Ni
and NiSn supported on zirconia (ZrO
2
) and on indium
(In)-incorporated zirconia (InZrO
2
) catalysts were prepared
by a wet chemical reduction route and tested for hydrogenation of
CO
2
to methanol in a fixed-bed isothermal flow reactor
at 250 °C. The mono-metallic Ni (5%Ni/ZrO
2
) catalysts
showed a very high selectivity for methane (99%) during CO
2
hydrogenation. Introduction of Sn to this material with the following
formulation 5Ni5Sn/ZrO
2
(5% Ni-5% Sn/ZrO
2
) showed
the rate of methanol formation to be 0.0417 μmol/(g
cat
·s) with 54% selectivity. Furthermore, the combination NiSn
supported on InZrO
2
(5Ni5Sn/10InZrO
2
) exhibited
a rate of methanol formation 10 times higher than that on 5Ni/ZrO
2
(0.1043 μmol/(g
cat
·s)) with 99% selectivity
for methanol. All of these catalysts were characterized by X-ray diffraction,
high-resolution transmission electron microscopy (HRTEM), scanning
transmission electron microscopy (STEM), X-ray photoelectron spectroscopy,
CO
2
-temperature-programmed desorption, and density functional
theory (DFT) studies. Addition of Sn to Ni catalysts resulted in the
formation of a NiSn alloy. The NiSn alloy particle size was kept in
the range of 10–15 nm, which was evidenced by HRTEM study.
DFT analysis was carried out to identify the surface composition as
well as the structural location of each element on the surface in
three compositions investigated, namely, Ni
28
Sn
27
, Ni
18
Sn
37
, and Ni
37
Sn
18
bimetallic nanoclusters, and results were in agreement with the
STEM and electron energy-loss spectroscopy results. Also, the introduction
of “Sn” and “In” helped improve the reducibility
of Ni oxide and the basic strength of catalysts. Considerable details
of the catalytic and structural properties of the Ni, NiSn, and NiSnIn
catalyst systems were elucidated. These observations were decisive
for achieving a highly efficient formation rate of methanol via CO
2
by the H
2
reduction process with high methanol
selectivity.
Furfural
(FFR) was selectively hydrogenated in a single pot to
tetrahydrofurfuryl alcohol (THFAL) over a Si–MFI molecular
sieve supported Pd catalyst. Studies on catalyst screening revealed
that both the metal function and the support were critical for directing
the selectivity to the ring-hydrogenated product, THFAL. The structural
feature of MFI as shown by XRD was completely retained in the used
sample of the 3% Pd/MFI catalyst confirming its stability under reaction
conditions. XRD, along with SEM characterization of the used samples,
established retention of morphology of the structured silicate, suggesting
a strong interaction between hexagonal porous silicate and Pd particles.
The complete conversion of FFR with an enhanced selectivity of 95%
to THFAL could be achieved by recycling the crude of the first hydrogenation
experiment over the same 3% Pd/MFI catalyst.
Non-chromium Cu:Al nano catalyst prepared by simultaneous co-precipitation and digestion method without any template or stabilizer, showed three times higher activity than the bulk Cu-Cr catalyst for hydrogenolysis of glycerol in both isopropanol and water solvents, with the selectivity to 1,2-Propanediol (1,2-PDO) as high as 91% at 493 K and H 2 pressure of 7 MPa in 5 h. XRD pattern showed the presence of Cu ? species in the activated Cu:Al nano catalyst. Although Cu ? is catalytically inactive in glycerol hydrogenolysis reaction, the presence of Cu ? helps to stabilize the particle size in a narrow range of 7-11 nm by inhibiting the sintering of copper particles under reaction conditions.
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