On the reactivity of zinc hydroxide acetate dihydrate in ethanol

Article abstract of DOI:10.1002/ejic.201300650

Zinc hydroxide acetate dihydrate, Zn₅(OH)₈(CH ₃CO₂)₂·2H₂O, reacts in ethanol at room temperature to yield a mixture of zinc oxide and anhydrous zinc acetate. The process is driven by dehydration of the starting salt. Dehydration of Zn₅(OH)₈(CH₃CO₂) ₂·2H₂O also occurs when it is heated in air, but the product obtained in that case depends on the heating rate, environment and temperature. For example, when it is kept in a sealed silica capillary at 100 °C, Zn₅(OH)₈(CH₃CO₂) ₂·1.5H₂O is formed after 15 min, whereas treatment in the range 90-100°C in an open environment results in the formation of anhydrous zinc hydroxide acetate. Heating of any of these products further causes their decomposition to Zn(CH₃CO₂)₂ and ZnO. The coordination bonding mode of the acetate groups in the anhydrous layered zinc hydroxide acetate prepared by reaction with ethanol was studied by using solid-state NMR spectroscopy. The presence of chelating, unidentate and bidentate bridging modes for the carbonyl carbon atom was revealed, but there was no evidence for the inclusion of ethanol in the resultant structure. Therefore, the reaction in ethanol offers a convenient strategy to prepare anhydrous zinc hydroxide acetate and/or zinc oxide, because it avoids the sensitivity of the thermally induced dehydroxlation process to time, temperature and environment. Decomposition of zinc hydroxide acetate dihydrate in ethanol can be exploited to generate ZnO nanoparticles at room temperature. The mechanism involves the removal of waters of hydration and the formation of Zn₅(OH)₈(CH₃CO₂)₂ followed by the generation of Zn(CH₃CO)₂ and ZnO. Copyright

Full text of DOI:10.1002/ejic.201300650

FULL PAPER
DOI:10.1002/ejic.201300650
On the Reactivity of Zinc Hydroxide Acetate Dihydrate in
Ethanol
[
a]
[a]
[a]
Amir Moezzi, Michael B. Cortie,* Ronald Shimmon, and
Andrew M. McDonagh[
a]
Keywords: Zinc / Solid-state reactions / Zinc hydroxide acetate / Zinc oxide / Intercalations
Zinc hydroxide acetate dihydrate, Zn
5
(OH)
8
(CH
3
CO
2
)
2
·
3 2 2
position to Zn(CH CO ) and ZnO. The coordination bonding
2
H
2
O, reacts in ethanol at room temperature to yield a mix-
mode of the acetate groups in the anhydrous layered zinc
hydroxide acetate prepared by reaction with ethanol was
studied by using solid-state NMR spectroscopy. The presence
of chelating, unidentate and bidentate bridging modes for
the carbonyl carbon atom was revealed, but there was no
evidence for the inclusion of ethanol in the resultant struc-
ture. Therefore, the reaction in ethanol offers a convenient
strategy to prepare anhydrous zinc hydroxide acetate and/or
zinc oxide, because it avoids the sensitivity of the thermally
induced dehydroxlation process to time, temperature and en-
vironment.
ture of zinc oxide and anhydrous zinc acetate. The process
is driven by dehydration of the starting salt. Dehydration of
Zn (OH) (CH CO ) ·2H O also occurs when it is heated in
5 8 3 2 2 2
air, but the product obtained in that case depends on the
heating rate, environment and temperature. For example,
when it is kept in a sealed silica capillary at 100 °C, Zn
5
-
(OH) (CH CO ·1.5H O is formed after 15 min, whereas
8
3
2
)
2
2
treatment in the range 90–100 °C in an open environment
results in the formation of anhydrous zinc hydroxide acetate.
Heating of any of these products further causes their decom-
2H
O.[9] Nevertheless, in this latter work, the precursor used
2
Introduction
for the intercalation of ethylene glycol was synthesized in
Zinc hydroxide acetate dihydrate, Zn (OH) (CH CO ) ·
[8]
5
8
3
2 2
anhydrous methanol. In work by Poul et al., where zinc
2
H O (often reported as zinc hydroxy acetate), is a layered
2
acetate was dissolved in diethylene glycol, 1,2-propanediol
or ethanol, it was noticed that other compositions for the
hydroxide salt comprised of sheets of zinc hydroxide with
intercalated acetate (CH CO ) groups.
–
[1,2]
Several synthetic
3
2
as-synthesizedmaterial[reportedasZn(OH)1.58(CH CO )
·
3
2 0.42
[
1,3–6]
routes have been reported including aqueous methods,
0
.31H O based on chemical analysis of Zn, C and H] might
2
methods using ammonium hydroxide[ as well as the for-
7]
be possible. Interestingly, the carbon content was ca. 13%
mation of Zn (OH) (CH CO ) ·nH O in alcoholic me-
5
8
3
2 2
2
higher than expected, which was suggested to arise from
[
2,8,9]
dia.
Inspection of the literature reveals that the re-
[11]
physical adsorption of alcohol on the particles.
In the
ported positions of low-angle XRD peaks, which are associ-
ated with diffraction from the sheets of this layered com-
pound, vary significantly. In some cases multiple low-angle
peaks (d-spacings) have been observed.[ Many of the dis-
parities between the d-spacing values can be attributed to
the method of synthesis, particularly those using organic
solvents such as methanol, ethanol, ethylene glycol and 1,2-
propanediol and also methods that use ammonia solutions.
Some reports have claimed that the expansion of the inter-
layer distance is due to the intercalation of more than a
stoichiometric amount of acetate groups in the gallery
work presented here, we show that Zn (OH) (CH CO ) ·
5
8
3
2 2
2
H O reacts in the presence of ethanol to form zinc oxide
2
as well as dehydrated zinc hydroxide acetate, with associated
changes in the modes of bonding between the acetate
anions and zinc centres. Although this process is relatively
slow at room temperature, it is an important consideration
when synthesizing or using this material in the presence of
alcohols that have a dehydrating capacity. However, because
of the formation of ZnO, the reaction is not suitable for
the purpose of preparing pure dehydrated zinc hydroxide
acetate.
10]
[
2]
spaces. Kasai and Fujihara showed the possibility of in-
tercalation of ethylene glycol to form a hybrid material with
a
composition of Zn (OH) (CH CO ) (HOC H OH) · Results and Discussion
5
8
3
2 2
2
4
2
Powder XRD data (Figure 1) show that, after suspending
[
a] Institute for Nanoscale Technology, University of Technology
Sydney,
Zn (OH) (CH CO ) ·2H O in ethanol for 96 h, the result-
5 8 3 2 2 2
Sydney, NSW 2007, Australia
E-mail: michael.cortie@uts.edu.au
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201300650.
ant material contains a significant amount of ZnO. A peak
associated with an interlayer distance of ca. 1.3 nm (2θ =
6.0°, Cu-K ) in the starting material is absent in the data
α
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collected for the reacted material, while a low-intensity peak tion of anhydrous zinc hydroxide acetate to favour the for-
associated with a d-spacing of ca. 1.75 nm is present both mation of ZnO at room temperature.
before and after suspension in ethanol. Previously, we
Changes in the X-ray diffraction pattern that occur upon
–1
showed that Zn (OH) (CH CO ) ·2H O is quite sensitive heating Zn (OH) (CH CO ) ·2H O at 2 °Cmin in air
5
8
3
2 2
2
5
8
3
2 2
2
to dehydration upon heating and that its characteristic were investigated for comparison (Figure 2). The Zn (OH) -
5
8
XRD peak for d = 1.34 nm disappears as the material is (CH CO ) ·2H O phase (peak at d = 1.34 nm) starts to dis-
3
2 2
2
[
6]
dehydrated. We hypothesized that ethanol may exert a appear at 89 °C and is gone at 97 °C, with the X-ray pattern
similar effect shown in Equation (1). Decomposition of indicating a lowering of the crystallinity of the sample and
Zn (OH) (CH CO ) ·xH O yields ZnO and zinc acetate widening of the interlayer spacing in that temperature
5
8
3
2 2
2
Zn(CH CO ) [Equation (2)]. We will show here that x can range. However, peaks from ZnO appear in the pattern only
3
2 2
be 1.5 or 0.
at ca. 104 °C, and anhydrous zinc acetate only at 115 °C.
Clearly, there is an intermediate solid phase between 97 and
EtOH
Zn
5
5
(OH)
(OH)
8
8
(CH
3
3
CO
2
)
2
2
·2H
2
O
Ǟ Zn
5
(OH)
8
(CH
3
CO
2 2 2
) ·xH O +
104 °C that was not well crystallised. Therefore, an experi-
(2–x) H
2
O
(1)
(2)
ment was carried out whereby the temperature was ramped
to 100 °C at 5 °Cmin–1 and then kept at there for 105 min,
while data were collected (Figure 3). In this case the simul-
taneous formation of the intermediate phase and ZnO is
clearly revealed by the development of a strong peak at d =
Zn
(CH
CO
2
)
·xH
2
O Ǟ 4 ZnO + Zn(CH
3
CO
2 2(s)
) +
(4+x) H
2
O
1.50 nm for the former and the strengthening of the charac-
teristic reflections of the latter. We assigned this intermedi-
ate compound as Zn (OH) (CH CO ) ·1.5H O (JC-PDF
5
8
3
2 2
2
[
8,10]
00-056-0569).
This in turn decomposed after a further
15 min at 100 °C to form anhydrous zinc acetate and more
ZnO.
5 8 3 2 2 2
Figure 1. (A) Powder XRD data: (I) Zn (OH) (CH CO ) ·2H O
obtained by the method described in ref.[ showing a characteristic
strong peak at d = 1.35 nm (also plotted on a logarithmic scale as
an inset); (II) freeze-dried product obtained after suspending (I) in
ethanol for 96 h. Peaks marked with “*” correspond to ZnO (JC-
PDF 01-089-0510). (B) (III) Low 2θ data for (II), showing a char-
acteristic peak at d = 1.75 nm; (IV) product of the reaction between
10]
5 8 3 2 2 2
Figure 2. Dehydration of Zn (OH) (CH CO ) ·2H O induced by
ramping of the sample at 2 °Cmin in a synchrotron powder dif-
fraction beamline.
–
1
Zn
5
(OH)
8
(CH
3
CO
2
)
2
·2H
2
O and ethanol dried at 50 °C under re-
duced pressure; (V) low 2θ data for (I) showing that it also contains
a small amount of a compound with a peak at ca. 1.7 nm.
Zinc acetate is reasonably soluble in ethanol (ca. 3 g/
00 mL ) and by recharging the reaction mixture with sonably slow and may be skipped if the ramp rate is too
fresh ethanol, we were able to drive the decomposition reac- high. Surprisingly, the Zn (OH) (CH CO ) reported
The formation of the 1.5H O intermediate phase is rea-
2
[
12]
1
[3,10]
to
3
4
3
2 2
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4
1
.5% is observed, and a broad exotherm is centred at ca.
97 °C. An overall mass loss of 30% would be expected if
anhydrous Zn (OH) (CH CO ) was converted to ZnO.
5
8
3
2 2
The measured mass loss of 20.3% is explained considering
the XRD data, which show that the reaction product al-
ready contained a significant amount of ZnO. However, as
we showed elsewhere, thermal treatment of Zn (OH) -
5
8
(
CH CO ) may also result in mass loss due to sublimation
3
2 2
6]
[
processes. It is difficult, therefore, to calculate the exact
ZnO/Zn (OH) (CH CO ) ratio in the material produced
5
8
3
2 2
here from the total mass loss values. Nevertheless, with the
aid of the knowledge about the decomposition mechanism
Figure 3. Conversion (arrowed) of Zn
mixture of Zn (OH) (CH CO ·1.5H
of isothermal heat treatment at 100 °C. Peaks characteristic of
Zn(CH CO and ZnO are marked “A” and “O”, respectively.
5
(OH)
8
(CH
3
CO
2
)
2
·2H
2
O to a
[6]
of Zn (OH) (CH CO ) ·2H O, a method was developed
5
8
3
2 2
2
5
8
3
2
)
2
2
O and ZnO after ca. 15 min
to estimate the ZnO/Zn (OH) (CH CO ) mass ratio by
5
8
3
2 2
3
2
)
2
using the mass loss of the first decomposition stage of
Zn (OH) (CH CO ) , which releases four mol of water.
5
8
3
2 2
This stage occurs prior to the temperatures required for any
sublimation processes. The formula below is applied over
the temperature range of 110–150 °C where X% is the mass
fraction of Zn (OH) (CH CO ) in the sample.
form after prolonged treatments at 90–100 °C (large peak
expected at d = 0.95 nm, 2θ = 4.7°) is absent in our data
collected at 100 °C. This puzzling discrepancy may have
arisen, because, at 100 °C, the silica capillaries used in our
5
8
3
2 2
synchrotron experiments retained H O driven from the
sample as steam or condensate thereby causing the sample
environment to have a high relative humidity. In contrast,
observed mass loss (%) at 110–150 °C
theoretical mass loss (%) of pure material at 110–150 °C
2
X% = 100
free H O would have been rapidly extracted from the solids
2
in the previously reported[
3,10]
powder diffraction experi-
ments as these samples were open to the atmosphere. The
compound with a peak at d ≈ 1.75 nm is also missing from
the data shown in Figure 2, possibly for the same reason.
TGA experiments revealed that the total mass loss value
for the product of the reaction of Zn (OH) (CH CO ) ·
5
8
3
2 2
2
H O with ethanol is 20.3% upon heating to 1000 °C,
2
which is significantly lower than that of Zn (OH) -
5
8
(
CH CO ) ·2H O (37.4%). There is ca. 0.9% mass loss up
3 2 2 2
to 110 °C but importantly, a dehydration stage is absent
Figure 4). This indicates that immersion in ethanol has re-
moved all of the waters of hydration. The mass loss of ca.
.5% between 110 and 150 °C is associated with an endo-
thermic process with a peak at 133 °C (Figure 5), and heat-
(
7
Figure 5. DTA of (I) Zn
freeze-dried product of the reaction between Zn
5
(OH)
8
(CH
3
CO
2
)
2
·2H
5
2
O and (II) the
(CH CO
(OH)
8
3
2 2
) ·
ing to ca. 190 °C results in ca. 6.6% mass loss, which is 2H O and ethanol. Curve (II) is available on an expanded vertical
2
associated with a small and broad endothermic peak at axis in the Supporting Information.
183 °C. Between 190 and 400 °C, a further mass loss of ca.
The theoretical mass loss of pure Zn (OH) (CH CO )
2 2
5
8
3
for this stage of the reaction is ca. 12.4%. Here, only 7.5%
mass loss was observed in this temperature range. The dif-
ference is assigned to the presence of ZnO in the product.
The ratio of the observed mass loss value for the product
to the theoretical value is calculated to be 60.5%. From
these data, the mass ratio of ZnO/Zn (OH) (CH CO ) is
5
8
3
2 2
calculated to be of the order of 2:3.
The composition of the reaction product was further ex-
amined by using Raman, FTIR and NMR spectroscopy.
Raman spectra of Zn (OH) (CH CO ) ·2H O and the
5
8
3
2 2
2
product of its reaction in ethanol are shown in Figure 6.
The Raman data are indicative of a material containing
ZnO as well as an acetate-containing compound. Peaks lo-
Figure 4. TGA data for (I) Zn
freeze-dried product of the reaction between Zn
O and ethanol.
5
(OH)
8
(CH
3
CO
2
)
2
·2H
5
2
O and (II) the
(CH CO
–1
cated at 2935 cm are associated with a symmetric CH3
(OH)
8
3
2 2
) ·
[
13]
–1
stretch.
The peaks centred at 940 cm are associated
2H
2
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with C–C stretching.[14] A sharp peak located at 438 cm–1
in the spectra of the reaction product corresponds to a non-
polar optical phonon of ZnO.[
15]
Figure 6. Raman spectra corresponding to (I) Zn
O and (II) the product of the reaction between Zn
CH CO ·2H O and ethanol, freeze-dried for 24 h.
5
(OH)
8
(CH
3
CO
(OH) -
2 2
) ·
8
2
(
H
2
5
3
2
)
2
2
Comparison of the FTIR spectrum of Zn (OH) -
5
8
(
CH CO ) ·2H O with that of the reaction product reveals
3 2 2 2
–1
significant differences in the regions 430–470 cm and
1
4
while peaks at 1614, 1583 and 1550 cm are assigned to a (CH
COO antisymmetric stretch, and peaks at 1456, 1419 and
–
1
300–1700 cm (Figure 7 and Table 1). A peak centred at
Figure 7. FTIR spectra corresponding to (I) Zn
5 8 3 2 2
(OH) (CH CO ) ·
–
1
[15]
37 cm is assigned to a Zn–O stretching vibration,
2H O and (II) the product of the reaction between Zn (OH) -
2
5
8
–
1
3 2 2 2
CO ) ·2H O and ethanol, freeze-dried for 24 h. Inset: Ex-
–
1
–
panded view of the region 1800–1300 cm .
–
1
–
1
400 cm are assigned to the COO symmetric stretch. The
–
separation between the COO antisymmetric and symmet- Table 1. FTIR spectral assignments for Zn
5 8 3 2 2
(OH) (CH CO ) ·
–
–
2H O.
ric stretches [Δνa–s = ν (COO ) – ν (COO )] have been
2
a
s
Wavenumbers [cm–1][a]
577, 3479, 3403
1612w, 1583w, 1552
1456w, 1419w, 1394
1336
Assignments
Ref.
reported to yield information about the bonding mode of
the acetate anion to the zinc centre.[ Types of carboxylate
bonding to divalent metal cations can be expressed as
16]
[13,17]
[3,13]
[20]
3
OH stretching vibrations
–
COO antisymmetric stretch
–
Δνa–s (unidentate) Ͼ Δνa–s (ionic) Ն Δν (bridging biden-
COO symmetric stretch
a–s
[
[
20,21]
20,21]
tate) Ͼ Δνa–s (chelating).[
16]
For Zn (OH) (CH CO ) ·
CH symmetric bending
3
5
8
3
2 2
1039w, 1016
3
CH rocking
–
1
2
H O, there is a difference of 1552–1394 = 158 cm . This
2
–
1
[a] Note: “w” denotes weak signal.
value is less than the 164 cm reported for sodium acetate,
which exhibits ionic bonding and thus might suggest a
bridging bidentate or chelating coordination mode.
[
16]
For Nevertheless the locations of the signals are in the same
the reaction product we have found separations of 164, 158 region associated with methyl (δ = 0–45 ppm) and carbonyl
–
1
–1
[22]
and 150 cm . The 164 cm separation is identical to that (δ = 160–190 ppm) groups.
No signal corresponding to
reported for sodium acetate[17,18] and suggests that ionic ethoxy carbon atom environments in the range of δ = 60–
carboxylate bonding might be involved.
50 cm suggests that a chelating mode exists in the struc- been incorporated in the reaction product structure. Five
[16]
[22]
A value of 110 ppm
was detected indicating that ethanol has not
–
1
1
ture.
[
16]
Therefore, the material appears to have at least signals assigned to resonances of the carbonyl carbon
three types of carboxylate bonding. However, resolving this atoms were detected at δ = 177.6, 178.3, 181, 181.5 and
[16]
issue based only upon FTIR data is problematic, and so 182.7 ppm. Also four signals assigned to resonances of the
[
19]
solid-state NMR
ducted.
spectroscopy experiments were con- carbon atoms associated with CH were detected at δ =
3
24.5, 25.4, 26.3 and 26.8 ppm. A signal at δ = 182.7 ppm
The CP-MAS 13C NMR spectrum of the product of the suggests the presence of a chelating coordination mode for
reaction between Zn (OH) (CH CO ) ·2H O and ethanol the carbonyl group, whereas a resonance at δ = 177.6 ppm
5
8
3
2 2
2
[
19]
is shown in Figure 8. In contrast to the spectrum of suggests a unidentate mode.
The intermediate signals
Zn (OH) (CH CO ) ·2H O, which contains only two major show a bidentate bridging state or a combination of modes.
5
8
3
2 2
2
peaks located at δ ≈ 180 and 25 ppm,[ the spectrum of the This finding confirms the presence of acetate in the material
6]
product of the reaction between Zn (OH) (CH CO ) · but with different types of coordination modes compared
5
8
3
2 2
2
H O and ethanol shows several signals in each region. with Zn (OH) (CH CO ) ·2H O.
2
5
8
3
2 2
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2
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FULL PAPER
the Australian Synchrotron with samples kept in spinning 0.3 mm
diameter silica capillary tubes (see Supporting Information for ex-
perimental details).
Supporting Information (see footnote on the first page of this arti-
cle): Method of preparation for Zn (OH) (CH CO ) ·2H O and
5 8 3 2 2 2
description of other experimental techniques used.
Acknowledgments
This work was supported by PT. Indo Lysaght (Indonesia). We also
thank Dr. K. Kannangara from the School of Science and Health,
UWS, Australia for solid-state NMR spectroscopy. The in situ
XRD data were obtained with the powder diffraction beamline at
the Australian Synchrotron, Victoria, Australia.
[
[
[
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for 24 h.
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[
[
[
[
2
Conclusions
3
We have shown that zinc hydroxide acetate dihydrate in
ethanol at room temperature undergoes dehydration to
form zinc oxide. A comparison with thermally treated zinc
3
hydroxide acetate dihydrate indicates that anhydrous zinc [10] A. Moezzi, A. M. McDonagh, A. Dowd, M. B. Cortie, Inorg.
hydroxide acetate, Zn (OH) (CH CO ) , readily forms ZnO
Chem. 2013, 52, 95–102.
5
8
3
2 2
[
[
11] M. Taibi, S. Ammar, N. Jouini, F. Fie’vet, J. Phys. Chem. Solids
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2006, 67, 932–937.
12] J. A. Dean, Lange’s Handbook of Chemistry, McGraw Hill,
Inc., New York, 1999.
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157, C363–C373.
exhibits more than one bonding mode between the acetate
anions and the zinc centres, but there is no evidence of co-
ordinated or intercalated ethanol. The reaction of zinc hy-
droxide acetate in ethanol is of practical interest, because it
provides a convenient way to prepare anhydrous zinc hy-
droxide acetate and/or nanocrystalline ZnO, and because it
has implications for instances where zinc hydroxide acetate
dihydrate is synthesized or used in alcoholic media.
[
[
14] J. Hedberg, S. Baldelli, C. Leygraf, E. Tyrode, J. Electrochem.
Soc. 2010, 157, C357–C362.
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[
[
[
[
16] G. B. Deacon, R. J. Phillips, Coord. Chem. rev. 1980, 33, 227–
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002, 41, 6426–6431.
6
1
Experimental Section
2
O,[6]
[20] R. Q. Song, A. W. Xu, B. Deng, Q. Li, G. Y. Chen, Adv. Funct.
Mater. 2007, 17, 296–306.
Zinc hydroxide acetate dihydrate, Zn (OH) (CH CO ) ·2H
5 8 3 2 2 2
was stirred in ethanol for a period of 96 h with fresh ethanol intro-
duced at 24 h intervals (see Supporting Information). The freeze-
dried product (close to 100% yield) was characterised by powder
X-ray diffraction (XRD), thermogravimetric analysis (TGA) and
differential thermal analysis (DTA), Raman, IR and 13C NMR
spectroscopy. In situ X-ray diffraction experiments at various tem-
peratures were conducted with the powder diffraction beamline at
[
[
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gawa, K. T. Nakamura, Spectrochim. Acta, Part A 1998, 54,
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22] A. De Marco, R. Spaccini, P. Vittozzi, F. Esposito, B. Berg, A.
Virzo De Santo, Soil Biol. Biochem. 2012, 51, 1–15.
Received: May 22, 2013
Published Online: August 9, 2013
Eur. J. Inorg. Chem. 2013, 5133–5137
5137
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim