Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu
We have investigated the synthesis and application of Au-Cu/CeO<sub>2</sub> (Cu: Au = 2) in the continuous gas phase (<i>P =</i> 1 atm; <i>T</i> = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2018-11-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/23/11/2905 |
| _version_ | 1831718673669160960 |
|---|---|
| author | Chiara Pischetola Laura Collado Mark A. Keane Fernando Cárdenas-Lizana |
| author_facet | Chiara Pischetola Laura Collado Mark A. Keane Fernando Cárdenas-Lizana |
| author_sort | Chiara Pischetola |
| collection | DOAJ |
| description | We have investigated the synthesis and application of Au-Cu/CeO<sub>2</sub> (Cu: Au = 2) in the continuous gas phase (<i>P =</i> 1 atm; <i>T</i> = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis revealed a close surface proximity of both metals in Au-Cu/CeO<sub>2</sub> <i>post</i>-TPR. XPS measurements suggest (support → metal) charge transfer to form Au<i><sup>δ</sup></i><sup>−</sup> and strong metal-support interactions to generate Cu<sup>0</sup> and Cu<sup>+</sup>. Au-Cu/CeO<sub>2</sub> promoted the sole formation of 2,5-dihydroxymethylfuran (DHMF) and 2-butanone in the HMF/2-butanol coupling with full hydrogen utilisation. Under the same reaction conditions, Au/CeO<sub>2</sub> was fully selective to DHMF in standard HMF hydrogenation (using an external hydrogen supply), but delivered a lower production rate and utilised less than 0.2% of the hydrogen supplied. Exclusive -C=O hydrogenation and -OH dehydrogenation is also demonstrated for the coupling of a series of <i>m-</i>substituted (-CH<sub>3</sub>, -CH<sub>2</sub>CH<sub>3</sub>, -CH<sub>2</sub>OH, -CF<sub>3</sub>, -N(CH<sub>3</sub>)<sub>2</sub>, -H) furaldehydes with alcohol (1-propanol, 1-butanol, 2-propanol, 2-butanol, cyclohexanol) dehydrogenation over Au-Cu/CeO<sub>2</sub>, consistent with a nucleophilic mechanism. In each case, we observed a greater hydrogenation rate and hydrogen utilisation efficiency with a 3⁻15 times lower E-factor in the coupling process relative to standard hydrogenation. Our results demonstrate the feasibility of using hydrogen generated in situ through alcohol dehydrogenation for the selective hydrogenation of <i>m-</i>furaldehydes with important industrial applications. |
| first_indexed | 2024-12-21T01:20:10Z |
| format | Article |
| id | doaj.art-0a60368f855a4c4b93fac10f276c8776 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-21T01:20:10Z |
| publishDate | 2018-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-0a60368f855a4c4b93fac10f276c87762022-12-21T19:20:39ZengMDPI AGMolecules1420-30492018-11-012311290510.3390/molecules23112905molecules23112905Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-CuChiara Pischetola0Laura Collado1Mark A. Keane2Fernando Cárdenas-Lizana3Chemical Engineering, School of Engineering and Physical Sciences, Heriot Watt University, Edinburgh EH14 4AS, Scotland, UKChemical Engineering, School of Engineering and Physical Sciences, Heriot Watt University, Edinburgh EH14 4AS, Scotland, UKChemical Engineering, School of Engineering and Physical Sciences, Heriot Watt University, Edinburgh EH14 4AS, Scotland, UKChemical Engineering, School of Engineering and Physical Sciences, Heriot Watt University, Edinburgh EH14 4AS, Scotland, UKWe have investigated the synthesis and application of Au-Cu/CeO<sub>2</sub> (Cu: Au = 2) in the continuous gas phase (<i>P =</i> 1 atm; <i>T</i> = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis revealed a close surface proximity of both metals in Au-Cu/CeO<sub>2</sub> <i>post</i>-TPR. XPS measurements suggest (support → metal) charge transfer to form Au<i><sup>δ</sup></i><sup>−</sup> and strong metal-support interactions to generate Cu<sup>0</sup> and Cu<sup>+</sup>. Au-Cu/CeO<sub>2</sub> promoted the sole formation of 2,5-dihydroxymethylfuran (DHMF) and 2-butanone in the HMF/2-butanol coupling with full hydrogen utilisation. Under the same reaction conditions, Au/CeO<sub>2</sub> was fully selective to DHMF in standard HMF hydrogenation (using an external hydrogen supply), but delivered a lower production rate and utilised less than 0.2% of the hydrogen supplied. Exclusive -C=O hydrogenation and -OH dehydrogenation is also demonstrated for the coupling of a series of <i>m-</i>substituted (-CH<sub>3</sub>, -CH<sub>2</sub>CH<sub>3</sub>, -CH<sub>2</sub>OH, -CF<sub>3</sub>, -N(CH<sub>3</sub>)<sub>2</sub>, -H) furaldehydes with alcohol (1-propanol, 1-butanol, 2-propanol, 2-butanol, cyclohexanol) dehydrogenation over Au-Cu/CeO<sub>2</sub>, consistent with a nucleophilic mechanism. In each case, we observed a greater hydrogenation rate and hydrogen utilisation efficiency with a 3⁻15 times lower E-factor in the coupling process relative to standard hydrogenation. Our results demonstrate the feasibility of using hydrogen generated in situ through alcohol dehydrogenation for the selective hydrogenation of <i>m-</i>furaldehydes with important industrial applications.https://www.mdpi.com/1420-3049/23/11/2905HMFcoupling hydrogenation/dehydrogenation<i>m-</i>furaldehydesalcoholsAu/CeO<sub>2</sub>Au-Cu/CeO<sub>2</sub> |
| spellingShingle | Chiara Pischetola Laura Collado Mark A. Keane Fernando Cárdenas-Lizana Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu Molecules HMF coupling hydrogenation/dehydrogenation <i>m-</i>furaldehydes alcohols Au/CeO<sub>2</sub> Au-Cu/CeO<sub>2</sub> |
| title | Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu |
| title_full | Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu |
| title_fullStr | Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu |
| title_full_unstemmed | Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu |
| title_short | Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu |
| title_sort | gas phase hydrogenation of furaldehydes via coupling with alcohol dehydrogenation over ceria supported au cu |
| topic | HMF coupling hydrogenation/dehydrogenation <i>m-</i>furaldehydes alcohols Au/CeO<sub>2</sub> Au-Cu/CeO<sub>2</sub> |
| url | https://www.mdpi.com/1420-3049/23/11/2905 |
| work_keys_str_mv | AT chiarapischetola gasphasehydrogenationoffuraldehydesviacouplingwithalcoholdehydrogenationoverceriasupportedaucu AT lauracollado gasphasehydrogenationoffuraldehydesviacouplingwithalcoholdehydrogenationoverceriasupportedaucu AT markakeane gasphasehydrogenationoffuraldehydesviacouplingwithalcoholdehydrogenationoverceriasupportedaucu AT fernandocardenaslizana gasphasehydrogenationoffuraldehydesviacouplingwithalcoholdehydrogenationoverceriasupportedaucu |