Colloid and Interface Science Communications 29 (2019) 9–16

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Colloid and Interface Science Communications

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

Shape dependent catalytic activity of unsupported gold nanostructures for T

the fast reduction of 4-nitroaniline
S.G. Jiji, K.G. Gopchandran
⁎

Department of Optoelectronics, University Of Kerala, Thiruvananthapuram 695581, India

ARTICLE INFO ABSTRACT

Keywords: A one step seed mediated strategy is adopted here for synthesizing spherical, dog bone and rod shaped gold
Gold nanorods nanoparticles. Usually noble metals decorated by supporting materials are used for chemical catalysis. Here, a
Gold nano dog bones variety of unsupported gold nanoparticles (spherical, dog bone and rod shaped) originating from the same
Para-nitroaniline growth procedure are used for the catalytic reduction of para-nitroaniline (4-NA). The product obtained, para-
Para-phenylenediamine
phenylenediamine, is an important material, especially in the field of dye industry. The reaction kinetic values
Catalysis
Turnover frequency
were analyzed based on to the Langmuir–Hinshelwood (LH) mechanism. A comparison of the rate constants
Langmuir–Hinshelwood (LH) mechanism obtained for gold nanoparticles of different shapes with almost similar volume pointy that gold nanorods are
superior to that of spherical and dog bone like nanoparticles. The turnover frequency obtained here is high
compared to other reported results and is found to be sensitive to the shape of the nanoparticles.

1. Introduction efficiency [5,6,10,11,14,16–18,20–22,37]. Recently, facet dependent

Manufacturing materials on nanometer scale is an important area in
the field of catalysis [1–14]. Reducing the dimension of materials in the
nanometer scale dramatically increases the surface to volume ratio and
upsurges active surface area of the catalysts and reaction efficiency.
Nanoscale gold as catalysts is a recently developed area of research and
has potential applications in many reactions, which are of industrial
and environmental importance [14–43]. Scientists believed that the
attractive ‘gold’ is chemically inert and a dreary metal from the point of
view of catalysis and was regarded as a poor catalyst [10,44]. However,
after the report made by Haruta et al (1997) that gold particles are
efficient CO oxidizer if deposited as nanoparticles on partly reducible
oxides, things has been changed and tremendous works are going on to
explore the use of Au nanoparticles as catalysts [1–25,34,36,44].
Later, many reports had been published about the ability of gold
nanoparticles as efficient catalysts both in homogeneous and hetero-
geneous medium. Many researchers studied the catalytic efficiency of
gold nanoparticle using other supporting materials [6,17,19,20].
During the growth stages, factors like type of reactants, concentration
of the reactants, temperature, pH of solution, atmospheric humidity,
rate of addition of the reactants, speed of rotation of the magnetic stir
etc. controls the morphology of the nanoparticles [45–47]. Morphology
dependent catalytic studies are important since factors such as size and
shape of particles, energy associated with facets, coordination of atoms,
and presence of protective ligands can largely affect its catalytic
catalytic activity of gold nanocubes, octahedra and rhombic dodeca-
hedra towards 4-NA was done by Chiu et al and reported that particles
with anisotropic shape can alter the reaction performance due to dif-
ference in crystal facets exposed [5]. Thus the concept of morphology-
dependent nanocatalysis of metal particles is a rapidly growing topic in
heterogeneous catalysis nowadays.
In this work, we emphasize shape dependent studies of hetero-
geneous catalysts consisting of gold nanoparticles under liquid phase
reaction conditions. The physical structure of these gold nanoparticles
is either elongated (rod and dog bone) or non-elongated (spherical).
Different from other reports, here the catalysts of different shapes with
almost similar volume are synthesized using the same seed mediated
one step procedure. This makes the comparison of catalytic efficiency of
these nanoparticles worthy. For studying the heterogeneous catalytic
reaction of the prepared structures, hydrogenation of p-nitroaniline is
used. The product formed, para-phenylenediamine (PPD) is of im-
portance in the chemical industry due to their versatility in biologically
active natural products, pharmaceuticals, dyes and ligands [5,40].
2. Experimental Section
2.1. Materials
The reagents, Hexadecyletrimethylammonium bromide (≥ 99.9%-
Sigma, CTAB), Sodium borohydride (99%-Aldrich, NaBH4), Silver

⁎
Corresponding author.
E-mail address: gopchandran@yahoo.com (K.G. Gopchandran).

https://doi.org/10.1016/j.colcom.2018.12.003
Received 26 September 2018; Received in revised form 16 December 2018; Accepted 26 December 2018
2215-0382/ © 2018 Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/BY-NC-ND/4.0/).
S.G. Jiji, K.G. Gopchandran Colloid and Interface Science Communications 29 (2019) 9–16

nitrate (99.99%,Sigma-Aldrich, AgNO3), Gold (III) chloride trihydrate
(99.9 + % - Aldrich, HAuCl4), 4-Nitroaniline (≥ 99%-Aldrich,
C6H6N2O2), L-Ascorbic acid (99%, HiMedia Laboratories Pvt.Ltd., AA)
and Nitric acid (NICE Chemicals Pvt.Ltd., HNO3) were used as such
without further purification. Double distilled water was used
throughout the experiment.
after the addition of NaBH4 was recorded separately. The same ex-
periment was repeated with nanoparticles with shape looking like that
of dog bones (AuNDBs) and spheres (AuNSs) as different catalysts. The
investigations were done at room temperature (~28 °C).
3. Instrumentation

2.2. Synthesis Absorption measurements were carried out by Shimadzu, UV- 3600
spectrophotometer with wavelength range of 250 to 1400 nm. Field
2.2.1. Preparation of CTAB Stabilized Gold Seeds emission scanning electron microscopy (FESEM) imaging technique was
A volume of 5 mL of 0.45 mM HAuCl4 and 5 mL of 0.1 M CTAB
surfactant were added to a beaker. The mixture was stirred for 5 min at
500 rpm. Concurrently, 800 μL of ice-cold, freshly prepared 0.01 M
NaBH4 solution was added to the above solution while stirring. The
resulting solution turned brownish yellow, immediately after adding
NaBH4, indicating the formation of gold nanoparticles. These seed
particles were aged for 2 h to decompose excess borohydride.

2.2.2. Synthesis of Rod Shaped Gold Nanoparticles

A growth solution, containing 5 mL of 0.1 M CTAB, 120 μL of
0.004 M AgNO3, 40 μL of nitric acid and 10 mL of 0.45 mM HAuCl4, was
prepared and mixed well. Then, 280 μL (0.02 M) of weak reducing
agent ascorbic acid was added and stirred for 2 min. Finally, 5 μL of the
seed solution was transferred to the above mixture and stirred for 10 s.
The solution was left undisturbed for 24 h., for the reaction to complete.
It was then centrifuged (at 8000 rpm for 30 min) and washed with
deionized water to concentrate the products. After centrifugation, the Scheme 1. Synthesis of AuNRs, AuNDBs,and AuNSs.
top solution containing excess of CTAB surfactant was carefully re-
moved with a pipette and the concentrated nanorods were diluted with
1.5 mL of deionized water for further analysis and uses.

2.2.3. Synthesis of Dog Bone Shaped Gold Nanoparticles

A growth solution containing the same constituents as discussed
above was prepared and mixed well. Then, 800 μL (0.02 M) of weak
reducing agent AA was added and stirred for 2 min. Finally, 5 μL of the
seed solution was transferred to the above mixture and stirred for 10 s.
The solution was left undisturbed for 24 h., for the reaction to complete.
It was then centrifuged at 8000 rpm for 30 min and washed with
deionized water to concentrate the products. After centrifugation, the
top solution containing excess of CTAB surfactant was carefully re-
moved with a pipette and the concentrated gold nano dog bones were
diluted with 1.5 mL of deionized water for further analysis.

2.2.4. Synthesis of Spherical Gold Nanoparticles

A growth solution, containing the same ingredients as discussed in
section 2.2.2 with minor modification in the volume of nitric acid as
200 μL, was prepared and mixed well. Then, 800 μL (0.02 M) of weak
reducing agent ascorbic acid was added and stirred for 2 min. Finally,
5 μL of the seed solution was transferred to the above mixture and
stirred for 10 s. Further steps including reaction time, CTAB removal
etc. were the same as described in the preceding sections. Finally, the
concentrated nano spheres were diluted with 1.5 mL of deionized water
for further analysis.
The optimum experimental conditions reported herein for synthe-
sizing gold nanostructures with different shapes (rods, dog bones and
spheres) using the same strategy were obtained by trial and error.

2.2.5. Sample Preparation for Catalysis

For the catalytic experiment, 1 × 10−3 M 4-nitroaniline was freshly
prepared and 800 μL of it was added to the 2 mL deionized water and
stirred well. Then 10 μL of the prepared gold nanorods (AuNRs) was
added to the 2 mL solution containing the 4-NA. The 0.1 M ice cold
NaBH4, acts as an excess reagent, was prepared separately and 1 mL of it
was added to the cuvette containing 4-NA and AuNR catalysts.
Instantly, the yellow colour of the 4-NA solution was disappeared and Fig. 1. TEM image and SAED pattern of (a)&(b) nanorods, (c)&(d) dog bones
became colorless. The absorption spectrum of the solutions before and and (e)&(f) spheres.

10
S.G. Jiji, K.G. Gopchandran Colloid and Interface Science Communications 29 (2019) 9–16

Fig. 2. Absorption spectra of AuNRs (black), AuNDBs (red) and AuNSs (blue).
(For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

used for the topographical analysis of the samples (FEI™ NOVA

NANOSEM 450) and detailed morphological analysis were done by
transmission electron microscopy (TEM, FEI TECNAI 30 G2 S-TWIN)
with an acceleration voltage of 300 KV. Dimension Edge (BRUKER)
microscope was used for getting atomic force microscopy (AFM)
images. X-ray diffraction (XRD) was carried out with PANalytical X'
pert diffractometer (λ =1.54056 Å).

4. Results and Discussion

4.1. Analysis of Gold Nanoparticles

In this study, the gold seeds were prepared using CTAB as the
capping agent. The absorption peak of the seed solution was ~ 484 nm
(supplementary data fig. S1). This highly blue shifted absorption wa- Fig. 4. (a) Absorption spectra of 4-NA with different molarities. (b) Plot
velength specifies the small size of the seed particles [42]. The novelty showing linear fit of absorbance vs. concentration of 4-NA.
of the synthesis method used herein for obtaining the gold nano-
particles is the single step procedure adopted, making it highly re-
procedure. The synthesis procedure is shown in Scheme 1. Fig. 1 shows
producible, once the growth solution and the seed are prepared. Most of
the TEM and SAED pattern of AuNRs, AuNDBs and AuNSs. They are
the earlier reports on synthesis of AuNRs and AuNDBs contain three to
richly formed and uniform shaped (supplementary data fig. S3). The
four numbers of steps and any change in these steps may lead to un-
average length and breadth of AuNRs are ~ 64 and 15 nm respectively.
expected growth procedure [7]. For studying the shape dependent ac-
AFM image and the corresponding length profile supported the result
tivity of different catalysts, intentionally we have synthesized AuNSs in
(supplementary data fig. S2). The HRTEM image of AuNRs is shown in
addition to the other two structures using the same seed mediated

Fig. 3. (A) X-ray diffraction patterns of (a)AuNRs, (b)AuNDBs and (c)AuNSs.(B) plot showing relative intensity vs 2ɵ.

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S.G. Jiji, K.G. Gopchandran Colloid and Interface Science Communications 29 (2019) 9–16

Fig. 5. Time-dependent absorption spectra for the borohydride reduction of 4-NA (0.1 mM) at room temperature (28 °C) with (a) AuNRs, (b) AuNDBs and (c) AuNSs;
(d) Concentration (In(C)) versus time plots for the reduction of 4-NA using different gold nanostructures as catalysts, for the evaluation of the reaction rates. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

supplementary data fig. S4. The average d spacing was calculated and
its value is 2.34 Å. This value is very close to the d value of (111) crystal
plane.
The absorption spectra of the gold nano catalysts are shown in
Fig. 2. The two peaks of the gold nanorods and dog bones can be at-
tributed to the transverse (TSPR) and longitudinal (LSPR) surface
plasmon resonance modes. The position of the LSPR band of AuNRs
obtained in this work is in good agreement with that predicted using
the discrete dipole approximation method (λmax. = 96 AR + 418, AR -
aspect ratio), considering the length distribution and the relatively
broad width of the band [42]. The position of observed and theoretical
values of λmax. is ~ 809 and 826 nm respectively. The average aspect
ratio of AuNDBs is ~ 3.07. The observed and theoretical values of λmax
for AuNDBs are 690 and 713 nm respectively. Considering the aspect
ratio unity, the observed and theoretical values of λmax is approxi-
mately 514 and 533 respectively for AuNSs. Comparing the LSPR bands
of AuNRs and AuNDBs, it is observed that the absorbance maximum
almost doubles for rods than dog bones. The TSPR band positions of the
prepared structures are 533, 519 and 510 nm for AuNSs, AuNDBs and
AuNRs respectively. That is AuNRs possess the greatest blue shifted
the pH value is low for structure obtained with spheres. This happens
because of the purposeful increase in the volume of weak reducing
agent so that it inhibited the elongation and reduction becomes speedy.
Fig. 3(A) shows the X-ray diffraction patterns of AuNRs, AuNDBs
and AuNSs. For all the samples the preferential growth is along (111)
crystallographic plane (supplementary data fig. S4). The X-ray diffrac-
tion patterns are indexed according to JCPDS data (Card No: 01–1172)
of cubic gold. Relative intensity vs 2ɵ corresponding to all the observed
peaks are shown in Fig. 3(B).
4.2. Catalysis
In order to evaluate the catalytic activity of our synthesized Au
nanostructures, we have performed the reduction process of 4-ni-
troaniline (4-NA) as a model catalytic reaction, which can easily be
Table 1
Intercepts, slopes and adj.R2 values from ln (C)a vs. time graph.
Intercept Slope

TSPR peak compared to the other two. Absorbance maximum is also of

Value[C0] Error Value[−k] Error Adj. R-Square
the increasing order for AuNRs, AuNDBs and AuNSs respectively. (s−1)
The pH values of the resultant solutions were 1.51, 1.58 and 1.01 for
AuNRs, AuNDBs and AuNSs respectively. The earlier reports on the Rod −17.78768 0.22198 −0.05064 0.00906 0.88311
Dog bone −16.8955 0.08946 −0.02238 0.00127 0.96294
synthesis of Au nanorods observed that low pH value promotes elon-
Sphere −16.42572 0.13184 −0.01057 0.00101 0.83886
gation in rod [48,49] and hence, under optimum growth conditions,
long nanorods results when the growth solution has a low pH. But here a
C is the concentration of 4-NA.

12
S.G. Jiji, K.G. Gopchandran
Scheme 2. Mechanism of catalysis.
monitored by its colour change. In this study 4-NA is reduced to in-
dustrially important product PPD by the heterogeneous gold catalysts
with the help of the donor NaBH4. The reduced or hydrogenated pro-
duct of aryl nitro compound is aryl amine, which are the key compo-
nent in various fields, such as pharmaceuticals, chemical, or dye in-
dustries. Keeping all the experimental parameters such as temperature,
concentration of reactants etc. are the same, different shaped nanos-
tructures possess different reaction rates. The elongated nanostructures
reduce 4-NA faster than non-elongated ones. A comparison with elon-
gated and non-elongated shaped nanostructures is also worthy because
of the similar roots maintained for the synthesis.
In this work, AuNRs, AuNDBs, and AuNSs were used as elongated
and non-elongated catalysts to assist the NaBH4 to reduce P-nitroaniline
to Para-phenylenediamine. The reduction of 4-NA to PPD is visible in
the absorption spectrum (Fig. 5 (a-c)). The characteristic absorption
peak of 4-NA is at 380 nm (Fig. 4 (a)) and the injection of the various
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Colloid and Interface Science Communications 29 (2019) 9–16
gold based nano-catalysts under investigation along with the electron
donor NaBH4 made the reduction to become faster. The characteristic
peak of 4-NA disappears and new peaks appear at around 239 and
304 nm regions and they are identified as peaks corresponding to the
characteristic peaks of the product anticipated, PPD (Fig. 5(a-c)).
Fig. 5(a) shows the absorption spectra of the reduction of 4-NA by
NaBH4 in the presence of the catalyst AuNRs having an average aspect
ratio 4.26. The 4 × 10−4M 4-NA is reduced to equivalent moles of PPD
with NaBH4 by adding AuNRs. In this investigation, the reduction of 4-
NA to PPD is found to be the fastest, when the nanorod having an
average aspect ratio 4.26 is used as catalyst. To evaluate the reaction
rates of the prepared nanostructures (AuNRs, AuNDBs and AuNSs),
plots of ln[C] vs time for the reduction of 4-NA was carried out using
AuNRs, AuNDBs and AuNSs as catalysts and are shown in Fig. 5 (d),
where C is the concentration of 4-NA. Absorbance values are converted
to concentrations in the groundwork of these plots (Fig. 4(a & b)). The
S.G. Jiji, K.G. Gopchandran Colloid and Interface Science Communications 29 (2019) 9–16

linear fits for these data points indicate that the reduction reaction
follows first-order kinetics (Fig. 5(d)). The excess amount of NaBH4
used is also consistent with the reaction order. The concentration of the
electron donor (NaBH4) used is 0.1 M, which is very high compared to
that of nitro compound (4 × 10−4M). Here, the reactant 4-NA is iso-
lated by making the concentration of NaBH4 very high, so that the
overall reaction appears to be of first order [21]. From the slope of the
fitted line, the rate constant (k) can be determined. Rate constants are
given in Table 1. The plots disclose that elongated nanoparticles
maintain the largest k values among the elongated and non-elongated
particle morphologies, so these nanoparticles are indeed the best cat-
alysts for the reduction reaction. The rate constant (k) of AuNRs are
5.064 × 10−2 s−1 which is the highest among the other two samples
(Table 1, Fig. 5). Similarly the rate constant obtained for AuNDBs and
AuNSs are 2.238 × 10−2 and 1.057 × 10−2 respectively.
Initially, BH4− and the aryl nitro compound R = NO2 are both ad-
sorbed on the gold surface. The adsorption of nucleophiles (BH4−) onto
the surface of the metal nanoparticles considerably increases its Fermi-
potential and thereby lowers its potential for reduction ie., the redox
potential of the metal becomes more negative and has a tendency to
donate electrons onto the surfaces of 4-NA [29]. Thus electron transfer
occurs from the negatively charged BH4− to the 4-NA via the gold
nanostructures and reduce the reactant to PPD [31]. Predominantly the
reduction process has three stages. At first nitro group is reduced to
nitroso group. It is then followed by the formation of hydroxylamine
compound by reductive addition of two hydrogen atoms. Finally amine
is reduced by eliminating water (Scheme 2).
In addition to this, at pure form, the surface of the nanoparticles is
not catalytically active but requires a certain reformation and this re-
structuring needs certain time. Thus the reaction progresses just after an
induction time t0, the time needed to obtain an active catalyst [50].
This time period is different for different nanostructures depending on
is more for nanoparticles with concentration of 4-NA at 0.3 mM. The
value becomes very less with concentration of 4-NA at 0.047 mM, be-
cause there are plenty of available active cites when concentration was
less.
Shape dependent catalytic studies in gold catalysts had already been
discussed in Chiu C.,et.al, and Kundu S. et al [5,18]. In one of the group
while discussing about rods and spheres, they found that spheres are
the most active gold catalyst while compared to rods [18]. They didn't
expect such a result and have given a clarification that, high aspect
ratio rods are closely packed and not oriented separately as single rods.
This might be the reason for the slow reaction rate of the high aspect
ratio rods compare to the sphere. It was reported earlier that special
orientation and packing pattern of NPs enhances the rate of reaction.
This study pointed out the much higher catalytic activity of elongated
gold nanoparticles than that of non-elongated ones, synthesized with
the same growth procedure.
To assess the activity of gold catalytic centers the turnover fre-
quency (TOF) is measured. In literature, the turnover frequencies are
reported in two different ways. It is either per total mol of the metal or
per mol of metal exposed at the surface of catalyst nanoparticle. In this
report the TOF values are calculated as a function of the total metal
mol. The TOF values of all the samples are given in Table 2 [32,35] The
TOF value is the highest for AuNRs (15,238 h−1) and the lowest for
AuNSs (2782 h−1) [20,32,34–36].
Table 2
The Reaction time and calculated turn over frequency (TOF).
Samples Reaction time (s) TOF (h−1)
Rod 42 15,238
Dog bone 122 5245
Sphere 230 2782

adsorption efficiency, active crystal planes and surface area [50,51].

The induction time t0 observed for AuNRs, AuNDBs and AuNSs is found
to be in an increasing order from AuNRs to AuNSs. In Fig. 6., the dotted Table 3
line shows the induction time of various nanoparticles having con- Volume of a single particle, number of particles and total surface area of the
centration of 4-NA 0.15 mM. By the catalytic analysis it is found that t0 particles in 10 μL.
increases with increase in concentration of 4-NA. This means that once Sample Volume of a single Number of gold Total Surface area
the concentration of 4-NA is increased, the nanoparticle takes more particle (cm3) particles in 10 μL in 10 μL (cm2)
time for the proper insertion of all the aniline compounds in the active
Rod 1.0420 × 10−17 4.4073 × 109 13.2 × 10−2
crystal surfaces and hence the surface reformation. The induction time
Dog bone 8.8118 × 10−18 5.2117 × 109 12.0 × 10−2
Sphere 3.1043 × 10−17 1.4793 × 109 7.06 × 10−2

Fig. 6. ln (At/A0) vs time plots for the reduction of 0.15 mM 4-NA and 0.1 M
NaBH4 using different gold nanostructures as catalysts. An induction time t0 is
marked with dotted line. (Here A0 is the initial absorbance and At is the ab- Fig. 7. Apparent kinetic constant dependence on concentration of 4 NA at 0.1 M
sorbance at a time t). NaBH4.

14
S.G. Jiji, K.G. Gopchandran
Table 4
Langmuir–Hinshelwood parameters.
Nanostructure Adj.R-Suare k (mol m−2 s−1)
AuNRs 0.93622 0.04514 ± 0.028
AuNDBs 0.95482 0.03651 ± 0.018
AuNSs 0.96533 0.03273 ± 0.017
The volume of a single particle, number of nanoparticles and total
surface area are given in Table 3. Liang's assumption is used here for
calculating the gold nanoparticles per unit volume approximately [22].
Primarily, most of the gold nanoparticles in solution were of the same
shape. In our synthesis ~100% of gold nanoparticles formed were the
same shape (supplementary data fig. S3). Secondly, gold nanoparticles
and bulk gold has the same density. Next, the yield of gold nano-
particles was assumed to be 100%. The total volume-surface area of
different samples are in the order of AuNRs > AuNDBs > AuNSs.. The
activity of the catalytic centers is also of the same order.
Results show that the effective surface area and hence the catalytic
activity is the highest for sample containing rod shaped nanostructures
and lowest for spherical nanostructures. As discussed in the preceding
section, the activity of metal nano catalysts depend on factors such as
shape, temperature, facets, crystal defects and the surfactants used.
Chiu.et al. reported the importance of crystal facet in determining the
activity of gold nanoparticles as catalysts. According to them, the facet
dependent reduction reaction follows an order consisting of
{110} > {100} > {111} surfaces [5]. In the case of CTAB assisted
nanorods, Liu and Guyot-Sionnest reported that the side faces consist of
{110} and {100} facets [39]. Murphy et.al, reported that the side faces
of the nanorods consist of {100} or {110} or a combination of both and
the end faces are of {111} facets [38]. Comparing elongated and non-
elongated nanostructures, elongated structures mostly consists of {110}
and {100} high energy facets. There for in addition to the large surface
area, facets such as {100} and {110} also influence the improved rate of
catalytic activity of the AuNRs.
The reaction kinetic values were analyzed based on to the
Langmuir–Hinshelwood (LH) mechanism. This model is centered on the
simultaneous adsorption of borohydride and 4-NA, which can be de-
scribed in terms of Langmuir isotherms. That is, both reactants are
adsorbed before they react. Once the reactants are adsorbed, the reac-
tion takes place and the product subsequently desorbs from the surface.
A surface rate constant k, and two thermodynamic adsorption con-
stants, KNA and KB for 4NA and NaBH4 respectively are the three
parameters used to describe the catalytic system. A surface rate con-
stant k, measures the surface reactivity of the species. Hence, the ki-
netically analyzed apparent rate constant contains not only the surface
rate constant but also the thermodynamic adsorption constants
[50–54]. Keeping these assumptions, the apparent rate constant Kapp is
written as
k SKNA KB [BH 4 ]
K app =
(1 + KNA [NA] + KBBH 4 )2 (1)
Where,
k - surface rate constant per square meter of the catalyst, which
describes the surface reactivity of the adsorbed species,
S - total surface area of metal nanoparticles normalized to the unit
volume of the solution,
KNA - adsorption constant of 4-nitroaniline,
KB - adsorption constant of borohydride,
[NA] and [BH4−] - concentration of 4-nitroaniline and borohydride,
respectively [52].
The LH model defined by the Eq. (1) is fitted accordingly and is
shown in Fig. 7. The values of fitted parameters are shown in the table
Table 4. From the fitted values it is found that the surface rate constants
are in an increasing order from AuNSs to AuNRs.
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Colloid and Interface Science Communications 29 (2019) 9–16
KNA (L mol−1) KB(L mol−1)
5656 ± 1578 0.44 ± 0.27
10,177 ± 1872 0.35 ± 0.18
10,736 ± 1844 0.32 ± 0.17
Summarizing all these data, obtained from original and fitted out-
comes, it is found that morphology, surface area, facets, crystal defects,
etc. influences the catalytic efficiency of a metal nanoparticle.
5. Conclusions
Gold nanospheres, dog bone like particles and nanorods were syn-
thesized using the same methodology-one step seed mediated strategy.
Broadly the particles were categorized as elongated and non-elongated
nanostructures. These gold nanoparticles were tested for application as
catalysts for the reduction of 4-NA. The reduction process was achieved
in the presence of catalysts with the help of electron donor. The pro-
cesses were described with time dependent absorption spectra and
pointing the much higher catalytic activity of elongated gold nano-
particles than that of non-elongated ones, synthesized with the same
growth procedure. The rate constants were measured and noted high
when nanorods were acted as catalysts. Turn over frequency was cal-
culated for all the cases and was found to be sensitive to the shape of
the catalysts. The reaction kinetic values were analyzed based on to the
Langmuir–Hinshelwood (LH) mechanism. The activities of the catalysts
were profound to both the shape and crystal facets of the nanoparticles.
Calculated TOF for gold nanorods was found to be high compared to the
other values in the literature.
Acknowledgements
The authors gratefully acknowledge financial support from
Department of Science and Technology (DST), India through PURSE
Programme.
Appendix A. Supplementary Data
Absorption spectrum of seed particles; AFM image, length profile,
EDS analysis and FESEM image of Gold nanorods; and FESEM images of
gold nanorods, dog bones and spheres; HETEM images and SAED pat-
tern of AuNRs. Supplementary data to this article can be found online at
https://doi.org/10.1016/j.colcom.2018.12.003.
.
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