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Highlights: [•] Addition of SiO2 to PtW/Zr greatly enhanced activity and 1,3-propanediol selectivity. [•] 54.3% conversion and 52.0% 1,3-propanediol selectivity were achieved over 5PtW/ZrSi. [•] A model scheme of WO x transformation due to SiO2 doping has been built. [•] Pt and polytungstate have been identified as the dominant active phases. [•] Glycerol hydrogenolysis conforms to the dehydration–hydrogenation mechanism. [Copyright &y& Elsevier]

Highlights: [•] Alkaline metals Li, K, Rb and Cs were efficient for tune acidity of H4SiW12O40. [•] Li modified Pt–H4SiW12O40/ZrO2 exhibited superior 1,3-propanediol selectivity. [•] 1,3-Propanediol yield was proportional to the concentration of Brønsted acid sites. [•] A mechanistic scheme for glycerol hydrogenolysis to 1,3-propanediol was proposed. [•] A 120h long-term performance for Pt–H4SiW12O40/ZrO2 was achieved. [ABSTRACT FROM AUTHOR]

• TiO 2 nanosheets supported Ru nanoparticles form strong interfacial Ru O Ti structure. • Ru/TiO 2 reached the highest TOF of 19,045 h−1for levulinic acid (LA) hydrogenation. • 99.1% yield of γ-valerolactone (GVL) was achieved over Ru/TiO 2. • DFT calculations clearly elucidate reaction mechanism of LA hydrogenation to GVL. • Ru/TiO 2 interface tunes rate-determining step from LA hydrogenation to cyclization. Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is still a challenge for Ru-based catalysts under mild condition. In this work, we have reported that ultrathin TiO 2 nanosheets supported Ru nanoparticles showed extraordinarily high catalytic activity, GVL yield (99.1%) and reusability owing to the formation of Ru O Ti interfacial structure. The turnover frequency (TOF) reached as high as 19,045 h−1 at 100 °C, much higher than those of Ru/SiO 2 , Ru/GO, Ru/MoS 2 , and commercial Ru/C. DFT calculation elucidates that the dominant reaction pathway of LA hydrogenation to GVL is preferentially hydrogenated to CH 3 CHOCH 2 CH 2 COOH*, followed by cyclization to CH 3 (OH)C 4 OH 4 OH* (GVL − OH) and final dehydroxylation, irrespective of surface structure. Compared to Ru (0 0 2) facet, Ru/TiO 2 interfacial structure changes the rate-determining step from initial hydrogenation to cyclization, which greatly declines the activation barrier from 0.81 eV to 0.48 eV. [ABSTRACT FROM AUTHOR]

Suppressing reverse water-gas-shift (RWGS) reaction is high desirable but challenging and underdeveloped for Cu/ZnO catalysts, particularly for commercial Cu/ZnO/Al 2 O 3 catalysts. Different from the current methodologies to reduce RWGS reaction, we report a simply surface silylation method for efficiently minimizing RWGS reaction over a commercial Cu/ZnO/Al 2 O 3 catalyst. This method suppresses STY CO (Space-time yield) from 97.4 to 0.7 g CO ·kg cat −1·h−1, improving STY MeOH from 20.2 to 39.9 g MeOH ·kg cat −1·h−1 and methanol selectivity from 15.1 to 92.9 mol%. The combination of characterization methods and density functional theory calculations provide insight into the suppressing mechanism of surface silylation on catalyst. A hydroxyl (on ZnO)-promoted RWGS reaction cycle is discovered, which can be efficiently inhibited by the consuming of hydroxyls via surface silyation. Our results provide a way to regulate RWGS reaction on Cu/ZnO-based catalysts and are expected to the further use of silylation strategy to tune the interconversion of CO and CO 2 via RWGS/WGS reaction on hydrogenation catalysts. [Display omitted] • Surface silylation suppresses RWGS reaction on Cu/ZnO/Al 2 O 3 for CO 2 hydrogenation, promoting S CH3OH from 15.3 to 92.9 mol%. • A Zn-OH promoted RWGS mechanism is found, i.e., H spillover from Cu to the reactants via the Zn-OHs boosts RWGS reaction. • Consuming hydroxyls via the surface silylation inhibits the H spillover and further RWGS reaction. [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]