Selective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over vanadium modified Ir/SiO2 catalyst

Pholjaroen, Boonrat; Li, Ning; Huang, Yanqiang; Li, Lin; Wang, Aiqin; Zhang, Tao

doi:10.1016/j.cattod.2014.08.011

Cited by 57 publications

(47 citation statements)

References 36 publications

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“…Thus, bimetallic surfaces terminated by 3d transition metals are expected to have higher binding energies to the furan ring than the monometallic surfaces. It is also hypothesized that the synergistic effect between the Ir particle and the oxophilic metal oxide promotes the cleavage of the C−O bond in the furan ring . In the current work, Co is selected as an oxophilic 3d metal to modify the ring‐opening activity of the Ir(1 1 1) surface.…”

Section: Introductionsupporting

confidence: 89%

“…However, instead of the of ring‐opened product, 1,5‐PeD or other diols, only H 2 ( m / e =2) and CO ( m / e =28) were observed by using TPD. One possibility is that in the reactor experiments, the water in the solvent phase provides protons to the ring‐opened intermediates necessary for diol formation . Unfortunately, under the UHV conditions, the reaction intermediate, 1,5‐pentanedioxy or other dioxy species, cannot be hydrogenated to 1,5‐PeD.…”

Section: Resultsmentioning

confidence: 99%

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Ring‐Opening Reaction of Furfural and Tetrahydrofurfuryl Alcohol on Hydrogen‐Predosed Iridium(1 1 1) and Cobalt/Iridium(1 1 1) Surfaces

et al. 2017

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The ring‐opening of furfural is crucial for its conversion into value‐added chemicals such as 1,5‐pentanediol (1,5‐PeD), an important polymer precursor. Ir‐based catalysts have shown activity in ring‐opening reactions, and the use of an oxophilic metal additive is reported to be beneficial. To better understand the effect of an oxophilic metal on Ir for the opening of the furan ring, a combination of DFT calculations and experimental surface science studies were performed to investigate the ring‐opening of furfural and tetrahydrofurfuryl alcohol. The experimental results suggest that Co/Ir(1 1 1) has a higher ring‐opening activity for an unsaturated furan ring, however, the difference in activities between Ir and Co/Ir(1 1 1) is insignificant for a saturated furan ring. The DFT results reveal that Co/Ir(1 1 1) has a stronger interaction with an unsaturated furan ring than Ir(1 1 1); both surfaces show a weaker interaction with the saturated furan ring, which causes the lower ring‐opening activity than that of furfural.

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Section: Introductionsupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Ring‐Opening Reaction of Furfural and Tetrahydrofurfuryl Alcohol on Hydrogen‐Predosed Iridium(1 1 1) and Cobalt/Iridium(1 1 1) Surfaces

et al. 2017

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“…Adsorbed hydrogen on metal sites then hydrogenates the intermediate to the final product. Another proposed role of the oxide species in the ring‐opening chemistry is to provide binding sites for oxygen‐containing side groups, and the hydrogenated furan ring is opened on adjacent metal sites . Therefore, results from the current study, along with previous work, suggest that the selective ring‐opening of furanic compounds is unlikely to occur on monometallic surfaces and requires more than multiple types of active sites.…”

Section: Resultsmentioning

confidence: 99%

Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium

et al. 2016

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The selective ring-opening of cellulose-derived furanic molecules is a promising pathway for the production of industrially relevant linear oxygenates, such as 1,6-hexanediol. 2,5-Dimethylfuran (DMF) is employed as a model compound in a combined experimental and computational investigation to provide insights into the metal-catalyzed ring-opening. Ring-opening to 2-hexanol and 2-hexanone and ring-saturation to 2,5-dimethyltetrahydrofuran (DMTHF) are identified as two main parallel pathways. DFT calculations and microkinetic modeling indicate that DMF adsorbs on Ru in an open-ring configuration, which is potentially a common surface intermediate that leads to both ring-opening and ring-saturation products. Although the activation barriers for the two pathways are comparable, the formation of DMTHF is more thermodynamically favorable. In addition, steric interactions with co-adsorbed 2-propoxyl, derived from the solvent, and the oxophilic nature of Ru play key roles to determine the product distribution: the former favors less bulky, that is, ring-closed, intermediates, and the latter retards O-H bond formation. Finally, we show that the hydrodeoxygenation of oxygenated furanics, such as 5-methylfurfural and (5-methyl-2-furyl)methanol, on Ru occurs preferentially at oxygen-containing side groups to form DMF, followed by either ring-opening or ring-saturation.

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“…There were intense studies carried out on the production of high value-added chemical intermediates and end products from HMF using heterogeneous catalysts [8][9][10][11]. Tetrahyrofurfuryl alcohol (THFA) can be obtained through hydrogenation of furfural at a very high yield [12], and from which various useful chemicals, such as 1,5-pentadiol (15PDO) [13][14][15][16][17][18][19][20][21][22][23][24][25], 3,4-2H-dihydropyran (DHP) [26][27][28], and 4-penten-1-ol can be produced [29,30]. 15PDO, via a ring closure pathway, can form tetrahydropyran (THP) through the participation of strong solid acid catalysts or high-temperature water [31].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Tetrahydropyran from Tetrahydrofurfuryl Alcohol over Cu–Zno/Al2O3 under a Gaseous-Phase Condition

Zhang

Wang

et al. 2018

Catalysts

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Tetrahydropyran (THP) represents an O-containing hetero-cyclic compound that can be used as a promising solvent or monomer for polymer synthesis. In this work, Cu-ZnO/Al 2 O 3 catalysts have been prepared by a facile precipitation-extrusion method and used for the synthesis of THP through gaseous-phase hydrogenolysis of tetrahydrofurfuryl alcohol (THFA). The effect of the molar ratio of Cu/Zn/Al, reaction temperature, and hydrogen pressure was investigated. An 89.4% selectivity of THP was achieved at 270 • C and 1.0 MPa H 2 . Meanwhile, the optimum molar ratio of Cu/Zn/Al was determined to be 4:1:10. The Cu-ZnO/Al 2 O 3 catalyst exhibited high catalytic activity and stability for 205 h on-stream. A possible reaction mechanism involving several consecutive reactions was proposed: THFA was firstly rearranged to 2-hydroxytetrahydropyran (2-HTHP), followed by the dehydration of 2-HTHP to 3,4-2H-dihydropyran (DHP) over acid sites; finally, the DHP was hydrogenated to THP. The synergy of acid sites and metal sites of Cu-ZnO/Al 2 O 3 played an important role during the production of THP.

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Selective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over vanadium modified Ir/SiO2 catalyst

Cited by 57 publications

References 36 publications

Ring‐Opening Reaction of Furfural and Tetrahydrofurfuryl Alcohol on Hydrogen‐Predosed Iridium(1 1 1) and Cobalt/Iridium(1 1 1) Surfaces

Ring‐Opening Reaction of Furfural and Tetrahydrofurfuryl Alcohol on Hydrogen‐Predosed Iridium(1 1 1) and Cobalt/Iridium(1 1 1) Surfaces

Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium

Synthesis of Tetrahydropyran from Tetrahydrofurfuryl Alcohol over Cu–Zno/Al2O3 under a Gaseous-Phase Condition

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