Highly Efficient Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over CoRe/TiO2 Catalyst.

Allylic alcohols typically produced through selective hydrogenation of α,ß-unsaturated aldehydes are important intermediates in fine chemical industry, but it is still a challenge to achieve its high selectivity transformation. Herein, we report a series of TiO2-supported CoRe bimetallic catalysts for the selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) using formic acid (FA) as a hydrogen donor. The resultant catalyst with the optimized Co/Re ratio of 1:1 can achieve an exceptional COL selectivity of 89% with a CAL conversion of 99% under mild conditions of 140 °C for 4 h, and the catalyst can be reused four times without loss of activity. Meanwhile, the Co1Re1/TiO2/FA system was efficient for the selective hydrogenation of various α,ß-unsaturated aldehydes to the corresponding α,ß-unsaturated alcohols. The presence of ReOx on the Co1Re1/TiO2 catalyst surface was advantageous to the adsorption of C=O, and the ultrafine Co nanoparticles provided abundant hydrogenation active sites for the selective hydrogenation. Moreover, FA as a hydrogen donor improved the selectivity to α,ß-unsaturated alcohols.

Highly Effective Activated Carbon-Supported Ni-Mn Bifunctional Catalyst for Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran.

Designing highly efficient and low-cost catalysts for conversion of renewable biomass into high value-added chemicals and biofuels is important and challenging. Herein, a non-noble Ni-Mn bifunctional catalyst supported on activated carbon (Ni-Mn/AC) was developed by an incipient wetness impregnation method. The catalyst was found to be economic and efficient for the selective hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural (5-HMF) to 2,5-dimethylfuran (2,5-DMF). The optimal Ni-Mn/AC (Ni/Mn=3) catalyst achieved 98.5 % 2,5-DMF yield with 100 % conversion of 5-HMF under mild reaction conditions of 180 °C, 2.0 MPa H2 for 4 h. Furthermore, the catalyst exhibited outstanding reusability and could be recycled eight times without loss of activity. The addition of Mn not only enhanced the reactivity of 5-HMF but also resulted in the dominant reaction pathway shift from the hydrogenation of the C=O bond to the hydrogenolysis of C-OH bond, which was attributed to the synergy of highly dispersed Ni metallic nanoparticles and moderate Lewis acid sites from MnOx as revealed by detailed characterizations.

Reductive Amination of 5-Hydroxymethylfurfural to 2,5-Bis(aminomethyl)furan over Alumina-Supported Ni-Based Catalytic Systems.

Mono- and bimetallic Ni-based catalysts were prepared by screening 6 supports and 14 secondary metals for reductive amination of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(aminomethyl)furan (BAMF), among which γ-Al2 O3 and Mn were the best candidates. By further optimization of the reaction conditions at 0.4 g catalyst loading for 0.5 g substrate of 5-HMF and 160 °C of reaction temperature, 10Ni/γ-Al2 O3 and 10NiMn(4 : 1)/γ-Al2 O3 achieved the highest BAMF yields of 86.3 and 82.1 %, respectively. Although the BAMF yield values were comparable with that over Raney Ni, the turnover frequencies based on the initial BAMF yield and unit weight of Ni for 10NiMn(4 : 1)/γ-Al2 O3 , 10Ni/γ-Al2 O3 , and Raney Ni were calculated as 0.41, 0.09, and 0.04 h-1 , respectively. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy showed that the existence of MnOx well dispersed on the γ-Al2 O3 support and its electron transfer effect with Ni particles on the surface of the support contributed to the high efficiency and better recyclability for the five-time reused 10NiMn(4 : 1)/γ-Al2 O3 catalyst.

One-Step Reductive Amination of 5-Hydroxymethylfurfural into 2,5-Bis(aminomethyl)furan over Raney Ni.

Simultaneous reductive amination of C=O and C-OH in 5-hydroxymethylfurfural (HMF) into C-NH2 in 2,5-bis(aminomethyl)furan (BAMF) is challenging. In this work, reductive amination of C=O in HMF was firstly studied, in which HMF can be converted into 5-hydroxymethyl furfurylamine (HMFA) with a 99.5 % yield over Raney Co catalyst. BAMF was then directly synthesized with 82.3 % yield from HMF over Raney Ni catalyst at 160 °C for 12 h. An even higher yield of 88.3 % could be obtained through a stepwise reductive amination process, in which the reaction started at 120 °C for the first 2 h over Raney Co mainly for amination of C=O and then continued at 160 °C for another 10 h over Raney Ni mainly for amination of C-OH. Under optimized reaction conditions, the catalyst could be reused four times without obvious loss in catalytic performance. XRD and XPS characterization of the reused catalyst indicated that the formation of Ni3 N and the adsorption of alkyl amines could be the main reasons for the deactivation of the catalyst. Moreover, plausible reaction pathways were proposed to originate the detected by-products according to the kinetic profiles.

Highly efficient selective hydrogenation of levulinic acid to γ-valerolactone over Cu-Re/TiO2 bimetallic catalysts.

Highly active and thermally stable Cu-Re bimetallic catalysts supported on TiO2 with 2.0 wt% loading of Cu were prepared via an incipient wetness impregnation method and were applied for liquid phase selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) in H2. The effect of the molar ratios of Cu : Re on the physico-chemical properties and the catalytic performance of the Cu-Re/TiO2 catalysts was investigated. Moreover, the influence of various reaction parameters on the hydrogenation of LA to GVL was studied. The results showed that the Cu-Re/TiO2 catalyst with a 1 : 1 molar ratio of Cu to Re (Cu-Re(1 : 1)/TiO2) exhibited the highest performance for the reaction. Complete conversion of LA with a 100% yield of GVL was achieved in 1,4-dioxane solvent under the reaction conditions of 180 °C, 4.0 MPa H2 for 4 h, and the catalyst could be reused at least 6 times with only a slight loss of activity. Combined with the characterization results, the high performance of the catalyst was mainly attributed to the well-dispersed Cu-Re nanoparticles with a very fine average size (ca. 0.69 nm) and the co-presence of Cu-Re bimetal and ReO x on the catalyst surface.

An Efficient and Reusable Embedded Ru Catalyst for the Hydrogenolysis of Levulinic Acid to γ-Valerolactone.

To achieve a higher activity and reusability of a Ru-based catalyst, Ru nanoparticles were embedded in N-doped mesoporous carbon through a hard-template method. The catalyst showed excellent catalytic performance (314 h-1 turnover frequency) and recyclability (reusable five times with 3 % activity loss) for the hydrogenolysis of levulinic acid to γ-valerolactone. Compared with the mesoporous carbon without N-doping and conventional activated carbon, the introduction of N-dopant effectively improved the dispersion of Ru nanoparticles, decreased the average size of Ru nanoparticles to as small as 1.32 nm, and improved the adsorption of levulinic acid, which contributed to the increase in the activity of the catalyst. Additionally, the embedding method increased the interaction between Ru nanoparticles and carbon support in contrast with the conventional impregnation method, thus preventing the Ru nanoparticles from migration, aggregation, and leaching from the carbon surface and therefore increasing the reusability of the catalyst.

Graphene-supported Pd catalyst for highly selective hydrogenation of resorcinol to 1, 3-cyclohexanedione through giant π-conjugate interactions.

The selective hydrogenation of resorcinol (RES) to 1, 3-cyclohexanedione (1,3-CHD) without the addition of alkali is a big challenge. In this article, a novel reduced graphene oxide (rGO) supported Pd catalyst was prepared through co-reduction method, over which we obtained 99.9% of resorcinol conversion and 94.2% of the ever-reported highest 1,3-cyclohexanedione selectivity at 25 °C in only CH2Cl2 solvent. The excellent selectivity was contributed to the strong π-π and p-π interactions between the graphene nanosheet and the benzene ring as well as hydroxyl in RES molecule. The followed adsorption experiment and Raman analysis also showed the existence of aromatic graphite structures in rGO, which exhibited stronger adsorption towards RES than towards 1,3-CHD.