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[Display omitted] • ZIF-8 derived ZnO@NC can anchor Ru nanoparticles to create Ru-O-Zn interface. • Ru/ZnO@NC achieved complete conversion and 99.2% GVL yield in LA hydrogenation. • Ru/ZnO@NC achieved excellent reaction activity with a TOF of 6032 h−1 at 40 °C. • Reaction mechanism of LA hydrogenation to GVL has been revealed by DFT calculation. • Ru-O-Zn interface can remarkably decline activation energy of rate-determining step. Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is of interest for biomass refinery, but it suffers from great challenge to design highly active Ru-based catalyst at low temperature. ZIF-8 derived ZnO@NC nanocomposite can firmly anchor Ru nanoparticles to create strong Ru-ZnO interfacial structure, as revealed by characterization techniques and DFT calculations. By optimizing Ru content and ZnO particle size, Ru/ZnO@NC achieved excellent reaction activity with a turnover frequency (TOF) of 6032 h−1 at low temperature of 40 °C, which is never reported before. After etching the accessible ZnO, the TOF value was significantly declined to 125 h−1 on Ru/ZnO@NC-HF owing to the lack of effective Ru-ZnO interface. DFT calculation results demonstrate that the Ru-ZnO interfacial structure can facilitate the activation of intermediate CH 3 CHOCH 2 CH 2 COOH* and remarkably decline the activation energy barrier of rate-determining step (CH 3 CHOCH 2 CH 2 COOH + H = HPA) from 1.28 eV to 0.82 eV, thus leading to excellent activity of LA hydrogenation at low temperature. [ABSTRACT FROM AUTHOR]

• Rod, cube and octahedral CeO 2 exposed (1 1 0), (1 0 0) and (1 1 1) facets in Ru/CeO 2. • Ru/CeO 2 -rod with exposed (1 1 0) facet achieved 99.4% GVL yield in EL hydrogenation. • DFT calculation elucidates reaction mechanism of EL hydrogenation to GVL on Ru/CeO 2. • The concentration of oxygen vacancy is linearly proportional to GVL production rate. • Surface CeO 2 structure and concentration of oxygen vacancy determine facet effect. Three Ru/CeO 2 catalysts with different CeO 2 morphology (nanorod, nanocube and nano-octahedra) mainly exposed (1 1 0) + (1 0 0), (1 0 0) and (1 1 1) facets for hydrogenation of biomass-derived ethyl levulinate (EL) to valuable γ-valerolactone (GVL). Ru/CeO 2 -rod with exposed (1 1 0) crystal plane obtained the highest GVL yield (99.4%) and best productivity (13140 h−1). The surface facets of CeO 2 supports not only affect the chemical states of Ru species but also tune the concentration of oxygen vacancy in Ru-CeO 2 interface. The concentration of oxygen vacancy shows a linear relationship with GVL production rate. DFT calculations indicate that the lactonization of CH 3 CHOCH 2 CH 2 CO* to produce GVL is the rate-determining step in EL hydrogenation, and Ru 10 /CeO 2 (1 1 0) with more oxygen vacancy has low activation energy barrier, compared to Ru 10 /CeO 2 (1 0 0) and Ru 10 /CeO 2 (1 1 1). [ABSTRACT FROM AUTHOR]

• CoNi alloy encapsulated in N-doped thin graphene shell was synthesized from MOF. • One-pot cellulose conversion to γ-valerolactone using formic acid as hydrogen donor. • γ-Valerolactone yield reached as high as 55.9 % over AgPW/CoNi@NG. • Reaction mechanism of formic acid as hydrogen donor was revealed over CoNi@NG400. One-step efficient conversion of cellulose into value-added γ-valerolactone (GVL) is of great interest because it not only integrates complex tandem reactions in one-step, but also does not need additional hydrogen sources. To achieve this goal, it is crucial to fabricate high-performance catalyst that can accelerate both hydrolysis of cellulose and further transformation of generated stoichiometric levulinic acid (LA) and formic acid (FA) into GVL. CoNi nanoparticles encapsulated in N-doped thin graphene shell gave GVL yield as high as 55.9 % at 200 °C combined with Ag+-exchanged heteropolyacid (AgPW). This composite catalyst is highly resistant to the corrosion of LA and FA, and hence shows high catalytic stability. LA-adsorption FTIR spectra and DFT calculations indicate that LA and FA can penetrate through shell graphene layers into core CoNi sites via cracks. Compared to H 2 , FA can much more rapidly reduce LA because of its low dissociation energy barrier and high dissociation rate. [ABSTRACT FROM AUTHOR]