Intermetallic RNi2Si2 (R = Ca, La, and Y) Catalysts with Electron-Rich Ni Sites for Continuous Flow Selective Hydrogenation of Maleic Anhydride

The industrial advancement of downstream products resulting from the directed hydrogenation of maleic anhydride is hindered by the limitations related to the activity and stability of catalysts. The development of nonprecious metal intermetallic compounds, in which active sites are adjustable in the local structures and electronic properties embedded within a distinct framework, holds immense potential in enhancing catalytic efficacy and stability. Herein, we report that nickel-based silicides catalysts, RNi₂Si₂ (R = Ca, La, and Y), afford high efficiency in the selective hydrogenation of maleic anhydride. Among the RNi₂Si₂ with the same tetragonal structure, CaNi₂Si₂ with complete isolation and highest electron density of Ni sites presents the low apparent activation energy (98.4 kJ/mol). Preferential adsorption of intermediate succinic anhydride via C═O bonds is achieved by the high oxygen affinity of CaNi₂Si₂, resulting in chemoselectivity to γ-butyrolactone (>80%). Additionally, the silicide with good resistance to sintering and acid corrosion presents remarkable stability for at least 130 h. The design of the silicide structure will offer fresh perspectives on the development of effective and enduring selective hydrogenation catalysts.