ZnAl-LDHs were synthesized on -Al2O3 by surface synthesis method

1. 5.0 g -Al2O3 was added into a three-necked flask containing 150

mL aqueous solution of Zn(NO3)2·6H2O (0.1 mol/L) and NH4NO3
(0.1 mol/L), stirring at 70°C for 24 h,
2. Adjusting the pH value of the solution to 7.0 or 8.0 through
adding diluted ammonia water (5%). To make the washing solution,
ammonia water and NH4NO3 were added into deionized water
3. Adjusting to the same pH value.
4. After washing for 5 to 7 times, the wet sample was then aged for
1 h in air and the precipitate was then dried at 70°C for 24 h, to
obtain ZnAl-LDHs/ -Al2O3. After that, the solid material was
further calcined at 400°C for 4 h in a muffle furnace, to obtain
the mixed metal oxide -Al@MMO.

To prepare the Cu/ZnAl catalyst

1. -Al@MMO, which was used as the support, was dipped into the
Cu(NO3)2·3H2O solution (10%, calculated by the concentration of
copper);
2. It was then dried at 110°C for 12 h
3. calcined at 500°C for 3 h.
4. The obtained Cu/ZnAl catalyst, which was used as the precursor,
was then dipped into the M(NO3)3·6H2O (M = Y, La, Ce, Gd and
Sm) solution (4%, calculated by the concentration of rare-earth
element M)
5. after that, it was dried at 110°C for 12 h
6. calcined at 500°C for 3 h, to obtain the rare-earth M-modified
M/Cu/ZnAl catalyst.
7. The solid catalyst sample was then pressed and ground to
particles of 0.28–0.45 mm
Table 3 gives the selectivity to CO for the methanol steam reforming
at a certain temperature that gives similar methanol conversion.
Among all these catalysts, Gd/Cu/ZnAl catalyst exhibits the lowest
selectivity to CO; over it at 260°C, the methanol conversion is 81% and
the CO content in the
reforming products is lower than 0.1%.
Next is the Ce/Cu/ZnAl catalyst, at 240°C, the CO content in the
reforming products is 0.9%, with a methanol conversion of 92%.
Taking both the methanol conversion and the selectivity to CO into
consideration, the Ce/Cu/ZnAl catalyst exhibits the best performance
in the methanol steam reforming for the production of hydrogen.

CONCLUSION
By using an in-situ synthesis method, Zn-Al layered double
hydroxides (ZnAl-LDHs) were obtained on -Al2O3; with
ZnAl-LDHs as the supports, a series of rare-earth element M
(M = Y, La, Ce, Sm and Gd) doped M/Cu/ZnAl catalysts were
then prepared through sequential wet impregnation method
and used in the methanol steam reforming to produce
hydrogen. Through extensive characterizations, the effect of
rare-earth metal doping on their catalytic performance in the
methanol steam reforming as well as the structure-properties
relationship of the M/Cu/ZnAl catalysts was then elucidated.
The results illustrate that the activity of Cu/ZnAl catalyst is
closely related to the copper surface area and the reducibility;
larger copper surface area and lower reduction temperature
lead to a higher catalytic activity in methanol steam reforming.
The addition of rare-earth elements including Ce, Sm and Gd
can improve the copper dispersion, surface copper area and
the catalyst reducibility, which is helpful to enhance the
activity of M/Cu/ZnAl catalysts. On the contrary, the
Y/Cu/ZnAl and La/Cu/ZnAl catalysts show lower activity due
to their lower Cu surface area and higher reduction
temperature. Especially, the Ce/Cu/ZnAl catalyst exhibits the
highest activity; over it, the methanol conversion is 100%
(about 40% higher than that over the Cu/ZnAl catalyst) and
the CO concentration in the product is only 0.39%, for the
methanol steam reforming at 250°C. Such results may provide
theoretic basis for the design of efficient catalyst for
producing hydrogen by methanol steam reforming.