This paper reports the synthesis of primary amines from alcohols and NH3 by an Al2O3-supported Ni nanoparticle catalyst as the first example of heterogeneous and noble-metal-free catalytic system for this reaction without additional hydrogen sources under relatively mild conditions. Various aliphatic alcohols are tolerated, and turnover numbers were higher than those of Ru-based homogeneous catalysts. The catalyst was recoverable and was reused. The effects of the Ni oxidation states and the acid–base nature of support oxides on the catalytic activity are studied. It is clarified that the surface metallic Ni sites are the catalytically active species, and the copresence of acidic and basic sites on the support surface is also indispensable for this catalytic system.

Pt/Nb2O5 shows more than 60 times higher TON than non-SMSI Pt catalysts and previous catalysts for the hydrodeoxygenation of stearic acid to n-octadecane at 180 °C in 8 bar H2. Nb2O5 can act as an activation site of carbonyl groups.

Valeric acid and valeric biofuels are obtained in high yield by direct hydrogenation of levulinic acid catalyzed by Pt/HMFI under relatively mild conditions (2 or 8 bar H2, 200 °C), driven by cooperation of the metal and support Brønsted acid sites.

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Herein, we report a heterogeneous TiO -supported Re catalyst (Re/TiO ) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N-methylation of amines, by using H and CO . Initially, Re/TiO was evaluated in the context of the selective hydrogenation of 3-phenylpropionic acid methyl ester to afford 3-phenylpropanol (pH2 =5 MPa, T=180 °C), which revealed a superior performance over other catalysts that we tested in this study. In contrast to other typical heterogeneous catalysts, hydrogenation reactions with Re/TiO did not produce dearomatized byproducts. DFT studies suggested that the high selectivity for the formation of alcohols in favor of the hydrogenation of aromatic rings is ascribed to the higher affinity of Re towards the COOCH group than to the benzene ring. Moreover, Re/TiO showed a wide substrate scope for the hydrogenation reaction (19 examples). Subsequently, this Re/TiO catalyst was applied to the hydrogenation of amides, the N-methylation of amines, and the N-alkylation of amines with carboxylic acids or esters.

TiO2-supported Re, Re/TiO2, was found to promote selective hydrogenation of carboxylic acids having aromatic and aliphatic moieties to the corresponding alcohols. Re/TiO2 showed superior results compared to other transition-metal-loaded TiO2 and supported Re catalysts for selective hydrogenation of 3-phenylpropionic acid. 3phenylpropanol was produced in 97% yield under mild conditions (5 MPa H-2 at 140 degrees C). Contrary to typical heterogeneous catalysts, Re/TiO2 does not lead to the formation of dearomatized byproducts. The catalyst is recyclable and shows a wide substrate scope in the synthesis of alcohols (22 examples; up to 97% isolated yield)

Pt and MoO(x) co-loaded TiO2 is found to be highly effective for direct methylation of aliphatic and aromatic secondary amines by CO2 and H2 under solvent-free conditions. This is the first additive-free and reusable heterogeneous catalytic system with acceptable turnover number.

Various supported metal catalysts are screened for hydrogenation of lauric acid and 2‐octanone as model reactions for the transformation of biomass‐derived oxygenates to liquid alkanes (biofuels) in a batch reactor under solvent‐free conditions. Among the catalysts tested, Pt and MoOx co‐loaded on TiO2 (Pt–MoOx/TiO2) shows the highest yields of n‐alkanes for both of the reactions. Pt–MoOx/TiO2 selectively catalyzes the hydrodeoxygenation of various fatty acids and triglycerides to n‐alkanes without C−C bond cleavage under 50 bar H2 and shows higher turnover numbers than the catalysts in the literature. Pt–MoOx/TiO2 is effective also for the hydrodeoxygenation of various ketones to the corresponding alkanes. In situ IR study of the reaction of adsorbed acetone under H2 suggests that the high activity of Pt–MoOx/TiO2 is attributed to the cooperation between Pt and Lewis acid sites of the MoOx/TiO2 support.