Ni Nanoparticles Inlaid Nickel Phyllosilicate as a Metal–Acid Bifunctional Catalyst for Low-Temperature Hydrogenolysis Reactions

Abstract

Hydrogenolysis of carbon–oxygen bonds is a versatile synthetic method, of which hydrogenolysis of bioderived 5-hydroxymethylfurfural (HMF) to furanic fuels is especially attractive. However, low-temperature hydrogenolysis (in particular over non-noble catalysts) is challenging. Herein, nickel nanoparticles (NPs) inlaid nickel phyllosilicate (NiSi-PS) are presented for efficient hydrogenolysis of HMF to yield furanic fuels at 130–150 °C, being much superior with impregnated Ni/SiO2 catalysts prepared from the same starting materials. NiSi-PS also shows a 2-fold HMF conversion intrinsic rate and 3-fold hydrogenolysis rate compared with the impregnated Ni/SiO2. The superior performance originated from the synergy of highly dispersed nickel NPs and substantially formed acid sites due to coordinatively unsaturated Ni (II) sites located at the remnant nickel phyllosilicate structure, as revealed by detailed characterizations. The model reactions over the other reference catalysts further highlighted the metal–acid synergy for hydrogenolysis reactions. NiSi-PS can also efficiently catalyze low-temperature hydrogenolysis of bioderived furfural and 5-methylfurfural, demonstrating a great potential for other hydrogenolysis reactions.

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO2 Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

“…It can be seen from Figure 6d that acidity of the catalysts remarkably increases with Ni content increasing thanks to the MÀ OH structure variation between Niphy and Cuphy. In our hydrogenation system, these functional acid sites (e. g. surface electron-defect Lewis acid sites which can be proved by Py-IR as reflected in Figure S6) from the surrounding of active NiÀ Cu nanoparticles may act as association sites to attract the electron-rich CÀ OH group at the terminal of adsorbed BED intermediate, [27,[44][45] thus stabilizing the allyl alcohol existing form over the active NiÀ Cu sites and further promoting the selectivity to BDO. 100 and 250°C, corresponding to the desorption of NH 3 from the weak (α) and medium (β) acid sites, respectively.…”

“…10Cu-phy@SiO 2 only displayed a sharp peak centered at 290°C attributing to the reduction of Cuphy species. [25,27] For the bimetallic NiCuphy@SiO 2 catalysts, an obvious three stages reduction behavior was observed. [26] Another comparison between 10Niphy@SiO 2 and Ni/SiO2-im also indicated that the Niphy species are relatively hard to reduce and even some Ni species cannot be reduced during reduction treatment, thus remaining to the tough framework.…”

Selective Hydrodeoxygenation of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Heterogeneous Iron Catalysts

“…[32] Considering the high cost and scarcityo fn oble metals, the HDO of HMF to DMF over non-noble-metal catalysts was investigated recently.T he activities and stabilities of six carbon-supported noble-o rn on-noble-metalc atalysts were comparedi n ac ontinuous-flow reactor by Gorte and co-workers. [39][40][41][42] They also studied the one-step continuous conversiono ff ructoset o DMF over combined HY zeolite and HT-Cu/ZnO/Al 2 O 3 in af ixed-bed reactor with aD MF yield of 40.6 %. [34] Subsequently,t hey studied the conversion of HMF over Cu 0.61 Mg 2.33 Al 0.98 Ru 0.02 and CuÀZn nanoalloy catalysts, and up to 97 %c ombined product yields were obtained at 200-220 8Ca nd 20-30 bar H 2 .…”

Effect of Size and Distribution of Ni Nanoparticles on γ-Al2O3 in Oleic Acid Hydrodeoxygenation to Produce n-Alkanes

“…For n-C 17 For n-C 18 Table 6 shows the calculated coefficient, Fisher-F, and p-value for the yield of n-C 18 (mol%). The criteria for determining the statistical significance are the same as those used for n-C 17 yield.…”