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Contents lists available at SciVerse ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Hydrothermal processing and in situ surface modification of metal oxide

nanomaterials
K. Namratha, K. Byrappa ∗
Center for Materials Science, University of Mysore, P.B. No. 21, NCHS Bldg., Manasagangothri, Mysore 570006, India

a r t i c l e i n f o a b s t r a c t

Article history: In situ surface modification of TiO2 and ZnO metal oxide particles has been carried out under hydro-
Received 23 July 2012 thermal conditions within a wide range of temperature and pressure (T = 150–400 ◦ C; P = up to 20 MPa).
Received in revised form The influence of the surfactant and selective doping with active metal ions on the crystal size, morphology,
30 December 2012
and photocatalytic activity of TiO2 and ZnO particles has been carried out. A systematic characterization
Accepted 2 January 2013
of the product has been carried out using powder XRD, FTIR, TGA, SEM/TEM, and UV–vis spectroscopy.
Similarly the photocatalytic activity in these metal oxides varies with the size, shape and dopant metals.
Keywords:
© 2013 Published by Elsevier B.V.
Metal oxides
TiO2
ZnO
Hydrothermal and solvothermal processing
In situ surface modification
Doping
Photocatalysis

1. Introduction
Metal oxides exhibit excellent electrical, magnetic, mechanical,
optical, and chemical properties with a broad range of applications
as semiconductors, optical devices, piezoelectric devices, surface
acoustic wave devices, sensors, transparent electrodes, solar cells,
antibacterial, antioxidant, drug delivery, hypothermia, etc. A few
metal oxides as fillers in some polymers would yield several new
materials with novel application potential for electronic, food pack-
aging, storing, etc. A major breakthrough occurred during the
1970s when Fujishima and Honda reported electrochemical pho-
tolysis of water at a semiconductor electrode (TiO2 ) [1]. TiO2 has
several other specific applications, and the common ones are as
photocatalyst, dye sensitized solar cells, white pigment, ceramic
glazes, sun screen and UV absorbers, also as electronic data stor-
age, and so on. Similarly, zinc oxide is well-known as an n-type wide
bandgap semiconductor (E = 3.37 eV at 300 K) with a large exciton
energy of 60 meV and thermal energy of 27 meV. Due to bright UV-
luminescence, ZnO is a perspective material for the manufacture of
UV-light emitting diodes, UV lasers operating at room temperature
and display devices. Moreover, ZnO quantum dots with very low
toxicity, high photostability, biofriendiness and biodegradability
have been demonstrated [2–5].
∗ Corresponding author. Tel.: +91 8212419720; fax: +91 8212515346.
E-mail address: kbyrappa@gmail.com (K. Byrappa).
During the 1960s the growth of TiO2 and ZnO as bulk single crys-
tals was very popular, and much of the earlier literature surveyed
shows such attempts, and a hydrothermal method was popularly
used to synthesize both these metal oxides under supercritical
hydrothermal conditions [6–8]. However, researchers experienced
several difficulties in the growth of large size single crystals of these
metal oxides, and their popularity was limited.
With the discovery of quantization effect during the late 1970s,
the size reduction in metal oxide semiconductors became a major
objective to achieve higher efficiency in their applications. Diffi-
culties in the growth of metal oxide nanocrystals were associated
with the control of size, morphology, coagulation, reproducibil-
ity of results and dispersability. During the 1990s several such
attempts were made on the use of organic molecules as ligands,
capping agents or surfactants. Also ex situ surface modification
was tried with limited success. Thus an alternate route was envis-
aged to obtain high quality nanocrystals of TiO2 and ZnO with
controlled size, morphology, dispersability and without any coag-
ulation using in situ surface modification through novel solution
processing consisting of hydrothermal, solvothermal and supercrit-
ical hydrothermal methods. The size could be reduced significantly
to a few nanometers without any coagulation, and the organic
coating was so uniform and thin that it did not alter the inher-
ent properties of the metal oxide core. The organics which are
insoluble and exist as separate phases under ordinary conditions
became homogeneous phases under hydrothermal/solvothermal
conditions. The small size and high surface to volume ratio of

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http://dx.doi.org/10.1016/j.supflu.2013.01.007

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the individual nanoparticles impart distinct size tunable physi-
cal and electronic properties that have prompted some to refer
to them as “artificial atoms”. A highly controlled self-assembly of
these hybrid nanocrystals when dispersed in organic solvents into
two-dimensional and/or three-dimensional ordered structures or
super-lattice structures remains a relatively unexplored area.
Although various experimental methods are available to syn-
thesize these metal oxides, the synthesis under hydrothermal and
solvothermal conditions produces high quality metal oxides with
tailor-made properties owing to their controlled diffusion, higher
activity of the solvent, and the homogenization of the surfactant
with the media under higher temperature and pressure conditions
[9,10]. The hydrothermal synthesis has been clearly identified as an
important technology for materials synthesis [11,12]. The hydro-
thermal technique is a promising alternative synthesis method
because of the low process temperature, and it is very easy to
control the crystal size. The hydrothermal process has several
advantages over the other growth processes such as the use of sim-
ple equipment, ease of operation, catalyst-free growth, low cost,
environmentally friendly process, etc. The low reaction temper-
atures make this method an attractive one for microelectronics
and plastic electronics [11]. Also the method is especially useful
for the synthesis of nanotubes, nanowires, nanoribbons, and other
nanostructures of these two metal oxides, which find some special
applications in the nanostructure forms. The in situ surface modifi-
cation under these conditions facilitates controlled shape, size and
dispersion for the metal oxide nanoparticles without any agglom-
eration. Further, the use of in situ surface modification has yielded
enormous success in the processing of a variety of nanoparticles
under hydrothermal conditions [13]. The use of a variety of organic
and inorganic solvents and various additives and surfactants or
other organic capping agents has resulted in greater success to con-
trol the process parameters. Similarly the addition of some selected
dopants enhances their application potential. The presence of these
organics in different forms has enhanced the reaction kinetics expo-
nentially, thereby reducing the reaction time by retaining high
quality of the metal oxides. In spite of the fact that doping has been
one of the oldest approaches crystal growers adopted in the earlier
times to modify the crystal morphology, still it is popular even in
the processing of nanoparticles. The researchers are also employing
the coupled doping to alter the semiconductor properties of these
metal oxides, and it has become an active area of research [13,14].
Here, the authors report, the role of experimental parameters
on the processing of metal oxides and the influence of the addi-
tion of organics, in situ surface modification, use of selective doping
including coupled doping on the photocatalytic properties.
2. Materials and methods
2.1. Hydrothermal experiments
The experiments were carried out in General Purpose autoclaves
using Teflon liners (for sub-critical hydrothermal experiments in
the temperature range 150–240 ◦ C) or Batch reactors (for super-
critical hydrothermal experiments at temperature 400 ◦ C) provided
with platinum or gold liners or capsules. Fig. 1 shows the flow
chart of the experimental methodology adopted in the synthesis
of these metal oxides. A wide range of solvents and surfactant (AR
grade obtained from Merck, Germany; and other Indian manufac-
turers like Ranbaxy, Loba Chemie, Qualigens, Glaxo) have been
used for both TiO2 and ZnO nanoparticles fabrication. Also the
molar concentration of the raw material TiO2 and ZnO was var-
ied to investigate the quality of the resultant products. The raw
materials were reagent grade TiO2 and ZnO (Ranbaxy, India). The
experimental duration was varied from 24 h to just 2 h depending
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upon the precursors used, especially based on the organic additives
and surfactants. The dopants were introduced in the solution form
in the desired molar concentration, and in some cases they were
introduced as metals directly into the hydrothermal and solvother-
mal systems. After the experimental run, the products were washed
and freeze-dried.
2.2. Solvents
Both acidic (HNO3 , HCl, HCOOH), alkali (KOH, NaOH) and
organic solvents (methanol, diethylene glycol, n-butyl alcohol,
diphenylether) were used as solvents, and the pH of the system
was measured before and after the experimental run to check the
pH variation.
2.3. Organic additives
The organic additives played a prominent role in the crystalliza-
tion mechanism of TiO2 and ZnO metal oxides, and in controlling
their particle size and agglomeration. Hexylamine has been used as
an additive in small quantity. It has low toxicity, low density, and
low melting temperature compared to other organics.
2.4. In situ surface modification
Different surface modifiers and chelates like n-butylamine,
caprylic acid, oleic acid, gluconic acid, benzylaldehyde, oleylamine,
sodium dodecyl sulphate, citric acid, triton X, and n-hexanol have
been used in order to control the size, shape and agglomeration.
2.5. Doping
A wide range of dopants like silver, indium, tin, tungsten, pal-
ladium, chromium, manganese, iron, antimony, neodymium, and
in some cases coupled dopants have been introduced to achieve
strong lattice relaxations, which in turn create larger scale atomic
level defects and reduce the bandgap energy that is accompanied
with an enhancement in the photocatalytic properties of metal
oxides.
2.6. Characterization
2.6.1. Powder X-ray diffraction
The powder X-ray diffraction patterns were recorded using
Rigaku Multiflex II Series, Japan, X-ray diffractometer in the 2
range 10–80◦ with Cu K␣ radiation, and the operating current and
voltage were 15 mA and 30 kV, respectively. The scanning speed
was 5◦ /min. The powder X-ray diffraction patterns were compared
with the JCPDS database using PCPDF Win version 2.01.
2.6.2. FTIR spectroscopy
The FTIR spectra were recorded using JASCO 460 Plus, Japan, IR
spectrophotometer. The sample was mixed with KBr and pressed
into a pellet and the spectrum was recorded within the range
400–4000 cm−1 .
2.6.3. SEM and TEM imaging
SEM images of the hydrothermally prepared selectively doped
metal oxide nanoparticles were recorded using JEOL, JSM 5410LV,
Japan. TEM images were recorded using JEM 2000FX II, JEOL Ltd.,
Japan.
2.6.4. UV–vis spectrophotometer
The optical properties were studied using UV–vis spectropho-
tometer, Model SA 165 – Elico, India. The bandgap energy was
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Fig. 1. Flow chart of the experimental methodology adopted in the synthesis of TiO2 and ZnO nanopaticles (depending upon the experimental temperature General Purpose
autoclaves or Batch reactors were used).
also calculated in addition to the optical absorption in the range
300–800 nm for the selectively doped metal oxide nanoparticles.
2.6.5. TGA
Thermogravimetric curves were recorded using Mettler Toledo
Model – TGA/DSC 1, Switzerland in the temperature range room
temperature to 600 ◦ C with a heating rate of 10 ◦ C/min to check
the evolution of organics and other components from the surface
modified metal oxide nanoparticles.
Fig. 2. Two-inch size ZnO crystals produced during one growth run [17].
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3
2.6.6. BET surface area
Surface area determination was carried out by the
Brunauer–Emmett–Teller (BET) method using Belsorp Mini II,
Japan, with nitrogen gas adsorption.
2.6.7. Zeta potential
Zeta potential was measured using Zetasizer 2000 instrument
(Malvern, UK), with pH variation from 2 to 12.
2.6.8. Photocatalytic degradation studies
Photocatalytic studies on the selectively doped metal oxide
particles were carried out using DRB200: Digital Reactor Block
30 mm × 16 mm vial wells, 230 Vac, Make: HACH Co., USA. The
studies were carried out on the virtual effluent solution using sev-
eral dyes like Brilliant Blue and Amaranth dyes – popularly used
in various industries. The source of light was both UV and sun-
light for the photocatalytic degradation study. The photocatalytic
degradation has been studied with respect to the concentration of
the photocatalyst, source of light, exposure time, etc.
3. Results and discussion
Contrary to the growth of TiO2 and ZnO metal oxide bulk sin-
gle crystals, the synthesis of TiO2 and ZnO nanoparticles is usually
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Fig. 3. Powder XRD patterns of characteristic samples of TiO2 and ZnO nanomaterials synthesized under hydrothermal and solvothermal conditions.
carried out under mild hydrothermal and solvothermal condi-
tions (usually T = <120–250 ◦ C, but in some cases up to 400 ◦ C and
P = either autogeneous (experiments in the General Purpose auto-
claves) or up to 20 MPa (experiments in the Batch reactors). The
earlier authors [6] have used supercritical conditions to grow rutile
phase TiO2 crystals using the seeds of TiO2 crystals obtained by the
Verneuil method, and achieved a growth rate of 0.26–0.31 mm/day
under the following experimental conditions:
Temperature: 500–550 ◦ C
Pressure: 500–800 atm
Mineralizer: 7–10% KF or NaF and 5–10% NH4 F
Anatase phase was obtained under the following experimental
conditions:
Temperature: 350–400 ◦ C
Pressure: ∼500 atm
Mineralizer: NaOH or Na2 CO3
Further reduction in the growth temperature results in the for-
mation of the brookite phase.
Similarly, the authors [7,8] have grown bulk crystals of ZnO
under moderately higher temperature. Perhaps the biggest crys-
tals of ZnO were grown by Ehrentraut et al. (2006), and the
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experimental conditions were similar to the ones used by Demi-
anets et al. as shown below [16,17]:
Temperature: 230–300 ◦ C
Pressure: 30–50 MPa
Mineralizer: KOH and LiOH
Fig. 2 shows the ZnO bulk single crystals obtained by Dirk et al.
(2007). In contrast to the earlier reports, the present authors deal
with the synthesis of TiO2 and ZnO at much lower temperature
through an appropriate selection of the solvent, surfactant and
additives.
Among the aqueous solvents, NaOH or HCl were found to be
good solvents. These solvents were added in the molar concen-
tration up to 1.5 M. The organic solvents were found to be more
effective under solvothermal conditions, and the experimental
temperature was significantly low when organic solvents were
used. Also, organic solvents provide highly crystalline anhydrous
impurity-free particles. Perhaps this is one of the main reasons why
in recent years the solvothermal routes of materials processing are
drawing a greater attention from Materials Scientists.
The important step in the processing of fine particles of
advanced materials is the use of surfactants to control the nuclea-
tion of a desired phase, such that the phase homogeneity, size,
shape and dispersibility can be achieved during the crystalliza-
tion of the fine particles. The surface modification of nanoparticles
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Fig. 4. (a and b) FTIR spectra of characteristic samples of TiO2 and ZnO nanomaterials (obtained under sub-critical hydrothermal conditions).
can be divided into partial chemical modification, mechanical and
chemical modification, external membrane modification (i.e., cap-
sule), high-energy surface modification, and surface modification
using precipitation, esterification, coupling and grafting reactions.
Chemical modification, which gives complete surface modifica-
tion, can be achieved either in situ or ex situ. The in situ surface
modification is more popular owing to its advantages. The surface
modifiers also help to inhibit the crystal growth that facilitates
the smaller particle size with a narrow particle size distribution.
In surface modification, pH of the medium, isolectric point (iep)
and another important parameter, viz. dissociation constant (pKa )
of the modifiers are very important. At pH below pKa , the modi-
fier does not dissociate. Moreover, below iep, the surface of metal
oxide nanoparticles is surrounded by positive charges (major) and
hydroxylic groups (minor). Under these conditions, there is no
chemical reaction occurring between the modifier and the metal
oxide nanoparticle surface, but it is only through strong hydrogen
bonding that the modifier can attach to the nanoparticle surface.
In contrast, at higher pH than pKa , dissociation of modifier takes
place and results in chemical reaction between dissociated parts of
the modifier and OH− from the particle surfaces. Thus, by dehydra-
tion reaction, the modifier attaches to the surface of the particles.
By considering the chemical reactions, mass balances, and charge
balance in the actual system, pH and the modifier can be fixed for
most of the systems [13,19]. In the present work, the authors have
used a wide range of surface modifiers with pKa values varying
from 3 to 11, however, best results were obtained in the presence
of surface modifiers with pKa values in the range 3.3–5 (as in the
case of gluconic and oleic acids). The other important point to be
noted here in these hydrothermal experiments with surfactants is
that the initial pH and final pH do not vary much, as in the case
of conventional hydrothermal experiments without surface modi-
fiers. These modifiers help to maintain the desired pH and the ionic
strength of the solvent in the hydrothermal media, and hence they
play a very important role during hydrothermal crystallization.
The role of organic additives has not been understood precisely
in the literature, although there are some excellent publications
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available. Here it is found from the present work that hexylamine
is one of the best organic additives available for ZnO and TiO2
nanomaterials fabrication without any agglomeration and it is less
toxic compared to other amines. Many times, such organic addi-
tives proved to be more effective than surfactant modified metal
oxides. Hexylamine has been used in both TiO2 and ZnO fabri-
cation. The experimental time was reduced from 24 h to 2 h in
different batches, such as 16 h experiments, 8 h experiments, 4 h
experiments and lastly 2 h experiments. Such a reduction in the
experimental temperature duration did not affect the degree of
crystallization of these metal oxides when hexylamine was used
as the additive. The organic additive was added in the range
0.1–1.0 mL. Good results were obtained when the additive con-
centration was maintained at 0.4 mL, and the pH in the range of
10–10.5 in NaOH solvents; and in HCl around 2–2.2. Such results
indicate a significant enhancement of the reaction kinetics, and also
reduction in the agglomeration. Normally, amines are used in the
synthesis of a wide range of structures including zeolites, mixed
hybrid framework structures, and so on [18]. These amines act as
structure directing agents, and often occupy the structural sites
interstitially. By such methods, several novel structural frameworks
have been prepared. In the present work, hexylamine, which is a
strong base when mixed with the strong Lewis acids like ZnO or
TiO2 , does not alter the pH significantly, but instead metal oxides
are completely dissolved in the alkali solutions of NaOH with a
rise in the experimental temperature, and the amines assist these
metal oxides recrystallizing as fine particles. The possible reaction
mechanism is given below:
NaOH + ZnO  HO Zn− ONa
HO Zn− ONa + RNH2  HO Zn− OH + RNHNa
HO Zn− OH + RNHNa  HO Zn− NHR + NaOH
HO Zn− NHR  ZnO + RNH2
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Fig. 5. Electron microscopy images of selectively doped TiO2 and ZnO nanomaterials: (a) manganese doped TiO2 with caprylic acid as surfactant; (b) neodymium doped TiO2
with n-butylamine as surfactant; (c) tungsten doped TiO2 with caprylic acid as surfactant; (d) ZnO with caprylic acid as surfactant; (e) indium doped ZnO without surfactant;
(f) indium doped ZnO with n-butylamine as surfactant; (g) amorphous black resultant products from supercritical hydrothermal experiments with amines.

the chosen dopant limiting the accessible extrinsic carrier density

NaOH
RNH2 + ZnO  RHN Zn− OH
RHN Zn− OH  ZnO + RNH2
In conventional surface modification, usually the outer organics
coatings may even mask the inherent properties of the inorganic
cores if not properly controlled. Therefore, the use of appropri-
ate organic additives is a better approach in the hydrothermal and
solvothermal synthesis of metal oxide nanoparticles. Besides, the
organics significantly enhance the reaction kinetics and bring down
the experimental duration to just 2 h.
Doping is an important part of the crystallization process
whether it is the growth of bulk materials or nanomaterials.
Dopants play an important role in controlling the crystallization
processes to some extent, particularly to control the morphology,
as they inhibit the crystal growth through their locations along
some directions in the crystal structure. There have been several
explanations put forward in explaining doping difficulties in wide
bandgap semiconductors [14,15]. First, there can be compensation
by native point defects, or dopant atoms that locate on interstitial
sites. The defect compensates for the substitutional impurity level
through the formation of a deep level trap. In some cases, strong
lattice relaxations can drive the dopant energy level deeper within
the gap. In other systems, one may simply have a low solubility for
[15]. Each dopant has a different character in this respect.
A systematic characterization of the metal oxide nanoparticles
synthesized has been carried out using several techniques like
powder X-ray diffraction, TEM, SEM, FTIR, BET surface area mea-
surements, UV–VIS spectroscopy and TGA. Also the photocatalytic
activity has been investigated for the characteristic samples of pure
and selectively doped TiO2 and ZnO nanomaterials.
The XRD patterns show homogeneous phase formation in most
cases except in experiments with surplus dopant metals, where
the resultant products are made up of mixtures of TiO2 or ZnO
and the respective dopant metal oxide or chlorides, or metal par-
ticles depending upon the solvent used. Fig. 3a and b shows the
characteristic X-ray patterns of the metal oxides synthesized in
the present work. In fact, the particles synthesized under sub-
critical and supercritical conditions did not differ in their phase
homogeneity and also in their properties, which prompted the
authors to advocate the mild hydrothermal or sub-critical hydro-
thermal processing of materials for a large variety of inorganic
compounds.
FTIR spectra show the presence of functional groups of metal
oxides and also organics depending upon the dopants, surfactants
and organic additives used. Based on the FTIR study we can con-
clude that the additive and surfactant used in the fabrication of
the metal oxide compounds have been completely removed after
washing thoroughly for 2–3 cycles and freeze drying. Fig. 4a and b

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Fig. 6. (a–e) UV–vis spectra of doped ZnO nanoparticles: (a) Pd; (b)Ag + Cr; (c)Ag + Pd; (d)Cr + Pd; (e) pure and Ag doped TiO2 [surfactant: gluconic acid; solvent: NaOH].

shows characteristic FTIR spectra of TiO2 and ZnO nanomaterials
and the respective absorption bands of various functional groups.
SEM and TEM images of some representative samples of selec-
tively doped TiO2 and ZnO nanomaterials were recorded using JEOL
and Hitachi electron microscopes, respectively. The characteristic
images are shown in Fig. 5a–f. The images of the undoped TiO2
and ZnO particles are already given in Ref. [10]. When surplus
dopants were used as in the case of silver, they form a separate
phase, and particles are attached to the host TiO2 and ZnO parti-
cles. In most cases, depending upon the experimental parameters,
dopant metals, and surfactants, the particles are unagglomerated
with a definite morphology. Without surfactants, bigger particles
and agglomerated particles were obtained although the other pro-
cess parameters were carefully monitored. When amines or triton X
were used in the supercritical hydrothermal experiments in Batch
reactors, metal oxides did not form as the amines or triton X decom-
pose and form coordination with the metals, and the final products
are amorphous, black and often sticky materials (Fig. 5g). Thus
only the fatty acids were used in high temperature supercritical
hydrothermal experiments.
The BET surface area measurement for the characteristic sam-
ples of selectively doped TiO2 and ZnO nanoparticles show values

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Fig. 7. TGA curve of Nb doped ZnO nanoparticles obtained with n-butylalcohol (solvent), n-butylamine (surfactant) under sub-critical hydrothermal conditions at 150 ◦ C.

Table 1 Table 2
BET surface area of ZnO nanoparticles. Zeta potential for selectively doped metal oxides.

Solvent Surfactant/chelate BET surface aream2 /g Particles type Sl. No. Compound Dopant Surfactant pH Zeta potential

NaOH Gluconic acid 2.17 Hydrophilic 1. ZnO Niobium n-Butylamine 2 −2.3 ± 1.2
NaOH n-Butyl amine 5.63 Hydrophilic 12 −81.7 ± 7.1
NaOH Triton X 405 2.33 Hydrophilic 2. ZnO Tungsten n-Butylamine 2 −7.9 ± 2.6
NaOH n-Hexanol 2.43 Hydrophilic 12 −80.8 ± 2.6
HCl Citric acid 3.61 Hydrophilic 3. TiO2 Nickel Hexylamine 2 +15.7 ± 0.5
HCl Caprylic acid 4.51 Hydrophobic 12 −72.6 ± 7.3
HCl n-Hexanol 6.11 Hydrophilic 4. TiO2 Tungsten Hexylamine 2 +6.7 ± 0.1
12 −55 ± 3.6
5. TiO2 Indium Hexanol 2 +24.5 ± 5.1
in the range 4–6 m2 /g in spite of their small sizes, indicating the role 12 −61.9 ± 3.6
of organics on the surface properties. The dynamic light scattering
studies show that the particle size varies from 40 nm to 350 nm
upon the type of surfactant used. Hexanol shows a higher decrease
depending upon the surfactant and the dopant used.
in zeta potential with increase in pH. The particles fabricated are
It was found that the BET surface area is 5.630 and 4.513 m2 /g
more positively charged at pH < 4.0. The modified particles synthe-
for surface modified ZnO nanoparticles using n-butylamine and
sized had lower agglomeration, which prevents their flocculation
caprylic acid, respectively. Wang et al. synthesized ZnO nanopar-
or coagulation tendency.
ticles having a BET surface area of 27.43 m2 /g under hydrothermal
The UV–vis spectroscopy studies reveal interesting observations
conditions [20]. Similarly, Saad and Riad found that the BET surface
related to the absorption bands and the corresponding bandgap
area for the ZnO catalyst increased from 6.8 to ≈10.5 m2 /g [21]. The
energy changes with respect to the type of dopants used in
results reveal that n-butylamine makes the surface area larger. In
these compounds. Although the surfactants were varied, signifi-
the present case, the reason for having such low surface area can be
cant changes were found only when dopant metal was used. Table 3
contributed to the complex formation of TiO2 and ZnO nanoparti-
gives the bandgap energy for pure and doped metal oxides. Fig. 6a–e
cles with caprylic acid. It is known that surface modifiers are used to
shows the UV–vis spectra for the representative samples of TiO2
reduce agglomeration and hence reduce the particle size by control-
and ZnO nanoparticles. Among all the dopants used in the present
ling its growth direction. However, it was found that the affinity of
work, silver is one of the best dopants for ZnO and TiO2 , and it
TiO2 and ZnO nanoparticles to give bigger particles is proportional
not only enhances the photocatalytic properties, but the bandgap
to the increasing concentration of the surfactant. Table 1 gives BET
surface area for ZnO particles obtained in the presence of differ-
Table 3
ent solvents, surfactants and or chelates. Higher surface area was Bandgap energy in pure and doped metal oxides.
obtained for ZnO nanoparticles obtained with n-hexanol.
Sl. No. Compound Dopant Wavelength (nm) Bandgap (eV)
The zeta potential measurement carried out for the character-
istic samples of selectively doped metal oxides at different pH 1 ZnO Nil 368 3.37
values and Table 2 show zeta potentials at pH 2 and 12 for dif- 2 ZnO Pd 376 3.3
3 ZnO Pd + Cr 379 3.27
ferent surfactants and dopants. The surface charge changes highly 4 ZnO Pd + Ag 382 3.24
with respect to the type of surfactant and dopant metal to both 5 ZnO Ag + Cr 382 3.24
the positive and negative side depending upon the pH values. As 6 TiO2 Pure 387 3.2
observed from Table 2, with an increase in the pH, the zeta potential 7 TiO2 5% Ag 411 3.0
8 TiO2 1% Ag 418 2.9
values decrease significantly in both metal oxides. It depends also

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1.6
a b
1.4 Amaranth Brilliant Blue FCF
2.0

-ln (C/C ) 1.2

1.0 1.5

-ln (C/C )
0.8

1.0
0.6

0.4
0.5
0.2

0.0 0.0
0 50 100 150 200 250 0 50 100 150 200 250

Time (min) Time (min)

c 2.5
d 2.5

Brilliant Blue CFC

2.0
Amaranth 2.0

1.5
-ln (C/C0)

1.5

-ln (C/C0)
1.0
1.0

0.5
0.5

0.0 0.0
0 50 100 150 200 250 0 50 100 150 200 250

Time (min) Time (min)

Fig. 8. (a and b) Photodegradation of BBF and Amaranth dye using ( ) 5 M % tungsten doped; ( ) 2 M % tungsten doped TiO2 nanoparticles modified with
n-butylamine, ( ) undoped TiO2 nanoparticles modified with n-butylamine, ( ) undoped TiO2 nanoparticles modified with caprylic acid, and ( )
reagent grade TiO2 ; (c and d) photodegradation of BBF and Amaranth dye using using ( ) 5 M % tungsten doped; ( ) 2 M % tungsten doped ZnO nanoparticles
modified with n-butylamine and ( ) reagent grade ZnO (these nanoparticles were obtained under sub-critical hydrothermal conditions). (For interpretation of the
references to color in this artwork, the reader is referred to the web version of the article.)

energy is also reduced significantly in both cases. When silver is
used with other metal, then it further brings down the bandgap
energy, as observed in Table 3.
The thermogravimetric analysis for the selectively doped, sur-
face modified ZnO nanoparticles, for example, shows the loss of
about 1.45 ␮g of organics with heating up to 600 ◦ C. It is inter-
esting to note that most of the organics and the fatty acids used
in the present work did not release higher quantities of organ-
ics than around 1.5 ␮g. This organic is usually coated around the
inorganic core of metal oxide particles, and it also proves that the
organic coating is more or less uniform and thin, and is unlike
the silane coupling which yields non-uniform coating around the
inorganic particles. A detailed discussion on this aspect related to
the thermogravimetric analysis of the surface modified, selectively
doped hybrid organic–inorganic nanoparticles with respect to the
experimental parameters and infrared spectroscopy data will be
published elsewhere. Fig. 7 shows the TGA curve for the represen-
tative sample of Nb doped ZnO nanoparticles with n-butylalcohol
as the solvent and n-butylamine as the surface modifier.
3.1. Photocatalytic property of TiO2 and ZnO
The photocatalytic studies carried out on some selected samples
of in situ surface modified TiO2 and ZnO with surplus surfactant do
not show very high values of photodegradation efficiency indicat-
ing that the surfactant concentration is very critical.
The effect of surface modified tungsten doped TiO2 and ZnO
nanoparticles on the photocatalytic degradation of Brilliant Blue
and Amaranth dyes has been studied in detail. In the photocatalytic
process, catalyst dosage is an important parameter. Photocatalytic
degradation of 2 mg/L BBF and Amaranth dye was carried out with
modified tungsten (2 M % and 5 M %) doped TiO2 and ZnO nanopar-
ticles. The process of the degradation of these dyes as a function
of fabricated TiO2 and ZnO nanoparticles and pure/reagent grade
TiO2 and ZnO dosage is presented in Fig. 8a–d.
As shown in Fig. 8, in the absence of TiO2 or ZnO, the removal
percentage of these dyes is zero. The addition of nanoparticles
enhances the removal of both contaminants with different speed.
The removal rate of these contaminants increases with dye concen-
tration. It is to be noted that there is no difference in the extent of
degradation based on the light source in the case of reagent grade
TiO2 and ZnO, but the degradation also occurred in visible light,
which confirms the effect of doping on photodegradation of these
dyes. An optimal result was achieved at a TiO2 dosage of 1.4 g/L,
and 1.6 g/L for ZnO dosage. The removal decreases with a further
increase in the catalyst dosage.
4. Conclusion
Hydrothermal processing of metal oxide nanomaterials is a
popular area of research owing to the high quality of the prod-
ucts obtained. The in situ surface modification, doping and organic

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additives play an important role in the resultant products and their
physico-chemical characteristics. The doping can significantly alter
the bandgap of these metal oxides. An appropriate organic additive
can greatly enhance the reaction kinetics and the quality of the
products without any organic coating around the inorganic core.
Acknowledgements
The authors wish to acknowledge Prof. T. Adschiri, for the elec-
tron images, and Prof. Mihir Joshi, Saurashtra University, Rajkot,
India, for the TGA curves recording. Also the first author thanks the
University Grants Commission, New Delhi, India, for the fellowship.
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