Efficient Base Nickel-Catalyzed Hydrogenolysis of Furfural-Derived Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol

Nickel(0) supported by strongly basic lanthanidehydroxides/oxyhydroxides (Ni-Ln, Ln = La, Pr, and Sm) is anefficient alternative noble metal-free catalyst for hydrogenolysis oftetrahydrofurfuryl alcohol (THFA) to 1,5-pentanediol (1,5-PeD) inorganic solvents (e.g., isopropanol). The catalytic performance ofNi-Lnwas studied both in batch and continuous modes. The highestyield of 1,5-PeD was 88% in a batch system and 73% in aflow systemusing40Ni-La reduced. Interestingly,40Ni-La reducedwas not onlyselective (>= 84%) but also stable in a long-term continuous run (386h). It is proposed that a metal support interface (Ni-Ln)isresponsible for cleaving the C-O bond of THFA via two initialsteps: deprotonation of THFA and activation of hydrogen. Addition-ally, transfer hydrogenolysis took place in the presence of H2insecondary alcohols, resulting in higher yields of 1,5-PeD under batch conditions. However, addition of H2had almost no influenceon catalyst selectivity to 1,5-PeD underflow conditions.