal–organic frameworks

Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural

Highly Selective Hydrogenation of Levulinic Acid to γ-Valerolactone Over Ru/ZrO2 Catalysts

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