Formic acid-assisted carbothermal shock synthesis of Ni–PrOx catalyst for selective hydrogenolysis of furfuryl alcohol to 1,5-pentanediol

The selective hydrogenolysis of biomass-derived furfuryl alcohol (FOL) to 1,5-pentanediol (1,5-PeD) is a crucial yet challenging transformation in biorefinery. Herein, a NiPr-CTS-F catalyst synthesized via a formic acid-assisted carbothermal shock (CTS) strategy, which features an ultrafast, energy-efficient, and low-pollution process with minimal carbon residue, is reported for this reaction. Comprehensive characterization confirms the successful construction of an intimate Ni–PrO x interface accompanied by oxygen vacancies. This structure creates synergistic ternary active centers, integrating metallic Ni sites for H 2 activation, interfacial oxygen vacancies for adsorbing the O atom of C–O–C in the furan ring, and basic sites for anchoring the hydroxyl group. Mechanistic studies reveal that this synergistic site steers the key intermediate, tetrahydrofurfuryl alcohol (THFA), into a bidentate adsorption configuration that selectively stretches and polarizes the C 2 –O 1 bond, thereby facilitating its selective cleavage. Furthermore, the isopropanol (IPA) solvent participates via a Meerwein–Ponndorf–Verley (MPV) mechanism, supplying hydride ions (H ⁻ ) and dynamically regulating the surface hydrogen concentration to ensure high selectivity while suppressing over-hydrogenolysis. Under optimal conditions (180 °C, 3 MPa of H 2 , 24 h), a high 1,5-PeD yield of 72.1% is achieved with FOL conversion of 99.4%. The catalyst also exhibits excellent stability over five consecutive cycles with negligible activity loss. This work not only provides an efficient catalyst for 1,5-PeD synthesis but also offers molecular-level insights into selective C–O bond cleavage, demonstrating how rationally designed interfacial sites and solvent participation can cooperatively govern reaction pathways. These findings present a new paradigm for designing multifunctional catalytic interfaces for biomass valorization.