Synthesis of double layered hydroxide

Joseph Cobo, Isaac Iglesias, Bryan Inlago & Jazmin Muñoz

Catalytic Process Engineering Laboratory

School of Chemical Sciences and Engineering, Yachay Tech University, Urcuqui,
Ecuador.

Objective

Synthesis of double layered hydroxide using Mg2+ and Al3+ by coprecipitation method.

Introduction

Layered double hydroxides (LDHs), also known as anionic clays, are materials that are
able to intercalate neutral guest molecules or to exchange inorganic and organic ions for
interlayer ions [1]. LDHs are available as naturally occurring minerals and as synthetic
materials. They were first prepared in the laboratory in 1942 when Feitknecht reacted
dilute aqueous metal salt solutions with base, although the first detailed structural
analyses of LDHs were not carried out until the late 1960s by Allmann and Taylor and
their co-workers [2]. LDHs consist of stacks of positively charged mixed metal hydroxide
layers that require the presence of interlayer anions to maintain overall charge neutrality.

The most important group of LDHs may be represented by the formula [M2+ 1-xM3+
n- 2+ 3+
x(OH)2]A x/n m(H2O), where M and M are divalent and trivalent cations, respectively;
x is equal to the ratio M3+ /(M2+ + M3+) and A is an anion of valence n. The structure of
LDHs is most clearly described by considering the structure of brucite, which consists
Mg(OH)2 , of Mg2+ ions coordinated octahedrally by hydroxyl groups [3].
The octahedral units share edges to form infinite, charge neutral layers. In an LDH,
isomorphous replacement of a fraction of the Mg2+ ions with a trivalent cation, such as
Al3+, occurs and generates a positive charge on the layers that necessitates the presence
of interlayer, charge balancing, anions. The remaining free space of the interlayer is
occupied by water of crystallization (Fig. 1).
In general, M2+ and M3+ ions that have an ionic radius not too different from that of Mg2+
(ionic radius of Mg2+ = 0.65 °A) can be accommodated in the holes of the close-packed
OH groups in the brucite-like layers to form LDHs. Observed M2+ and M3+ species
include Mg2+, Fe2+, Co2+, Cu2+, Ni2+, Cd2+ or Zn2+ and Al3+, Cr3+, Ga3+ or
Fe3+, respectively [3]. Furthermore, LDHs containing more than two species of the second
cation have been prepared. The charge density on the hydroxide layers of the LDH will
clearly depend upon the M2+/M3+ ratio. A particular advantage of LDHs, therefore, is that
the anion-exchange capacity of the LDH, and hence the number and arrangement of the
charge balancing anions in the LDH, may be controlled by varying the M2+/M3+ ratio.

A second class of LDHs, which have not been as extensively studied, contains
monovalent and trivalent matrix cations. An example is which consists of sheets
[LiAl2(OH)6] +A- mH2O, of aluminum octahedra with vacancies filled by lithium
atoms.
In naturally occurring LDHs, the most common anion found is carbonate. In practice,
however, there is no significant restriction to the nature of the charge balancing anion
that can occupy the interlayer region; for example, halides, oxo-anions, silicates,
polyoxometalate anions, complex anions as well as organic anions, may all be
incorporated.

Materials

 Hot plate with a magnetic stirrer

 Magnetic stirrer bar
 200 ml Erlenmeyer Flask
 500ml Beaker
 Burette Thermometer
 Filter paper
 Funnel

Reagents

 2.00 gr de Al(NO3)39H2OAL
 3.00 gr Mg(NO3)25H2O
 2.4 gr of Na2CO3
 3.50 gr of Na(OH)
 150 ml H2O

Experimental Procedure

Initially, 2.4 gr of NaCO3 and 3.50 gr of Na(OH) were weight and put in a beaker, after,
150 ml of H2O was added. Baker was placed in hot plate with a magnetic stirrer to
dissolve to 60 °C. In the same time, 2.00 gr de Al(NO3)39H2OAL and 3.00 gr
Mg(NO3)25H2O were weight to preparade a solution of 50ml. This solution was placed
in a burette using a funnel. Then, the solution contained in the burette was dropped drop
by drop in the baker. This mixture leaved under stirring for 24 hours with a constant
temperature. After this time, the product was filtered by gravity using a filter paper.
Finally, the filter paper was placed in a stove with a temperature of 50°C.

Observation and Results

Previous Calculations

Aluminum moles

1𝑚𝑚𝑚 𝑚𝑚 𝑚𝑚
2g Al (NO3)3 9H2O ∗ 375,13𝑚 𝑚𝑚(𝑁𝑂 = 𝟎, 𝟎𝟎𝟓𝟑 𝒎𝒐𝒍 𝒅𝒆 𝑨𝒍
3 )3 ∗ 9𝐻2 𝑚

M2+ moles

𝑚2+ 𝑚2+
= 3 = 0,0053= 0,015 mol de M2+
𝑚3+

Mg (NO3)2 *6H2O grams

256,40𝑚 𝑚𝑚(𝑁𝑂3 )2 ∗6𝑚2𝑚

0,0015 mol de M2+ * = 3.84g de Mg(NO3)2 5H2O
1 𝑚𝑚𝑚 𝑚𝑚 𝑚2+

Efficiency

Final product weight

Product = 0 ,729 g

Theorical product weight

1 𝑚𝑚𝑚 [𝑚𝑚6 𝑚𝑚2 (𝑚𝑚)16 ]𝑚𝑚3 ∗4𝑚2 𝑚 603.8 𝑚 [𝑚𝑚 𝑚𝑚2 (𝑚𝑚)16 ]𝑚𝑚3 ∗4𝑚2 𝑚
0,005 𝑚𝑚𝑚 𝑚𝑚 (𝑚3+ )* * 1 𝑚𝑚𝑚 [𝑚𝑚 6
2 𝑚𝑚𝑚 𝑚𝑚 𝑚𝑚 6 𝑚𝑚2 (𝑚𝑚)16 ]𝑚𝑚3 ∗4𝑚2 𝑚
=1.50 g [Mg6Al2(OH)16 ]CO3*H2O

𝑹𝒆𝒂𝒍 𝒘𝒆𝒊𝒈𝒉𝒕 𝟎.𝟕𝟐𝟗

% efficiency =𝑻𝒉𝒆𝒐𝒓𝒊𝒄𝒂𝒍 𝒘𝒆𝒊𝒈𝒉𝒕*100 = = 49%
𝟏.𝟓𝟎

Aluminum hydroxide precipitates first, this occurs by the ion exchange and the greater
affinity of the anion towards the metal sheets than the anions of the precursor metal salt.
Product of this precipitation, white substance was observed in the beaker.
Low efficiency may be due to poor filtration technique. One of the variables to consider
is the pore size of the filter paper, due to was no longer retain enough material and a large
amount of the product transferred was left in the waste. Another of the variables to
consider is the number of repetitions or washes that were given, only one wash was carried
out due to the lack of time availability, however, it was advisable to perform at least 3
washes. By other hand, the most important variable can be the not reaction of the reacts
to form the product.

Conclusion

It is particularly important the way that the disposition of the anions within the interlayer
can be modified by changing the charge on the layers, the degree of hydration.
Efficiency calculation help to determine a yield of less than 50% was obtained. This low
result can be due to poor filtration technique, lost product in the beaker or possibly due to
the non-reaction of the reactants for the formation of the desired product. LDHs materials
can be used in adsorption, catalysis, photochemical and ionic conductivity experiments.

References

[1] De Roy, A., Forano, C., El Malki, K., & Besse, J. P. (1992). Anionic clays: trends in
pillaring chemistry. In Expanded Clays and other microporous solids (pp. 108-169).
Springer, Boston, MA.

[2] Allmann, R., & Jepsen, H. P. (1969). Die struktur des hydrotalkits. Neues Jahrbuch
für Mineralogie Monatshefte, 1969, 544À551.

[3] Newman, S. P., & Jones, W. (1998). Synthesis, characterization and applications of
layered double hydroxides containing organic guests. New Journal of
Chemistry, 22(2), 105-115.

[4] Carrado, K. A., Kostapapas, A., & Suib, S. L. (1988). Layered double hydroxides
(LDHs). Solid State Ionics, 26(2), 77-86.