Journal of Sol-Gel Science and Technology 29, 71–79, 2004

c 2004 Kluwer Academic Publishers. Manufactured in The United States.

Non-Basic Solution Routes to Prepare ZnO Nanoparticles

EIJI HOSONO, SHINOBU FUJIHARA∗ , TOSHIO KIMURA AND HIROAKI IMAI

Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi,
Kohoku-ku, Yokohama 223-8522, Japan
[email protected]

Received September 17, 2003; Accepted December 11, 2003

Abstract. Nanocrystalline ZnO particles were prepared from alcoholic solutions of zinc acetate dihydrate without
using base such as NaOH or LiOH through a colloid process carried out at a low temperature of 60◦ C. A comparative
study of chemical reactions from zinc acetate dihydrate to ZnO was made using different types of monool solvents,
i.e. methanol, ethanol, and 2-methoxyethanol. It was revealed that layered hydroxide zinc acetate was formed as
an intermediate and its transformation into ZnO was a key reaction step in any of the solutions. Reaction time
necessary for the precipitation of ZnO was greatly influenced by the solvents used. Methanol was useful for the
preparation of the ZnO nanoparticles, which were chemically pure in terms of cation impurities and exhibited green
photoluminescence by the ultraviolet excitation.

Keywords: ZnO, nanoparticles, formation mechanisms, photoluminescence

1. Introduction acetylacetonate) are dissolved in alcoholic or other

organic solvents to which basic solutions containing
Semiconductor nanoparticles have attracted interests of NaOH, LiOH or NH4 OH are added [18–27]. It is be-
many academic and industrial researchers because of lieved that formation of colloidal ZnO follows several
their unusual optoelectronic properties based on quan- reaction steps, of which the last is transformation of
tum size effects [1]. Numerous reports are found in zinc hydroxide to zinc oxide under basic solution con-
the literature regarding synthetic techniques as well as ditions,
potential or practical applications of nanosized semi-
conductors such as CdS, CdSe, ZnS, TiO2 , Fe2 O3 , and Zn(OH)2 ↔ ZnO + H2 O (1)
ZnO [2–7].
Wurtzite ZnO is an n-type semiconductor with a
This reaction is likely to be valid for the process us-
wide band-gap of 3.3 eV. Nanosized ZnO can be
ing Zn(ClO4 )2 because ClO− 4 ions are inert in terms
utilized in electrochemical fields including chemical
of ability of complex formation with Zn2+ in al-
sensors [8], photocatalysts [9], phosphors [10] and
coholic solutions [28, 29] and do not impede the
dye-sensitized solar cells [11–14]. Nanocolloids or
formation of zinc hydroxyl complexes. In contrast,
nanopowders of ZnO have been prepared by adopting
Zn(Ac)2 ·2H2 O (Ac = CH3 COO) provides much more
synthetic methods developed by Koch et al. [15], Bah-
complicated reaction precursors for ZnO because of
nemann et al. [16], or Spanhel and Anderson [17]. Basi-
higher reactivity of Ac ions (CH3 COO− ) with Zn2+
cally, zinc salts such as Zn(ClO4 )2 , Zn(NO3 )2 , Zn(CH3
[30]. In the presence of the Ac ions in the basic
COO)2 ·2H2 O, or Zn(CH3 COCHCOCH3 )2 ·H2 O (zinc
solutions, the precursors of ZnO are reported to be
Zn10 O4 (Ac)12 , Zn4 O(Ac)6 , or Zn5 (OH)8 (Ac)2 ·2H2 O
∗ To whom all correspondence should be addressed. [7, 26, 31]. Hydrolysis and condensation of these
72 Hosono et al.

precursors lead to the precipitation of ZnO in the pres- For the EtOH or the 2-ME solution, the same amount of
ence of base. Zn(Ac)2 ·2H2 O was added to 196 mL of EtOH or 2-ME
In view of fundamental studies as well as indus- under the same conditions. In contrast to the MeOH so-
trial applications of nanoparticles, chemically pure or lution, Zn(Ac)2 ·2H2 O was not dissolved completely in
compositionally well-defined ZnO is required. This is these two solutions. Then 4 mL of water was added
because electrical and luminescent properties undergo to each solution and the resultant mixtures were ul-
dramatic changes by impurities doped in ZnO [32, 33]. trasonicated for 10 min, leading to the clear, transpar-
Moreover the growth manner and kinetics of nanopar- ent solutions. Taking account of the hydration water
ticles are also influenced by foreign cationic species. in Zn(Ac)2 ·2H2 O, a molar ratio, H2 O/Zn, calculated
While effort has been made to remove alkali ions (Li+ was 2 for the MeOH solution and 9.4 for the EtOH and
or Na+ ) by washing in order to obtain pure ZnO [7], 2-ME solutions.
development of the process without addition of base The solutions were placed into 200 mL Erlenmeyer
is a prime requirement for future applications of the flasks and heated at 60◦ C under reflux for various peri-
ZnO nanoparticles. Kumar et al. [34] reported sono- ods of time using rotary evaporation apparatus. Careful
chemical synthesis of nanosized ZnO from aqueous attention was paid in order not to lose the solvents dur-
solutions of Zn(Ac)2 ·2H2 O using a high-intensity ul- ing heating. After white precipitates were observed, the
trasonic horn under 1.5 atm of argon at room temper- solutions were removed from the apparatus and cooled
ature. Very recently, Poul et al. [35] have suggested a to room temperature. The precipitates were then cen-
possible synthesis of the nanoparticles through hydrol- trifuged at 13000 rpm for 10 min. Final products were
ysis of zinc salts in polyol media (diethyleneglycol or dried at room temperature in the ambient atmosphere
ethyleneglycol). following the removal of supernatant.
In this study, nanocrystalline ZnO particles were For the precipitates prepared from the MeOH so-
successfully prepared through controlled hydrolysis lution, washing was done with methanol by repeat-
of Zn(Ac)2 ·2H2 O under moderate conditions such ing centrifugation. As described later, washing was
as neutral solutions, a low temperature of 60◦ C, effective to remove by-products such as Zn5 (OH)8
an atmospheric pressure, and an ambient atmo- (Ac)2 ·2H2 O and obtain single-phase ZnO nanoparti-
sphere. A comparative study was made to investi- cles.
gate reaction, nucleation and crystal growth mecha-
nisms underlying the colloid process using different
types of monool solvents, i.e. methanol, ethanol, and
2-methoxyethanol. 2.2. Analysis and Measurement

Crystal structure identification was made by X-ray

2. Experimental diffraction (XRD) with a Rigaku model RAD-C
diffractometer using Cu Kα radiation in the 2θ range
2.1. Colloid Process 3–60◦ . Particle sizes were observed by high resolu-
tion transmission electron microscopy (HRTEM) with
Zinc acetate dihydrate, Zn(Ac)2 ·2H2 O, with 99.9% pu- a Philips model TECNAI F20 microscope. Optical ab-
rity was obtained from Wako Pure Chemicals Co., sorption spectra were recorded with a Hitachi model
Ltd., Japan. Methanol (MeOH), ethanol (EtOH), and U-3300 ultraviolet (UV) visible spectrophotometer.
2-methoxyethanol (2-ME) were used as received from Photoluminescence (PL) spectra were measured at
Taisei Chemical Co., Ltd., Imazu Chemical Co., Ltd., room temperature with a Shimadzu model RF-5700PC
and Wako, Japan, respectively, without further purifi- using a Xe lamp (150 W) as a UV light source.
cation. Fourier transform infrared (FTIR) spectra were mea-
Three kinds of Zn(Ac)2 ·2H2 O solutions were pre- sured using the KBr method with a BIO-RAD model
pared by using MeOH, EtOH, or 2-ME as solvents. FTS-60A spectrophotometer. Thermal behavior was
For the MeOH solution, a 6.5853 g (0.03 mol) sam- examined by thermogravimetry-differential thermal
ple of Zn(Ac)2 ·2H2 O was dissolved in 200 mL of analysis (TG-DTA) with a Mac Science model 2020S
MeOH under vigorous stirring at room temperature thermal analyzer using a heating rate of 5◦ C/min in air.
and atmospheric pressure and then ultrasonicated for The pH value of the solution was measured by a Horiba
10 min. The clear, transparent solution was obtained. model F-21 pH meter.
 Non-Basic Solution Routes to Prepare ZnO Nanoparticles 73

3. Results

3.1. MeOH Solution

The pH of the as-prepared MeOH solution was mea-

sured to be 6.3 at 25◦ C. Generally the pH of methanolic
solutions is not equivalent to –log aH (aH : hydrogen ion
activity) or −log [H+ ] [36]. The autoprotolysis con-
stant of methanol is 10−16.6 and hence the pH is equal
to 8.3 at a neutral condition. Therefore the present so-
lution has a relatively acidic nature and is far from
the basic conditions that have been adopted by many
researchers so far.
The transparent methanolic solution of Figure 2. Reflux-time dependence of the ZnO (101) peak (
) and
the crystallite size () for particles after washing.
Zn(Ac)2 ·2H2 O turned turbid with a white color
during heating at 60◦ C under reflux. The XRD
analysis of particles obtained by centrifugation of from LHZA. It should be noted that a broad peak
colloidal products revealed that they were a mixture around 21–24◦ in the pattern is due to a glass holder
of crystalline ZnO and Zn5 (OH)8 (Ac)2 ·2H2 O called for the XRD measurement. Higher peak intensities
layered hydroxide zinc acetate (LHZA). The typical in the pattern in Fig. 1(b) are attributed to the larger
XRD pattern is shown in Fig. 1(a) for the particles amount of ZnO measured. Lattice constants of the
obtained from colloids after refluxing for 12 h. A ZnO nanoparticles thus prepared were determined to
diffraction peak at a low angle of 2θ = 6.0◦ is ascribed be a = 0.3256 and c = 0.5217 nm, which is slightly
to (001) planes of LHZA which has a large c-axis larger than those of bulk ZnO (a = 0.324982 and
length of 1.475 nm [37]. Peaks due to ZnO are also c = 0.520661 nm; JCPDS No. 36-1451).
seen in the pattern. It was found that LHZA was Particles obtained from centrifuged colloids with the
effectively removed from the mixture particles by different reflux time were also single-phase ZnO after
washing with MeOH using different solubility. The washing. The XRD patterns of all the washed parti-
pattern of the particles after washing shown in Fig. 1(b) cles were high quality enough to analyze crystallinity
is a clear evidence of the single-phase ZnO separated of ZnO. Figure 2 shows a reflux-time dependence of a
(101) peak intensity observed in the XRD patterns that
were recorded for the same amount of ZnO and a crys-
tallite size determined using the Scherrer’s equation,

D = 0.9λ/(β cos θ) (2)

where λ is the X-ray wavelength, β is the broadening of

the diffraction peak, and θ is the diffraction angle. Both
the intensity and the crystallite size increase monotoni-
cally with increasing reflux time, indicating that growth
of the ZnO particles proceeds and the crystallinity is
improved with time.
Typical HRTEM images of particles obtained from
colloids after refluxing at 60◦ C for 6 or 24 h are shown
in Fig. 3. The particles are predominantly spherical in
shape and have sizes of 5 and 10 nm for reflux time of 6
and 24 h, respectively. In Fig. 3(a), a lattice image due to
Figure 1. XRD patterns of particles obtained from colloids in the
phase contrast is also shown. The distance between the
MeOH solution after refluxing for 12 h: (a) as-prepared, (b) washed. adjacent lattice fringes corresponds to the interplanar
ZnO and LHZA peaks are labelled (•) and (∇), respectively. distance of ZnO (100), which is d100 = 0.282 nm.
74 Hosono et al.

Figure 4. Optical absorption spectra of ZnO colloid solutions with

the different reflux time.

Quantum size effects such as blue-shift of the band-

gap are observed in ZnO having particle sizes 7 nm
[15]. In the present case the particles from the solutions
refluxed for not more than 12 h would meet this criteria
as estimated from above experimental results. We ob-
served the quantum size effect in the PL measurements.
Figure 5 shows the PL spectra recorded at room tem-
perature for the as-prepared colloid solutions with the
shorter reflux time of 6, 8, and 12 h. An excitation wave-
length of 290 nm was used. UV emissions due to a re-
Figure 3. HRTEM images of particles obtained from the MeOH combination of photogenerated electron-hole pairs are
solution after refluxing for (a) 6 and (b) 24 h.
seen at wavelengths around 360 nm. This indicates that

Figure 4 shows the optical absorption spectra

recorded at room temperature for the as-prepared col-
loid solutions with the different reflux time. With in-
creasing reflux time from 12 to 72 h, the absorbance
at wavelengths less than ca. 380 nm increases progres-
sively indicative of the increased number of the ZnO
particles formed in the solution. In addition, scatter-
ing effects are enhanced with increasing reflux time
in the visible light region. The wavelength of 380 nm
corresponds to the bulk band-gap of 3.26 eV for ZnO.
Although the optical band-gap is generally determined
from the absorption spectra, too small absorbance of
the solutions refluxed for the shorter periods made such
the determination impossible. It was also difficult to
judge whether nanosized ZnO was formed with the re-
flux time of less than 12 h because of much smaller Figure 5. PL spectra of ZnO colloid solutions with the shorter reflux
absorbance observed. time of 6, 8, or 12 h.
 Non-Basic Solution Routes to Prepare ZnO Nanoparticles 75

ZnO was formed even in the solutions with the shorter

reflux time. With increasing reflux time, the emission
peak exhibits red-shift from 363.8 nm (3.41 eV) for 6
h to 368.0 nm (3.37 eV) for 8 h and 373.2 nm (3.32
eV) for 12 h. Because the UV emission is identified to
a direct band-gap transition, the ZnO particles formed
in the solutions show evidently the quantum size effect
and their size increases with increasing reflux time.
The well-known green emission at 530 nm also ap-
pears in all the particles shown in Fig. 5. The present
samples are free from cation impurities that are pos-
sibly doped in ZnO prepared using LiOH or NaOH.
The origin of the visible emission has been ascribed
to singly ionized oxygen vacancies for bulk powders
and additionally to surface fluorescence centers for
nanoparticles [19, 38].
In summary for the MeOH solution, ZnO was formed
from Zn(Ac)2 ·2H2 O without using base. The colloids
formed in the solutions were the mixture with LHZA
which could be removed by centrifugation and wash-
ing. The particles grew progressively in the solution
with increasing reflux time.

Figure 6. XRD patterns of particles obtained from colloids in the

3.2. EtOH Solution EtOH solution after refluxing for 10, 12, 24, or 48 h. ZnO, LHZA
and a-LHZA peaks are labelled (•), (∇), and (), respectively.
The ethanolic solution of Zn(Ac)2 ·2H2 O showed quite
different behavior in the precipitation of solid phases.
Figure 6 shows the XRD patterns for particles obtained and (004), respectively. The origin of the peaks at 9.5
from colloids after refluxing the solutions at 60◦ C for and 12.4◦ is currently unknown.
10, 12, 24, or 48 h. Relatively strong five peaks ap- With the reflux time of 24 h, an additional peak ap-
pear in the range 2θ 20◦ for the particles with the pears at 2θ = 6.0◦ , which in turn agrees with that of
reflux time of 10 or 12 h. Such the pattern is typical LHZA (001). The particles are finally transformed into
of zinc compounds with highly layered structures as the wurtzite ZnO after refluxing for 48 h. The crystallite
LHZA. The crystal structure of LHZA has been re- size derived from the Scherrer’s equation is 13.4 nm.
ported to be similar to that of Zn5 (OH)8 (NO3 )2 ·2H2 O Thus the nanocrystalline ZnO particles are obtained
[37, 39]. Brucite-type [Zn3 (OH)8 ]2− layers exist in the from the EtOH solution of Zn(Ac)2 ·2H2 O without us-
structure with intercalated NO− −
3 or Ac . Although a ing base through the formation of the intermediate com-
solid Zn(OH)2 phase is stable in the so-called ε-form pounds.
having a β-cristobalite structure, the layered structure Attempts were made to identify at least a compo-
actually exists in the presence of foreign anions and sition of the phase appeared with the shorter reflux
is recognized as the α-form of Zn(OH)2 [40, 41]. For time. Figure 7 shows the FTIR spectrum for the par-
the XRD pattern of LHZA, the (001) diffraction peak is ticles from the solution refluxed for 10 h. The spec-
strongest and appears at 2θ = 6.0◦ . Much weaker (002) trum has three major peaks in the range 1300–1600
and (003) peaks appear at 12.0 and 18.1◦ , respectively cm−1 and one broad peak around 3435 cm−1 . The lat-
[37]. In the present case, the particles from the solu- ter is assigned to the stretching vibration of the OH
tion refluxed for 10 or 12 h have slightly shifted peaks groups, ν(OH), indicative of the presence of hydroxyl
in due order at 2θ = 5.0, 9.5, 12.4, 15.1 and 20.2◦ . ions and/or water in the crystal. The 1300–1600 cm−1
Assuming that the peak at 5.0◦ corresponds to (001), region serves as a fingerprint of the Ac group. A peak
a c-axis lattice parameter is calculated to be 1.766 nm at 1575 cm−1 and peaks at 1405 and 1338 cm−1 re-
and the peaks at 15.1 and 20.2◦ can be assigned to (003) sult from the asymmetric stretching mode of COO,
76 Hosono et al.

Figure 7. IR spectrum of particles from the EtOH solution refluxed Figure 8. TG-DTA curves of particles from the EtOH solution re-
for 10 h. fluxed for 10 h.

3.3. 2-ME Solution

ν(COO), and the deformation mode of CH3 , δ(CH3 ),
respectively [42]. Thus the crystal contains the OH and The 2-methoxyethanol solution of Zn(Ac)2 ·2H2 O was
the Ac groups in its structure, which is possibly related clear at least for 48 h during refluxing at 60◦ C. Af-
to the LHZA structure as suggested by the XRD anal- ter 48 h, white precipitates were observed in the solu-
ysis. The distinction between hydroxyl ions and wa- tion. Figure 9 shows the XRD patterns for the particles
ter is difficult since the bending mode of H2 O around obtained from colloids after refluxing the solutions at
1595 cm−1 is obscured by the ν(COO) mode. 60◦ C for 48 or 72 h. The particles after refluxing for
The absence of water in the crystal structure was 48 h are the mixture of LHZA, a-LHZA, and ZnO. Af-
suggested by the thermal analysis of the particles. A ter 72 h, the particles are transformed into single-phase
slight weight loss accompanied by a small and broad
endothermic peak is typically observed at temperatures
below 100◦ C in the TG-DTA curve for the layered hy-
droxide compounds containing water [37]. In contrast,
no sign of the removal of water is seen in the present
particles as shown in Fig. 8. The weight is kept almost
constant until a temperature of 128◦ C where a strong
endothermic peak appears. This peak is attributed to
the dehydroxylation reaction with 7.9% of weight loss
taking the fact into account that any form of zinc hy-
droxide decomposes into ZnO by the reaction (1) in
the temperature range 70–140◦ C [41]. A further grad-
ual weight loss, which comes to 24.0%, at tempera-
tures above 135◦ C corresponds to the combustion of
the Ac groups. Assuming that the crystal is composed
only of zinc, the OH and the Ac groups, a composi-
tion of Zn5 (OH)7.5 (Ac)2.5 is obtained using the ratio of
weight loss in two stages, 7.9% : 24.0%, as indicated
in Fig. 8. Then the phase is tentatively regarded as an Figure 9. XRD patterns of particles obtained from colloids in the
acetate-rich modification of LHZA (called a-LHZA, 2-ME solution after refluxing for 48 or 72 h. ZnO and LHZA peaks
hereafter). are labelled (•) and (∇), respectively.
 Non-Basic Solution Routes to Prepare ZnO Nanoparticles 77

ZnO. Accordingly the reflux time necessary for the gel processing through a polymerization reaction be-
formation of ZnO increases with the solutions in order, tween mononuclear hydroxyl complexes [44]. That is,
MeOH  EtOH < 2-ME. “Zn (OH) Zn” bridges are formed by an olation re-
action resulting in polynuclear zinc hydroxide clus-
ters. Under strongly basic conditions, an oxolation
4. Discussion reaction forming “Zn O Zn” bridges occurs further
to precipitate finally solid ZnO. Although the present
4.1. Formation of ZnO in the Absence of Base MeOH solution is free from the OH− ions, there ex-
ist the Ac− ions, the total amount of which is double
In any of the processes investigated in the present work, of that of zinc. The Ac− ions can act as a strong base
it has been found that LHZA or the other compound because of the smaller dissociation constant, K a , of
related to LHZA plays an important role as the inter- acetic acid. For example, K a value is as small as 10−9.7
mediate of ZnO. The formation mechanism of LHZA in methanol [45]. Then the discussion can go further
in the methanolic solution has been reported elsewhere based on a comparison with OH− -containing basic so-
based on non-aqueous solution reactions [43]. Briefly, lutions of [Zn(OH)2−n 2−n
n ]x . The stability of [Zn(OH)n ]x
Zn(Ac)2 ·2H2 O dissolved in MeOH undergoes a se- depends on the pH of the solutions [46]. At pH >
quence of reactions such as solvation by MeOH, forma- 9.0, [Zn(OH)2−n
n ]x is converted into ZnO because of
tion of methoxyacetate complexes, hydrolysis by water a higher chemical potential of OH− in an equilibrium,
originating from Zn(Ac)2 ·2H2 O itself, polymerization
of the complexes, and crystallization into LHZA. The
OH− + OH− ↔ O2− + H2 O (5)
kinetics of hydrolysis and polymerization was greatly
influenced by water concentrations in the solutions. The
The dehydration reaction of [Zn(OH)2−n
n ]x is funda-
overall chemical reaction to form LHZA is
mentally described as
5Zn(Ac)2 ·2H2 O → Zn5 (OH)8 (Ac)2 ·2H2 O + 8AcH
Zn(OH)2−n
n + Zn(OH)2−n
n ↔ Zn2 O(OH)4−2n
2n−2 + H2 O
(3)
(6)
In this report, we discuss the conversion of LHZA In the present case, a higher chemical potential of basic
into ZnO. First, reactions in the MeOH solution are species is derived from the Ac− ions. Then the follow-
considered. The pertinent reaction is expressed by ing equilibrium instead of (5) is conceivable,

Zn5 (OH)8 (Ac)2 ·2H2 O → 5ZnO + 2AcH + 5H2 O OH− + Ac− ↔ O2− + AcH (7)
(4)
The deprotonation reaction of [Zn(OH)2−n
n ]x can be
It is assumed that the reaction (4) occurring in the described as
non-aqueous solution is a result of hydrolysis and de-


protonation of LHZA. Hydrolysis is regarded as the Zn(OH)2−n
n x
+ xAc− ↔ ZnO(OH)1−n
n−1 x + xAcH
removal of the intercalated Ac− ions. Zinc hydroxyl (8)
complexes, namely [Zn(OH)2−n n ]x , are produced from
the brucite-related “Zn5 (OH)8 ” layers in the LHZA
Thus the “Zn O Zn” bonds are constructed and the
structure. The water concentration in the solution does
complexes are finally transformed into solid ZnO. Be-
not exceed double of the zinc concentration because
cause ZnO is sparingly soluble in MeOH, the reaction
water was supplied only from the starting material,
(4) is favored to the right.
Zn(Ac)2 ·2H2 O. Therefore the hydrolysis reaction is ex-
pected to proceed considerably slowly. Indeed it took
more than 6 h to obtain finally the ZnO nanoparticles. 4.2. Solvent Effects on the Non-Aqueous
In the absence of base (OH− ) in the solution, the Solution Reactions
n value should be less than 2 and the [Zn(OH)2−n n ]x
complexes should have a positive charge. Such the All the solvents used in this study are characterized as
complexes correspond to those evolved in general sol- amphiprotic monools. The most important difference
78 Hosono et al.

among the solvents is their dielectric constant, 32.6, zinc acetate dihydrate to ZnO was made using differ-
24.3, and 16.9 for MeOH, EtOH, and 2-ME, respec- ent types of monool solvents, i.e. methanol, ethanol and
tively [45]. The dielectric constant primarily deter- 2-methoxyethanol. It was revealed that layered hydrox-
mines solubility of electrolytic salts. As we observed in ide zinc acetate was formed as the intermediate and its
the present work, Zn(Ac)2 ·2H2 O was more soluble in transformation into ZnO was influenced by the solvents
MeOH than in EtOH or 2-ME. Therefore the dissolu- used. The methanolic solution was most useful for the
tion of Zn(Ac)2 ·2H2 O had to be assisted by the addition preparation of the ZnO nanoparticles.
of water having higher dielectric constant of 78.5.
In the MeOH solution, the dissolution of
Acknowledgment
Zn(Ac)2 ·2H2 O accompanies solvation of zinc by
MeOH molecules. The zinc ion has a solvation
This work was supported by Grant-in-Aid for the 21st
number of six and forms an octahedral inner coor-
century COE program “KEIO Life Conjugate Chem-
dination sphere, [Zn(MeOH)6 ]2+ [47]. In contrast,
istry” from the Ministry of Education, Culture, Sports,
the EtOH or the 2-ME solution containing water
Science, and Technology, Japan.
will have the zinc coordination in which the water
molecule also participates as a solvate. In any case,
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