Catalytic interplay of metal ions (Cu 2+ , Ni 2+ , and Fe 2+ ) in MFe 2 O 4 inverse spinel catalysts for enhancing the activity and selectivity during selective transfer hydrogenation of furfural into 2-methylfuran
2-Methylfuran obtained via the hydrogenation of furfural is an important biomass-derived liquid fuel. However, the large-scale production of 2-methylfuran from furfural requires cost-effective, active, and selective heterogeneous catalysts. Herein, we have performed experimental and DFT investigatio...
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| Published in | Catalysis science & technology Vol. 12; no. 15; pp. 4857 - 4870 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
01.08.2022
|
| Online Access | Get full text |
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| Summary: | 2-Methylfuran obtained
via
the hydrogenation of furfural is an important biomass-derived liquid fuel. However, the large-scale production of 2-methylfuran from furfural requires cost-effective, active, and selective heterogeneous catalysts. Herein, we have performed experimental and DFT investigations on MFe
2
O
4
(M = Cu
2+
, Ni
2+
, and Fe
2+
) inverse spinel catalysts to selectively hydrogenate furfural into 2-methylfuran
via
transfer hydrogenation, and to determine the nature of active sites. CuFe
2
O
4
afforded 99.4% furfural conversion and 97.6% 2-methylfuran selectivity at 200 °C in 1.5 h. In contrast, NiFe
2
O
4
and Fe
3
O
4
catalysts afforded furfuryl alcohol as a major product. The comprehensive characterization of the catalysts revealed that the acidity of these inverse spinel catalysts originates from the Lewis acid sites. Further, the strength of Lewis acid sites and the associated catalytic activity trend directly correlate with the binding energy of Fe
n
+
ions in MFe
2
O
4
catalysts. DFT calculations revealed the energetically favorable interactions of furfural and furfural alcohol with the Fe
3+
sites of Fe
3
O
4
and Fe sites (most likely Fe
3+
) of CuFe
2
O
4
and NiFe
2
O
4
catalysts, whereas Cu
2+
and Ni
2+
sites present in CuFe
2
O
4
and NiFe
2
O
4
catalysts have stronger interactions with the isopropanol molecule. Hence, it is proposed that the Fe
3+
sites present in CuFe
2
O
4
are the active Lewis acid centers to selectively convert furfural into 2-methylfuran
via
transfer hydrogenation. Literature reports on the metal oxide catalyzed transfer hydrogenation of furfural into 2-methylfuran are rare. The present findings on the elucidation of the active sites of cost-effective, recyclable mixed metal oxide catalysts for the selective transfer hydrogenation of furfural into 2-methylfuran using isopropanol are attractive from the green chemistry perspective, and therefore extremely important for the academic catalysis community and to industrialists. |
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| ISSN: | 2044-4753 2044-4761 |
| DOI: | 10.1039/D2CY00970F |