Selective Hydrogenation of Cinnamaldehyde over Co-Based Intermetallic Compounds Derived from Layered Double Hydroxides

Selective hydrogenation of unsaturated carbonyl compounds plays a key role in the production of fine chemicals and pharmaceutical agents. In this work, two kinds of intermetallic compounds (IMCs: CoIn3 and CoGa3) were prepared via structural topotactic transformation from layered double hydroxide (L...

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Veröffentlicht in:ACS catalysis 2018-12, Vol.8 (12), p.11749-11760
Hauptverfasser: Yang, Yusen, Rao, Deming, Chen, Yudi, Dong, Siyuan, Wang, Bin, Zhang, Xin, Wei, Min
Format: Artikel
Sprache:eng
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Zusammenfassung:Selective hydrogenation of unsaturated carbonyl compounds plays a key role in the production of fine chemicals and pharmaceutical agents. In this work, two kinds of intermetallic compounds (IMCs: CoIn3 and CoGa3) were prepared via structural topotactic transformation from layered double hydroxide (LDH) precursors, which exhibited surprisingly high catalytic activity and selectivity toward hydrogenation reaction of α,β-unsaturated aldehydes (CO vs CC). Notably, the CoGa3 catalyst shows a hydrogenation selectivity of 96% from cinnamaldehyde (CAL) to cinnamyl alcohol (COL), significantly higher than CoIn3 (80%) and monometallic Co catalyst (42%). A combination study including XANES, XPS, and CO-IR spectra verifies electron transfer from Ga (or In) to Co, leading to the formation of CoGa (or CoIn) coordination. FT-IR measurements and DFT calculation studies substantiate that the electropositive element (Ga or In) in IMCs serves as an active site and facilitates the adsorption of polarized CO, while CC adsorption on the Co site is extremely depressed, which is responsible for the markedly enhanced selectivity toward hydrogenation of CO. This work reveals the key role of functional group adsorption in determining the hydrogenation selectivity of α,β-unsaturated aldehydes, which gives an in-depth understanding on the structure–property correlation and reaction mechanism.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.8b02755