Inverse-Phase CoCe Catalyst with Balanced Hydrogenation and Adsorption Sites for Selective Ring-Opening Hydrogenolysis of 2-Furoic Acid to 5-Hydroxypentanoic Acid and Its Derivatives

The selective transformation of biomass-derived feedstocks into value-added chemicals via targeted C-O bond cleavage remains challenging due to the presence of multiple reducible bonds and typically low catalytic selectivity. Herein, we report a robust non-noble metal CoCe catalyst for the selective ring-opening hydrogenolysis of 2-furoic acid (2-FA), an industrialized biomass-derived platform molecule, to 5-hydroxypentanoic acid (5-HVA) and its derivatives, which have potential applications as fuel additives. The optimized 90CoCe catalyst with inverse phase demonstrates superior catalytic performance, achieving a total yield of more than 85% for 5-HVA and its derivatives under mild reaction conditions (130 °C, 2 MPa H2). Extensive characterizations reveal that the inverse-phase 90CoCe catalyst possesses abundant oxygen vacancies at the Co-CeOx interface, with the formation of Co-Ov-Ce interfacial species. The interfacial Co-Ov-Ce sites serve as specific adsorption centers for the 2-FA molecule, orienting it into a titled adsorption configuration that is highly favorable for the C2-O1 bond cleavage in the furan ring. Meanwhile, adjacent Co0 sites efficiently dissociate hydrogen into active hydrogen species for the hydrogenolysis of the C2-O1 bond to form ring-opening products. The synergistic balance between the hydrogenation Co0 sites and the interfacial Co-Ov-Ce adsorption sites is crucial to the high catalytic activity and selectivity of the CoCe catalyst. Moreover, the 90CoCe catalyst maintains stable catalytic performance during a 40 h continuous test in a fixed-bed reactor, demonstrating its great potential for industrial applications.