Advances in Cyclopentanone Production via Furfural Hydrogenation

This review focuses on the catalytic hydrogenation of furfural (FFA), a biomass-derived platform chemical, to produce cyclopentanone (CPO)—a high-value industrial compound. The primary objective is to systematically analyze recent progress in catalyst design, reaction mechanisms, and process optimization to overcome the limitations of conventional CPO production methods reliant on fossil resources. The scope encompasses the evaluation of catalytic systems to enhance selectivity, stability, and cost-effectiveness in FFA conversion. Catalysts are classified into noble metals (Pd, Pt, Ru, Au) and non-noble metals (Cu, Ni, Co), with emphasis on their structural and electronic properties. Key strategies include metal-support interface engineering, Lewis/Brønsted acid site modulation, and bimetallic synergism. The reaction mechanism involves the following sequential steps: (1) FFA adsorption and selective C=O hydrogenation to furfuryl alcohol (FA); (2) acid-catalyzed ring-opening and rearrangement to 2-cyclopentenone (2-CPEO); and (3) 2-CPEO hydrogenation to CPO. Critical parameters such as temperature (110−180 ℃), H2 pressure (1−5 MPa), and aqueous-phase conditions are discussed. Noble metal catalysts, particularly Pd-based systems, demonstrate exceptional performance. For instance, Pd/NiMoO4 achieves 96.6% CPO yield at 150 ℃ and 4 MPa H2, while Pd/La2Ti2O7 attains 98% yield under similar conditions. Bimetallic catalysts (e.g., Pd-Cu/C) and variants supported on metal-organic frameworks (MOFs) (e.g., Pd@Fe-MIL-101) enhance stability and recyclability. Non-noble catalysts, such as Cu/ZrO2 (85.3% yield) and Ni/SiC-CrCl3 (88.1% yield), exhibit competitive performance through synergistic metal-acid interactions. Reaction parameters critically influence selectivity: aqueous solvents could suppress side reactions (e.g., tetrahydrofurfuryl alcohol (THFA) formation), while optimal temperatures (140−150 ℃) help balance hydrolysis and hydrogenation kinetics. The review highlights the potential of FFA-to-CPO conversion as a sustainable alternative to fossil-based routes. Noble metal catalysts excel in activity but face economic constraints, whereas non-noble systems (Cu, Ni) offer cost advantages with tunable selectivity. Key challenges include catalyst deactivation and harsh rection conditions. Future efforts should prioritize (1) improving the stability of non-noble catalysts via alloying and defect engineering; (2) integrating continuous-flow reactors with in situ product separation; and (3) exploring liquid hydrogen donors (e.g., alcohols) to reduce H2 pressure dependence. The mechanistic role of FFA adsorption geometry (vertical vs. horizontal binding) on catalytic selectivity provides a foundational framework for rational catalyst design. Furthermore, the synergy between metallic sites and acidic carriers (e.g., MOFs, zeolites) in stabilizing reaction intermediates offers novel pathways for enhancing CPO yield. These insights advance biomass valorization and support broader applications in green chemistry and renewable energy sectors.