Keto-alcohols, which
are traditionally
produced from fossil resources with multisteps, are considered as
important intermediates for diversified high-value-added fine chemical
synthesis due to their involved carbonyl and hydroxyl groups. Herein,
direct cellulose hydrogenolysis to C3-C4 keto-alcohol
products (hydroxyacetone and 1(3)-hydroxy-2-butanone) was achieved
over Ni-WO
x
/C catalysts with an W/Ni atom
ratio of 1.0–5.0. The keto-alcohol yield was proposed to strongly
depend on the W/Ni ratio and the catalyst annealing temperature. The
highest keto-alcohol yield of 63% was obtained at the optimal balance
of basic/acidic WO
x
species and metallic
Ni. The introduction of Ni facilitated the formation of the basic
W5+ sites, which enhanced the formation of basic sites
at the Ni-WO
x
interface. The synergistic
effect between the basic W5+ and acidic oxygen vacancy
(Vö) could activate the target C–O/CO bonds,
promoting the isomerization of glucose and C3-C4 aldehyde intermediates with the assistance of the interfacial Ni.
The cooperative adsorption of the −OH and −CO
groups at the Ni-O-W-Vö interface stabilized the adjacent ketone
and hydroxyl groups and kept the other hydroxyl groups for hydrogenolysis,
obtaining the final C3-C4 keto-alcohols. This
work expanded the application of cellulosic biomass, enabling the
green and sustainable synthesis of the high-value C3-C4 keto-alcohol products using lignocellulosic biomass as a
raw material.
Lactic acid (LA), a key platform chemical from biomass, is an ideal
feedstock for biodegradable plastic synthesis. The conversion of glycerol
to LA was investigated over graphitic-carbon-layer-encapsulated Ni–NiO
x
core/shell (Ni–NiO
x
@C) catalysts, which were prepared by controlled oxidation
from pristine Ni@C. The oxidation temperature greatly influenced the
percentage of NiO
x
and thus the amount
of Lewis acid. In the conversion of glycerol, the catalyst oxidized
at 200 °C provided hitherto the highest LA formation rate (5.67
mol/(m3·gcat·s)), which is at least
15 times faster than those obtained over the reported Cu and noble
metal catalysts under comparable reaction conditions. The excellent
performance of Ni–NiO
x
@C was attributed
to the synergistic effect of the homogenous base, metallic Ni, and
acidic NiO
x
sites, which accelerates the
bond cleavage of α-C–H and C–O and promotes ultrafast
formation of LA within 30 min.
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