Rational design of Ni-based catalysts derived from hydrotalcite for selective hydrogenation of 5-hydroxymethylfurfural

Abstract

ARTICLE This journal isSelective hydrogenation of 5-hydroxymethylfurfural (HMF) is of great importance for future energy and chemical supply. Herein, we propose for the first time that non-noble Ni-Al 2 O 3 catalysts derived from hydrotalcite-like compounds can efficiently and selectively convert HMF to 2,5-dimethylfuran (DMF), 2,5-dimethyltetrahydrofuran (DMTHF) and 2,5dihydroxymethyltetrahydrofuran (DHMTHF). Homogeneous elemental distributions of hydrotalcite-like precursor facilitate the good dispersion of Ni and Al 2 O 3 species and strong interaction between them over the resulted catalysts. The catalysts therefore exhibited superior reactivity. Through fine modulation of surface metal-acid bifunctional sites and control of reaction conditions, high yields of DMF (91.5%), DMTHF (97.4%) and DHMTHF (96.2%) can be diversely achieved. The results demonstrate the feasibility of Ni catalysts for selective hydrogenation of C=O, C=C and C-O bonds, which have great potential for biomass utilization. ARTICLEThis journal is © The Royal Society of Chemistry 2015Green Chem., 2015, 00, 1-3 | 9 TPD) and CO temperature programmed desorption (CO-TPD) were performed on a Tianjin XQ TP-5080 instrument. Temperature programmed desorption of NH 3 (NH 3 -TPD) experiments were conducted on the AutoChem II. 2920 instrument (Micromeritics, USA) equipped with a mass spectrum detector. (See supporting information for details about the characterizations). Catalyst tests:The tests were performed over a 100 mL tank reactor. For a typical procedure, the reactor was fed with HMF (1.5 g), NiAl-CT and 1,4-dioxane (35 mL), then sealed and purged by H 2 (5 times). After that, the reactor was filled with H 2 in desired pressure and heated to objective temperature. After the test, the reactor was quenched in icewater, and then the liquid and gas products were analysed by a GC instrument with a FID detector. Notes and references

Studies of synergy between metal–support interfaces and selective hydrogenation of HMF to DMF in water

“…It is quite well known that characteristics of the support play an important role in determining the catalytic activity of materials [20]. Noble metals such as Pd, Pt, and Ru supported on carbon prove to be excellent catalysts for hydrogenation of biomass-derived chemicals [21][22][23][24]. The main shortcoming of this material is leaching of metal nanoparticles during catalysis, which is mostly due to less interfacial interaction between the support and the metal nanoparticles.…”

Efficient synthesis of 2,5-dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxymethylfurfural using mineral-derived Cu catalysts as versatile catalysts

“…13 For DMF production, Dumesic et al 7 reported for the first time a Ru-Cu catalyst with a yield of 76-79%. 18) and Ni-W 2 C/AC 19 ) catalysts emerged for DMF synthesis; on the other hand, they were difficult to be employed in DHMF synthesis due to the strong CC hydrogenation ability of Ni. However, few reports on the development of non-noble substitutes existed, due to their low reactivity.…”

Heterogeneous Nb-containing catalyst/N,N-dimethylacetamide–salt mixtures: novel and efficient catalytic systems for the dehydration of fructose

“…[1][2][3][4][5] Among various processes explored for biomass transformation, dehydration of carbohydrates, an important type of biomass, to produce 5-hydroxymethylfurfural (HMF) is one of the most successful routes. [6][7][8][9] As one of the top building block compounds obtained from biomass, 10 HMF can be transformed into many kinds of value-added compounds and materials, [11][12][13][14] which are currently produced mainly from petroleum.…”