Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments
Supported Fe-Ni catalysts have been reported for their activity and selectivity in the hydrogenation of unsaturated organic molecules. However, the control of the size and composition of the bimetallic nanoparticles remains a bottleneck when oxide-supported catalysts are prepared by impregnation, an...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Journal article |
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Elsevier
2018
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| _version_ | 1797082771117572096 |
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| author | Shi, D Yang, Q Peterson, C Lamic-Humblot, A Girardon, J Griboval-Constant, A Stievano, L Sougrati, M Briois, V Bagot, P Wojcieszak, R Paul, S Marceau, E |
| author_facet | Shi, D Yang, Q Peterson, C Lamic-Humblot, A Girardon, J Griboval-Constant, A Stievano, L Sougrati, M Briois, V Bagot, P Wojcieszak, R Paul, S Marceau, E |
| author_sort | Shi, D |
| collection | OXFORD |
| description | Supported Fe-Ni catalysts have been reported for their activity and selectivity in the hydrogenation of unsaturated organic molecules. However, the control of the size and composition of the bimetallic nanoparticles remains a bottleneck when oxide-supported catalysts are prepared by impregnation, and alternative procedures should be investigated. Starting with Ni(II) and Fe(II) sulfates as precursor salts, deposition-precipitation with urea (DPU) on SiO2 in an inert atmosphere initially leads to the formation of an ill-crystallized Fe-containing Ni(II) 1:1 phyllosilicate, which reduces under hydrogen at 700°C into bimetallic fcc Fe-Ni nanoparticles of 5.4 nm in average. Compared with the composition of the DPU solution (50 Fe at %, 50 Ni at %), an excess of Ni is detected on the catalyst (32 Fe at %, 68 Ni at %), due to the preferential reaction of Ni2+ ions with silica. In situ X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy show that the reduction of Fe ions to the metallic state is triggered by the formation of reduced Ni centers above 350°C, and, from then, proceeds progressively, resulting in an excess of Fe in the outer shells of the bimetallic particles. The composition of individual Fe-Ni particles evidences a standard deviation of 8%. The bimetallic Fe-Ni/SiO2 catalyst gives high yields in furfuryl alcohol in the hydrogenation of furfural, in contrast with an analog Ni/SiO2 catalyst that favours side-reactions of etherification, hydrogenolysis and hydrogenation of the furan ring. |
| first_indexed | 2024-03-07T01:32:34Z |
| format | Journal article |
| id | oxford-uuid:94155505-570d-4ad1-a9e0-bee047deb03d |
| institution | University of Oxford |
| last_indexed | 2024-03-07T01:32:34Z |
| publishDate | 2018 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | oxford-uuid:94155505-570d-4ad1-a9e0-bee047deb03d2022-03-26T23:36:47ZBimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatmentsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:94155505-570d-4ad1-a9e0-bee047deb03dSymplectic Elements at OxfordElsevier2018Shi, DYang, QPeterson, CLamic-Humblot, AGirardon, JGriboval-Constant, AStievano, LSougrati, MBriois, VBagot, PWojcieszak, RPaul, SMarceau, ESupported Fe-Ni catalysts have been reported for their activity and selectivity in the hydrogenation of unsaturated organic molecules. However, the control of the size and composition of the bimetallic nanoparticles remains a bottleneck when oxide-supported catalysts are prepared by impregnation, and alternative procedures should be investigated. Starting with Ni(II) and Fe(II) sulfates as precursor salts, deposition-precipitation with urea (DPU) on SiO2 in an inert atmosphere initially leads to the formation of an ill-crystallized Fe-containing Ni(II) 1:1 phyllosilicate, which reduces under hydrogen at 700°C into bimetallic fcc Fe-Ni nanoparticles of 5.4 nm in average. Compared with the composition of the DPU solution (50 Fe at %, 50 Ni at %), an excess of Ni is detected on the catalyst (32 Fe at %, 68 Ni at %), due to the preferential reaction of Ni2+ ions with silica. In situ X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy show that the reduction of Fe ions to the metallic state is triggered by the formation of reduced Ni centers above 350°C, and, from then, proceeds progressively, resulting in an excess of Fe in the outer shells of the bimetallic particles. The composition of individual Fe-Ni particles evidences a standard deviation of 8%. The bimetallic Fe-Ni/SiO2 catalyst gives high yields in furfuryl alcohol in the hydrogenation of furfural, in contrast with an analog Ni/SiO2 catalyst that favours side-reactions of etherification, hydrogenolysis and hydrogenation of the furan ring. |
| spellingShingle | Shi, D Yang, Q Peterson, C Lamic-Humblot, A Girardon, J Griboval-Constant, A Stievano, L Sougrati, M Briois, V Bagot, P Wojcieszak, R Paul, S Marceau, E Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments |
| title | Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments |
| title_full | Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments |
| title_fullStr | Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments |
| title_full_unstemmed | Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments |
| title_short | Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments |
| title_sort | bimetallic fe ni sio2 catalysts for furfural hydrogenation identification of the interplay between fe and ni during deposition precipitation and thermal treatments |
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