chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

Size-controlled synthesis of copper nanoparticles

in supercritical water

Lu Zhou a, , Shuzhong Wang b , Honghe Ma a , Suxia Ma a , Donghai Xu b ,

Yang Guo b
a Department of Thermal Engineering, School of Electrical and Power Engineering, Taiyuan University of Technology,
Taiyuan 030024, Shanxi, China
b Key Laboratory of ThermoFluid Science and Engineering of MOE, School of Energy and Power Engineering,

Xian Jiaotong University, Xian 710049, Shaanxi, China

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

Article history: In this work the particle size control method of copper nanoparticles synthesized in super-
Received 25 December 2014 critical water was investigated. The experiments were respectively carried out in a ow-type
Received in revised form 28 March reaction apparatus and in a batch-type quartz tube apparatus. Results show that particle
2015 size of the products was very sensitive to the concentration of copper sulfate and alkalin-
Accepted 3 April 2015 ity of the reactant. When the concentration of copper sulfate increased from 0.05 mol/L to
Available online 11 April 2015 0.5 mol/L, the average particle size increased from 14 nm to 50 nm. When the molar ratio of
NaOH to copper ion increased from 0:1 to 2:1, the average particle size decreased from 85 nm
Keywords: to 14 nm. The homogeneity and dispersity of the products were improved by increasing the
Supercritical water concentration of complexing agent ethylenediamine tetraacetic acid (EDTA). The adsorption
Hydrothermal synthesis mechanism of EDTA on the surfaces of nanoparticles was researched by a Fourier transform
Reductive infrared spectroscopy. It was speculated that EDTA adsorbed on the surfaces of nanoparti-
Copper nanoparticles cles by the dehydration reaction of carboxyl groups in the molecule of EDTA and hydroxyl
groups on surfaces of copper nanoparticles ( Cu OH). These results are expected to be of
great interest as basic data for the preparation of size-controlled copper nanoparticles by
supercritical hydrothermal synthesis method.
2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Among these methods, the supercritical hydrothermal syn-

Copper nanoparticles are widely used in conductive coatings,
metal surface wear resistant coatings, microelectronics, and
lubricant additives (Xuan and Li, 2000; Lu et al., 2000).
Compared with single atoms and bulk materials, copper
nanoparticles have high application value because of their
special size-related properties. As for the preparation of the
copper nanoparticles, numerous methods have been devel-
oped, including electrolysis method, gas evaporation method,
chemical reduction method, supercritical hydrothermal syn-
thesis method and so on (Masoud and Fatemeh, 2009; Ding,
1996; Dang et al., 2011; Huaman et al., 2011).
thesis method is unique. It has been widely used to produce
metal oxide nanoparticles from metal salt aqueous solutions
using supercritical water as the reaction medium (Noguchi
et al., 2008). The extremely low dielectric constant of the
supercritical water can lead to a high hydrothermal synthe-
sis reaction rate and a low solubility of metal oxides, which
help to produce ne particles. In addition, the supercritical
water has specic property of high solubility of most reduc-
ing gases, which makes it suitable for the synthesis of metal
nanoparticles (Adschiri et al., 2001, 1992; Sue et al., 2006a,b).
So far, various metal (e.g. Ag, Ni, Pd, Fe, and Cu) nanoparti-
cles have been synthesized using hydrogen as reducing agent

Corresponding author. Tel.: +86 29 6010281.
E-mail address: zhoulu19870905@163.com (L. Zhou).
http://dx.doi.org/10.1016/j.cherd.2015.04.004
0263-8762/ 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643
at supercritical reaction conditions (Arita et al., 2011; Kubota
et al., 2014). These ndings suggest that the thermodynamic
equilibrium constant of the reduction reaction may have sig-
nicant impact on the phase composition of nal product.
Among these metal nanoparticles, pure zero-valent copper
nanoparticles could be prepared with the least consumption
of hydrogen (Arita et al., 2011).
In the eld of supercritical hydrothermal synthesis, con-
trol of the morphological structure and particle size of the
nanoparticles is one of the research emphases. As reported in
some previous research papers (Ziegler et al., 2001; Gadhe and
Gupta, 2007; Arita et al., 2011; Seong et al., 2011; Kubota et al.,
2014; Sue et al., 2006a,b), particle size control of metal oxide
nanoparticles during the supercritical hydrothermal synthesis
has been extensively studied. However, only a limited number
of investigations deal with the particle size control of the metal
nanoparticles during the reductive supercritical hydrothermal
synthesis. This problem was tackled by Sue et al. (2004). They
synthesized Ni ne particles in near-critical and supercritical
water. During the reaction, 1,10-phenanthroline was used as
complexing agent that can complex with nickel ion to form
stable chelate compounds at lower temperatures, which may
contribute to the control of the reduction rate of nickel ion
and thus the particle size of nal products. To the best of
authors knowledge, no systematic and experimental study
has been found for investigating the effects of the synthetic
parameters on the particle size of copper nanoparticles that
are synthesized in supercritical water.
In this study, it was aimed to determine the effect of reac-
tant concentration on the particle size and morphology of
copper nanoparticles that were produced under supercritical
reaction condition. Ethylene diamine tetraacetic acid (EDTA),
which is a carboxylate forming relatively stable complex with
copper ion, was used as the complexing agent. The adsorp-
tion mechanism of EDTA on the surfaces of nanoparticles was
researched by Fourier transform infrared spectroscopy, and a
reductive hydrothermal synthesis scheme for the preparation
of copper nanoparticles was speculated.
2. Experiments
2.1. Materials
All chemicals used in the experiments were of analytical
reagent grade and were used without further purication.
In all the experiments, copper sulfate (CuSO4 5H2 O, purity
>99.9 wt%) was used as the copper ion source. Ethylenedi-
amine tetraacetic acid disodium salt (EDTANa2 2H2 O, purity
>99.0 wt%) was used as the complexing agent. Sodium hydrox-
ide (NaOH, purity >99.5 wt%) was used to regulate the
alkalinity of the starting material. Formaldehyde (HCHO,
30 wt%) was employed as the reducing agent. The reducing
agent was not stable in supercritical water. It could decom-
pose into reducing gases such as CO and H2 (Osada et al., 2004;
Watanabe et al., 2003) which were miscible with the supercrit-
ical water to form a homogeneous reductive reaction system.
2.2. Experimental apparatus and procedure
In this study, two kinds of experimental apparatuses were
used in the experiments, namely, a ow-type reaction appa-
ratus and a batch-type quartz tube apparatus. The ow-type
apparatus was used for the experiments with copper sulfate
37
concentration of 0.050.2 mol/L, while the quartz tube reactor
was used for the experiments with copper sulfate concen-
tration of 0.5 mol/L. Initially, we also employed the ow-type
apparatus for the experiments with the copper sulfate con-
centration of 0.5 mol/L. However, plugging of the lines by solid
products frequently occurred. Thus, the quartz tube reactor
was adopted as an alternative experimental apparatus.
2.2.1. Continuous ow-type reactor
Details of the continuous ow-type apparatus and experimen-
tal procedure were described in a previous work (Zhou et al.,
2014). For the present experiments, the reaction temperature
and pressure were xed at 400 C and 25 MPa, respectively.
The ow rate was adjusted by the pump so that the residence
time of reactants in the reactor was 3 min. Prior to the exper-
iments, the aqueous solution of copper sulfate was rstly
prepared, to which a certain amount of mixed solution con-
taining EDTA, NaOH, and HCHO was slowly added with stirring
at room temperature. After the experiments, the collected cop-
per nanoparticles was alternately washed with pure water and
alcohol. Finally, the products were dried in a vacuum dryer at
60 C for further examination.
2.2.2. Batch-type reactor
The experiments with the batch-type quartz reactor were
performed using the following procedure. Firstly, the quartz
reactor was loaded with the prepared precursor solution (as
described above). Then the open end of each quartz reactor
was attached with a piece of rubber tube. After that all these
quartz reactors were put into a horizontal tube chamber (1.0 m
in length and 100 mm in i.d.), the two ends of which were
connected respectively with a vacuum pump and a nitrogen
cylinder. The air in the chamber was pumped out by the vac-
uum pump, and these quartz reactors were left under vacuum
for over 10 h to ensure that the air was completely eliminated
from these capillaries. Then the valve of nitrogen cylinder was
opened and the chamber was lled by nitrogen. Before these
reactors were removed from the chamber, the rubber tube on
the reactor was rapidly fastened with a clip to prevent air
entering the reactor. Thereafter, the quartz reactor (350 mm in
length and 2 mm in i.d.) was sealed by using acetylene ame
at a certain distance to the cutting edge, and placed in an
electric furnace (preheated to 400 C). According to the den-
sity of loaded precursor solution at the reaction temperature,
the pressure of reaction media was 25 MPa. The reaction was
performed for 3 min and terminated by submerging the reac-
tor in a water bath at room temperature for cooling. Finally,
alcohol was introduced to the reactors to collect the produced
nanoparticles.
2.3. Characterization and product analysis
The concentrations of copper ion in the liquid products
were measured by the biscyclohexanone oxalyldihydrazone
(BCO) photometric method using individual Merck cell test
on a Spectroquant NOVA60 instrument, with results reported
directly in concentration units. Particle morphology was
observed by transmission electron microscopy (TEM, JEM-
2100F). Average particle size and the standard deviation (SD)
were determined on the basis of over 200 particles measured
from TEM images. Powder XRD analysis was performed using
an X-ray diffraction meter (Rigaku D/MAX-2400) with Cu K
radiation. The system was operated at 100 mA and 40 kV, and
the scan speed was xed at 10 /min. The surface functional
38 chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643
Fig. 1 XRD proles of the nanoparticles synthesized at
different molar ratios of HCOH to Cu2+ ([HCHO]/[Cu2+ ]): (a)
1:2, (b) 1:1, and (c) 3:1.
groups adsorbed on the surfaces of copper nanoparticles were
determined by a Fourier transform infrared spectroscopy (FT-
IR, Vetex70).
3. Results and discussion
Table 1 shows the experimental conditions and results.
According to the analyses of the recovered solutions, the con-
versions of copper ion for all experimental runs were reached
almost 100%.
3.1. Production of copper nanoparticles
First of all, the amount of reducing agent required to produce
zero-valent copper was determined. The effect of reducing
agent was investigated by varying the molar ratio of formalde-
hyde to copper ion from 1:2 to 3:1 (see Run 13 in Table 1).
Fig. 2 TEM micrographs of copper nanoparticles synthesized at different copper sulfate concentrations: (a) 0.05, (b) 0.1, (c)
0.2, and (d) 0.5 mol/L.
Fig. 1 shows the XRD proles of the samples. When the molar
ratio of formaldehyde to copper ion was 1:2, in addition to
zero-valent Cu, small amounts of Cu2 O were also identied in
the product. When the molar ratio increased to 1:1 or higher,
pure zero-valent Cu was obtained. This result shows that the
formaldehyde required to produce Cu nanoparticles by the
supercritical hydrothermal synthesis method was much lower
than that of the traditional chemical reduction method (Wen
et al., 2003).
3.2. Control of particle size
3.2.1. Effect of copper sulfate concentration
The effect of copper sulfate concentration on the particle size
of copper nanoparticles was studied (see Run 6 and 810 in
Table 1). Fig. 2 shows the TEM images of the synthesized
nanoparticles under different copper sulfate concentration.
When the concentration of copper sulfate increased from
0.05 mol/L to 0.5 mol/L, the average particle size of the
nanoparticles increased from about 14 nm to 50 nm. It seems
that the nanoparticles may obtain sufcient growth at higher
copper sulfate concentrations. This result is consistent with
the ndings of prior studies on the preparation of -AlO(OH)
(Hakuta et al., 2005) and Fe2 O3 (Sue et al., 2010) nanoparticles
by supercritical hydrothermal synthesis method.
In addition, the particle size distribution of the prod-
ucts became wider as the concentration of copper sulfate
increased (see Fig A.1 in Appendix A). When the copper sul-
fate concentration increased to 0.5 mol/L, the particle size of
the products showed obvious heterogeneous distribution. It
suggests that the copper sulfate concentration may have a
signicant impact on the crystallization kinetics of copper
nanoparticles. At low copper sulfate concentration, primary
nuclei were rapidly generated at supercritical water, which
greatly reduced the concentration of copper ion and thus
suppressed the formation of secondary nucleus. In this case,
the growth time of nanoparticles was limited and small
 chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643 39

Table 1 Experimental conditions and results.

Run T ( C) [Cu2+ ] (mol/L) [EDTA]/[Cu2+ ]a [NaOH]/[Cu2+ ]b [HCHO]/[Cu2+ ]c Phase composition Average size S.D. (nm)

1. 400 0.5 2:1 2:1 3:1 Cu

2. 400 0.5 2:1 2:1 1:1 Cu
3. 400 0.5 2:1 2:1 1:2 Cu2 O, Cu
4. 400 0.5 0:1 2:1 2:1
5. 400 0.5 1:1 2:1 2:1 97 32
6. 400 0.5 2:1 2:1 2:1 50 17
7. 400 0.5 4:1 2:1 2:1 49 14
8. 400 0.2 2:1 2:1 2:1 36 8
9. 400 0.1 2:1 2:1 2:1 27 5
10. 400 0.05 2:1 2:1 2:1 Cu 14 3
11. 400 0.05 2:1 1:1 2:1 Cu 24 6
12. 400 0.05 2:1 0:1 2:1 Cu2 O, Cu 85 33

a
Molar ratio of EDTA to copper ion.
b
Molar ratio of NaOH to copper ion.
c
Molar ratio of HCOH to copper ion.

particles with good uniformity were readily produced.
Whereas, at high copper sulfate concentration, the nuclea-
tion period was prolonged. Repeated heterogeneous phase
nucleation thus occurred, which ultimately resulted in het-
erogeneous distribution of nanoparticles.
3.2.2. Effect of EDTA concentration
The effect of EDTA concentration on the particle size of cop-
per nanoparticles was studied (see Run 47 in Table 1). Fig. 3
shows the TEM photographs of the samples. It can be seen that
dispersible ellipsoidal copper nanoparticles were obtained.
Fig A.2 in Appendix A shows that the ranges of particle size
at molar ratios of EDTA to copper ion of 1:1, 2:1, and 4:1
were 24405 nm, 17114 nm, and 2288 nm, respectively. The
result indicates that increasing the concentration of EDTA
was advantageous to the homogeneity and dispersity of the
nanoparticles. This could be because increasing the concen-
tration of EDTA provided enough atoms to coordinate with
copper ions to form stable chelate compounds during the
heating process, which prevented premature nucleation of the
nanoparticles.
3.2.3. Effect of sodium hydroxide concentration
Previous researches have shown that alkalinity of reactant
solution may be a key factor affecting the size of nanopar-
ticles in supercritical hydrothermal synthesis reactions (Sue
et al., 2006a,b; Sahraneshin et al., 2012; Lu et al., 2013). In
this study, the alkalinity of reactant solution was adjusted
by the concentration of NaOH. The TEM images of the prod-
ucts obtained at the different NaOH concentrations are shown
in Fig. 4 (see Run 1012 in Table 1). The corresponding par-
ticle size distributions are shown in Fig A.3 in Appendix A.
When the molar ratio of NaOH to copper ion increased from
0:1 to 2:1, the particle size range of the products signicantly
decreased from 21210 nm to 519 nm, and the corresponding
average particle size decreased from about 85 nm to 14 nm.
This nding is understandable because increasing alkalinity
of the reactant solution led to the increase of the degree of the

Fig. 3 TEM images of copper nanoparticles synthesized at different EDTA concentrations. (a) Without EDTA, (b)
[EDTA]/[Cu2+ ] = 1:1, (c) [EDTA]/[Cu2+ ] = 2:1, and (d) [EDTA]/[Cu2+ ] = 4:1.
40 chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643
Fig. 4 TEM images of copper nanoparticles synthesized at different NaOH additions. (a) [NaOH]/[Cu2+ ] = 2:1, (b)
[NaOH]/[Cu2+ ] = 1:1, and (c) without NaOH.
Fig. 5 FT-IR spectra of copper nanoparticles synthesized at
different NaOH additions. (a) Without NaOH, (b)
[NaOH]/[Cu2+ ] = 1:1, and (c) [NaOH]/[Cu2+ ] = 2:1.
supersaturation. This result agrees with Sues (2006) analysis
in that particle size of the nanoparticles varies inversely to
their solubilities or supersaturations in the supercritical water.
Based on the above analysis, the particle size and dis-
tribution of the copper nanoparticles were affected by the
above three factors, in which the alkalinity of reactant solution
(NaOH concentration) affected it most obviously.
3.3. Mechanism analysis
3.3.1. Characterization of the nanoparticle surface
In this section, characterization of the nanoparticle surface
was studied. Prior researches have shown that some organic
Fig. 6 Adsorption mechanism of EDTA on the surfaces of
copper nanoparticles.
ligands can adsorb on the surfaces of nanoparticles through
their polar functional groups (Rangappa et al., 2008; Lu et al.,
2012; Mousavand et al., 2007). To investigate the chemical
bonding between EDTA and surface of copper nanoparticles,
Fourier transform infrared (FT-IR) analysis was conducted.
Fig. 5 shows the FT-IR spectra of the copper nanoparticles
synthesized with EDTA at different NaOH concentrations (see
Run 1012 in Table 1). The spectra showed broad hydroxyl
( OH) stretch peaks at 3400 cm1 , even for the nanoparticles
synthesized without NaOH. It indicates that the unsaturated
bonds on the surfaces of nanoparticles tended to be combined
with hydroxy that was hydrolyzed from water. The absorption
bands, corresponding to CH2 and CH3 stretching vibration
on the particles, were observed at 2885 cm1 and 2947 cm1 .
The bands at 1047 cm1 and 1640 cm1 were the vibration
bands of C OH and C O stretching vibration, which attributed
to the adsorption of carboxyl group ( COOH). The bands at
620 cm1 corresponded to the stretching vibrations of Cu O.
Based on above analysis, the adsorption mechanism of EDTA
on the surfaces of copper nanoparticles was proposed. As
shown in Fig. 6, the complexing agent adsorbed on the sur-
face of nanoparticles by the dehydration reaction of carboxyl
groups in the molecule of EDTA and hydroxyl groups on sur-
face of copper nanoparticles ( Cu OH).
 chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643
Fig. 7 XRD patterns of samples prepared at various
addition amounts of NaOH. (a) Without NaOH, (b)
[NaOH]/[Cu2+ ] = 1:1, and (c) [NaOH]/[Cu2+ ] = 2:1.
3.3.2. Synthesis mechanism of the copper nanoparticles
In this section, the mechanism of the synthesis of copper
nanoparticles in supercritical water was analyzed. Kubota
et al. (2014) have investigated the reaction mechanism of the
preparation of copper nanoparticles using hydrogen as the
reducing agent in supercritical water. In their experiments,
Cu2 O was detected in the nal products and the content of
which decreased with the reaction time. The reason, they sug-
gested, is that the hydrothermal synthesis rate of CuO was
fast while the releasing rate of hydrogen from the decompo-
sition of formic acid was relatively slow. Seong et al. (2011)
synthesized cobalt nanoparticles and they also believed that
cobalt oxide was rstly produced by the hydrothermal synthe-
sis reaction and then was reduced to metal cobalt by hydrogen.
Unlike these earlier studies, however, formaldehyde rather
Fig. A.1 Particle size distribution of copper nanoparticles synthesized at different copper sulfate concentrations: (a) 0.05,
(b) 0.1, (c) 0.2, and (d) 0.5 mol/L.
41
than formic acid was adopted as the source of reducing agent
in this study.
The experimental results in Section 3.1 have shown that
the incomplete reduction product Cu2 O was detected in the
sample when the formaldehyde concentration was low. It indi-
cates that there existed the reduction process of CuO Cu2 O
or Cu2+ Cu+ . To further explore the reaction mechanism,
the phase compositions of the nanoparticles obtained at var-
ious NaOH concentrations were determined (see Run 1012 in
Table 1), where the concentration of NaOH was varied to adjust
the synthesis rate of CuO. Fig. 7 shows the XRD proles of these
samples. It can be seen that Cu2 O was detected in the product
that was obtained without NaOH (see Fig. 7a). Under this con-
dition, the hydrothermal synthesis of CuO was suppressed due
to the acidic reaction medium. Whereas, when the molar ratio
of NaOH to copper ion increased to 1:1 or 2:1, pure zero-valent
Cu was obtained (see Fig. 7b and c). These results suggest
that zero-valent copper was readily produced when the for-
mation rate of CuO was faster. Thus, it is speculated that the
main reduction reaction path was CuO Cu2 O Cu in this
study.
According to the results above, the shape-controlled
hydrothermal synthesis strategy of copper nanoparticles with
EDTA as complexing agent is considered to progress as follows.
The CuO precursors were rapidly produced by supercritical
hydrothermal synthesis reaction (hydrolysis and dehydra-
tion). In this process, EDTA chelated copper ion to form stable
chelate compound during the heating process, which helped
the formation of homogenous nucleation in the reaction sys-
tem. Then the reduction reaction occurred to form primary
particles of zero-valent Cu. Subsequent growth of these pri-
mary particles resulted in the nal copper nanoparticles with
a particular size. In this process the adsorption of EDTA on the
surfaces of nanoparticles formed coated layers and thereby
inhibiting further growth of the nanoparticles.
42 chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643

4. Conclusions
In this work size-controlled copper nanoparticles were pre-
pared by supercritical hydrothermal synthesis method. The
average particle size of the products increased from about
14 nm to 50 nm when the concentration of copper sulfate
increased from 0.05 mol/L to 0.5 mol/L. Moreover, the results
indicate that the uniformity of the particle size distribution
became worse with the increase of copper sulfate con-
centration. Alkalinity of the reactant was found to be the
most critical inuence on the particle size. When the molar
ratio of NaOH to copper ion increased from 0:1 to 2:1, the

Fig. A.2 Particle size distribution of copper nanoparticles synthesized at different EDTA concentrations. (a)
[EDTA]/[Cu2+ ] = 1:1, (b) [EDTA]/[Cu2+ ] = 2:1, and (c) [EDTA]/[Cu2+ ] = 4:1.

Fig. A.3 Particle size distribution of copper nanoparticles synthesized at different NaOH concentrations. (a)
[NaOH]/[Cu2+ ] = 2:1, (b) [NaOH]/[Cu2+ ] = 1:1, and (c) without NaOH.
 chemical engineering research and design 9 8 ( 2 0 1 5 ) 3643
average particle size signicantly decreased from about 85 nm
to 14 nm. An increase in the concentration of the complex-
ing agent EDTA led to the formation of homogeneous and
monodispersed nanoparticles, probably due to that EDTA pre-
vented premature nucleation during the heating process. Test
results of FT-IR showed that EDTA adsorbed on the surfaces
of copper nanoparticles by dehydration reaction of carboxyl
group ( COOH) in the molecule of EDTA and hydroxyl group
on the copper surface ( Cu OH). The zero-valent Cu was spec-
ulated to be produced mainly by the reduction reaction path
of CuO Cu2 O Cu.
Acknowledgements
The authors acknowledge the nancial supports from the
Qualied Personnel Foundation of Taiyuan University of Tech-
nology (QPFT) (no. tyut-rc201430a) and (no. tyut-rc201316a),
the Young Foundation of Taiyuan University of Technology (no.
2013Z042), and the Program for New Century Excellent Talents
in University of Chinese Education Ministry (Grant NCET-07-
0678).
Appendix A.
Here below are the gures about the effects of the concentra-
tions of copper sulfate, EDTA, and NaOH on the particle size
distribution of the synthesized copper nanoparticles (particle
number fraction vs. particle size). The particle size distribu-
tions were statistically calculated on the basis of over 200
nanoparticles measured from the TEM images of the prod-
ucts.
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