Catalytic Transfer Hydrogenation of Glucose to Sorbitol with Raney Ni Catalysts Using Biomass-Derived Diols as Hydrogen Donors

Abstract

The catalytic transfer hydrogenation (CTH) of glucose to sorbitol has been studied using a wide collection of different biomass-derived alcohols and diols as hydrogen donors. Catalytic activity results reflect the feasibility to conduct this transformation in the presence of conventional, commercially available Raney Ni-type sponges as catalysts. Sacrificial diols displayed a superior performance as hydrogen donors as compared to short-chain alcohols, including secondary alcohols. Among them, terminal diols such as 1,4-butanediol and 1,5-pentanediol were revealed as excellent hydrogen donors, providing a high selectivity in the conversion of glucose into sorbitol. As for the catalysts, molybdenum promotion provided a very high catalytic activity to sponge nickel catalysts, even under mild temperature conditions. The transformation was also studied in a fixed-bed reactor under continuous-flow operation conditions. Results demonstrate that the catalysts are highly stable and able to operate for at least 550 h on stream with a high selectivity in the CTH of glucose to sorbitol.

Catalytic Transfer Hydrogenation of 5‐Hydroxymethylfurfural with Primary Alcohols over Skeletal CuZnAl Catalysts

“…The deactivation was presumably caused by the oxidation of the catalyst during recycling procedures (air exposure), which may be effectively avoided if a continuous-flow reactor was applied instead (not discussed here) or by slightly increasing the reaction temperature to 140 °C (83 % yield was obtained; Table 2, entry 16). The reduction of the recovered skeletal catalysts with H 2 or NaBH 4 were also investigated to regenerate the catalyst's reactivity; unfortunately, the results turned out to be disappointing as only 16 and 39 % BHMF yield were obtained, respectively. These results further indicated the distinct property of the skeletal catalysts from traditional supported metal catalysts.…”

“…Catalytic transfer hydrogenation (CTH) is definitely an appealing candidate that has long been developed by sacrificing the H atoms from hydrogen source for hydrogenation. [16] Representative hydrogen sources are alcohols, [17] silanes, [18] and formic acid, [19] among which alcohols are the most frequently used ones featuring good reactivities, cost-effectiveness, and pH-neutrality. For example, a secondary alcohol, isopropanol (i-PrOH), has been well acknowledged with good reactivity in the CTH reaction; in particular, it can promote the HMF-to-BHMF conversion in the presence of Ru/Co 3 O 4 , [20] Co 3 O 4 @MC, [21] or Zr-DTPA [22] (MC = mesoporous carbon, DTAP = diethylenetriaminepentaacetic acid) catalysts.…”

“…Catalytic transfer hydrogenation (CTH) is definitely an appealing candidate that has long been developed by sacrificing the H atoms from hydrogen source for hydrogenation [16] . Representative hydrogen sources are alcohols, [17] silanes, [18] and formic acid, [19] among which alcohols are the most frequently used ones featuring good reactivities, cost‐effectiveness, and pH‐neutrality.…”

Nano Ag/AgBr/g-C3N4 catalyzed the production of hydrogen and reduction of d-glucose to sorbitol under visible light irradiation

“…It was observed that as the catalysis increased in the presence of NaHSO 3 co-catalyst under visible light irradiation conditions, and the % conversion yield of these products was improved. [4][5][6] From the aforementioned results, it was noted that Ag/AgBr/ g-C 3 N 4 nanocomposites were effective catalysts for hydrogenation reaction under visible light conditions at a concentration of 100 ppm after 8 h under ambient conditions (Table 3, entry 9). Whereas by adding higher concentrations of nanocatalyst at 150 ppm or 200 ppm, there were no observed changes in the % conversion of sorbitol (Table 3, entries 10 and 11).…”

“…3 Recent studies have demonstrated the direct synthesis of sorbitol. [4][5][6] It was shown that high selectivity for the production of D-sorbitol was obtained when RANEY s Ni catalysts, in the presence of diols as hydrogen donors were used after 550 h. 4 In another study, the % conversion to sorbitol was 99% glucose conversion at 140 1C in 150 min reaction time when tannic acid-based porous carbon spheres supported Ni-Ru bimetallic catalysts. 5 Again, the potential effect of RANEY s nickel in the catalytic transfer hydrogenation reaction for the reduction of glucose to sorbitol proceeded at elevated temperatures (130-190 1C) after 6 h. 6 This work aims to explore an alternative reaction pathway for the transformation of glucose into sorbitol by exploring the feasibility of photocatalysis without the use of H 2 gas under pressure.…”