Construction of Dot‐Matrix Cu⁰‐Cu₁Ni₃ Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Abstract Using cheap Cu‐based catalysts for highly selective hydrogenation of furfural (FAL) is of great importance of upgrading this biomass‐derived platform molecule but is still challenging for large‐scale application due to the low conversion efficiency and the easy aggregation of Cu active sites. To address these issues, a nitrogen‐autodoped porous biochar derived from rubber seed shell ( rss AC) was fabricated for anchoring Cu sites on a nanoscale. Moreover, by the co‐crystallization strategy of Cu and the second metal (M, M=Ni, Zn, Co, Ce), stable Cu−M nanoalloys were constructed on the surface of the rss AC support. The FAL hydrogenation experiments showed that the type, proportion and loading amount of the second metal had great effect on the catalytic efficiency. Compared with the other metals, Ni‐doped Cu/ rss AC catalyst exhibited the best hydrogenation performance due to their extraordinary adsorption and activation capacity for hydrogen. Further, the highest catalytic efficiency was observed using 20 % Cu 1 Ni 1 /rss AC catalyst. The characterization results showed that the key to its success was highly‐dispersive anchoring of the CuNi active sites onto the inner/outer surface of the nanopores of rss AC support by the strong interaction between the surface N‐containing functional groups and metals. Of note, the formed CuNi alloys with the Cu/Ni atomic ratio of 1 : 3 played an important role in the stabilization of the adjacent nano‐dot matrix Cu 0 species. Kinetic test indicated that the formation step of furfuryl alcohol (FOL) from FAL was still the key step and the hydrogenation products can be converted between FOL and tetrahydrofurfuryl alcohol (THFA). The life evaluation test showed that the catalyst still kept high activity and selectivity after being reused five times. The advanced synthesis method co‐using N‐doped support anchoring and the second metal alloying strategy sheds light on preparing effective catalysts for hydrogenation of biomass‐based compounds.