NiSn intermetallic nanoparticles with geometrically isolated Ni sites for selective C-O cleavage of furfural

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Selective C-O bond cleavage is critical in upgrading biomass derivatives to chemicals and fuels. However, eliminating side reactions from the aromatic rings is challenging, in large part because of the difficulty in precisely modulating the local atomic structure of the active sites. Herein, we report a Ni3Sn intermetallic nanoparticle with geometrically isolated Ni sites for hydrodeoxygenation of furfural, which shows considerable activity and 91 % selectivity toward 2-methylfuran at 96 % conversion, in stark contrast to the performance of Ni nanoparticle that mainly produces furan, CH4 and C4 products derived from the ring chemistry. Experimental and theoretical calculations demonstrate that the isolated Ni sites in Ni3Sn surface limits the furan ring interaction, while the electron donation from Sn to Ni facilitates the carbonyl O bonding to Ni sites. It therefore prevents side reactions from ring chemistry, but allows a facile sequential reaction of selective carbonyl hydrogenation followed by C-OH scission to 2-methylfuran.