Controlled hydrogenation of a biomass-derived platform chemical formed by aldol-condensation of 5-hydroxymethyl furfural (HMF) and acetone over Ru, Pd, and Cu catalysts

Gilcher, Elise B.; Chang, Hochan; Huber, George W.; Dumesic, James A.

doi:10.1039/d1gc04650k

Cited by 17 publications

(33 citation statements)

References 49 publications

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“…Apparent activation energies over Ru-523/C exhibit the highest energy barriers. This result is consistent with previous findings and describes the slow conversion to final products over the 313–393 K temperature range. Interestingly, the conversion of I-PHAHO to I-PHAH-OH is not observed over this catalyst.…”

Section: Resultssupporting

confidence: 94%

“…Additionally, conversion of the fully hydrogenated ketone, FHAHO, to the fully hydrogenated triol product, FHAH-OH, does not occur over Pd, leading to the formation of two final products. This agreement confirms the utility of the 5-step lumped reaction model examined previously …”

Section: Resultssupporting

confidence: 88%

“…The predictions of these models used to calculate these energy barriers are shown in the Supporting Information for the 313–393 K temperature range (Figures S3–S8). Upon incorporation of the intermediates, I-PHAHO and I-PHAH-OH, many trends in the expanded scheme agree with those observed in the lumped scheme examined in our previous work, but greater resolution in the detailed scheme highlights new understanding. Over Pd/Al 2 O 3 , the sequential hydrogenation of HAH to PHAHO is confirmed to be nearly barrierless (step 1).…”

Section: Resultssupporting

confidence: 81%

“…Furthermore, after the reaction at 453 K for 8 h, full conversion to the two products FHAHO and FHAH-OH was observed (Figure S2), indicating that the complete conversion of I-PHAHO and I-PHAH-OH to final products is possible over Pd at higher reaction temperatures. Over Ru/C catalysts, all intermediate products are fully converted to FHAH-OH at sufficiently long reaction times within the examined temperature range, as described in previous work …”

Section: Resultssupporting

confidence: 58%

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Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

et al. 2022

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We have developed lumped reaction schemes to optimize the yields of products from selective hydrogenations of HAH, a biomass-derived platform chemical produced by two-step aldol condensations of 5-hydroxymethyl furfural (H) with acetone (A). Reaction schemes consisting of 7, 9, and 11 steps were examined to describe the rates of formation of the observed products and reaction intermediates for hydrogenation of HAH over Ru and Pd catalysts, and a 3-step scheme was studied over Cu catalysts. Rate constants and activation energies were calculated using these reaction schemes, and we then apply the schemes to explore the effects of water addition on the hydrogenation pathways. The effects of water addition to isopropanol (IPA) solvents on the hydrogenation of HAH were markedly different over Pd, Ru, and Cu catalysts. Over the Pd catalyst, the addition of water to IPA increased hydrogenation rates and promoted the hydrogenation of furan rings. The addition of water to IPA yielded significant carbon losses over the Ru catalyst, and slowed hydrogenation steps over Cu, while significantly inhibiting hydrogenation of the ketone group. This behavior opened routes toward increased production rates of PHAHO (a partially hydrogenated, P, form of HAH containing a CO bond), a product in which the diene groups of the furan rings were not hydrogenated. The addition of water also allowed increased feed concentrations of HAH that were previously not possible in pure IPA solvents. The insights presented in this work provide a more mechanistic description of the hydrogenation of HAH, the behavior of specific intermediates, and the reactivity of key functional groups.

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Section: Resultssupporting

confidence: 94%

Section: Resultssupporting

confidence: 88%

Section: Resultssupporting

confidence: 81%

Section: Resultssupporting

confidence: 58%

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Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

et al. 2022

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“…Recently, there has been an increased concern about the development of sustainable methodologies [ 24 , 25 , 26 , 27 ], including procedures in water [ 28 , 29 , 30 , 31 , 32 ]. With this in mind, our group (i) focused on the valorization of raw renewable materials such as furfural and hydroxymethylfurfural (HMF) [ 33 , 34 , 35 ] and (ii) reported on the use of water as a green reaction media for the production of cyclopentenones [ 36 ] and, more recently, aminals from the condensation of aryl aldehydes with amines [ 37 ]. This addresses one of the 12 principles of green chemistry [ 24 ], namely the use of less hazardous/toxic chemicals.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Thioaminals in Water

2022

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The presence of sulfur–carbon bonds is transversal to several areas of chemistry, e.g., drug discovery, materials, and chemical biology. However, a lack of efficient and sustainable procedures for the preparation of thioaminals, the N,S-analogues of O,O-acetals, contributes to this functional group often being overlooked by the scientific community. In this work is described the formation of thioaminals in water promoted by copper(II) triflate.

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Mechanism and kinetics of self‐sensitized photocycloaddition of cyclohexenone and norbornene

Chen,

Zhang,

Guo

et al. 2024

AIChE Journal

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Solar‐driven conversion of renewable biomass resources into high‐density hydrocarbon fuels can effectively realize biomass valorization and renewable energy conversion. In this work, an efficient self‐sensitized [2 + 2] photocycloaddition process is explored to develop highly strained fuel with high yield using norbornene and biomass‐derived cyclohexenone as feedstocks. The enhancement mechanism is revealed by phosphorescent measurement and theoretical calculation, and a reasonable reaction path for self‐sensitized [2 + 2] co‐cycloaddition is proposed. When using methanol as solvent, the apparent activation energy of co‐cycloaddition is 21.37 W/mol, which is lower than that of self‐cycloaddition (31.57 W/mol). Importantly, the jet‐fuel‐range highly strained fuel has high density (0.986 g/cm3) and high volumetric net heat of combustion (41.14 MJ/L), which are 5.34% and 4.39% higher than those of JP‐10, respectively. This work proposes a green and effective pathway for the preparation of high‐performance hydrocarbon fuel with polycyclic‐asymmetric structure.

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Controlled hydrogenation of a biomass-derived platform chemical formed by aldol-condensation of 5-hydroxymethyl furfural (HMF) and acetone over Ru, Pd, and Cu catalysts

Abstract: We studied the hydrogenation at temperatures from 313 – 393 K of a biomass-derived platform molecule, 5-hydroxymethyl furfural (HMF)-Acetone-HMF (HAH) over Pd, Ru, and Cu based catalysts. HAH was selectively...

Cited by 17 publications

References 49 publications

Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

Preparation of Thioaminals in Water

Mechanism and kinetics of self‐sensitized photocycloaddition of cyclohexenone and norbornene

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