applied

sciences
Article
Gold Nanotriangles as Selective Catalysts for
Cyclohexanol and Cyclohexanone Production
Inês A. S. Matias 1 , A. P. C. Ribeiro 1 , Rui P. Oliveira-Silva 2 , Duarte M. F. Prazeres 2 and
Luísa M. D. R. S. Martins 1, *
1 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa,
1049-001 Lisboa, Portugal; [email protected] (I.A.S.M.); [email protected] (A.P.C.R.)
2 IBB–Institute for Bioengineering and Biosciences, Department Bioengineering, Instituto Superior Técnico,
Universidade de Lisboa, 1049-001 Lisboa, Portugal; [email protected] (R.P.O.-S.);
[email protected] (D.M.F.P.)
* Correspondence: [email protected]; Tel.: +351-218-419-389




Received: 24 October 2018; Accepted: 14 December 2018; Published: 17 December 2018


Featured Application: The sustainable synthesis of cyclohexanol and cyclohexanone mixture

(ketone and alcohol (KA) oil) is of primordial importance for the synthesis of nylon 6,6. The present
industrial process uses a cobalt catalyst, dioxygen as oxidant, requires high temperatures (150 ◦ C),
being only able to reach 5–12% yields in order to assure a selectivity of approximately 85%. Thus,
more efficient catalytic systems and milder reaction conditions are needed. Herein, an alternative
catalytic system based on gold nanotriangles is presented.

Abstract: The search for sustainable catalytic oxidation processes remains a challenge. One process
of utmost industrial and economic importance is the selective oxidation of cyclohexane, in the route
of nylon-6,6 production, which requires urgent improvement. Herein, Au nanotriangles (Au NTs)
were prepared following a three-step (seed preparation, growth and shaping) procedure and applied,
for the first time, as catalysts for the selective oxidation of neat cyclohexane to ketone and alcohol
(KA) oil (cyclohexanol and cyclohexanone mixture). The Au NTs successfully yield KA oil (up to
14%) under mild conditions (50 ◦ C), using an alternative energy source (microwave irradiation) as
reaction promotor.

Keywords: gold nanoparticles; gold nanotriangles; cyclohexane; selective oxidation; KA oil;

cyclohexanol; cyclohexanone; microwave

1. Introduction
Studies on the catalytic properties of gold nanostructures in oxidation reactions showed that
such nanoparticles stabilized and well dispersed on various supports (metal oxides [1–6], carbon
materials [7–12], metal–organic frameworks [13], zeolites [14], modified aluminums [15,16], ionic
liquids [17], etc.) are able to successfully catalyze several oxidation reactions, as well as the selective
partial oxidation of cyclohexane.
The preference for cyclohexane as a model substrate arises from the significance of the oxidized
products (cyclohexanol and cyclohexanone) in the production of adipic acid, a building block for
different processes in the pharmaceutical, chemical, and food industries. In fact, adipic acid is an
important chemical commodity produced globally (over 3.5 million metric tons/year, growing ca.
5%/year) [18,19] mainly in the synthesis of Nylon-6,6 polyamide (primary use), but can also be used
in the production of polyurethane resins and polyester [18].

Appl. Sci. 2018, 8, 2655; doi:10.3390/app8122655 www.mdpi.com/journal/applsci

Appl. Sci. 2018, 8, 2655 2 of 11

Despite the efforts made to prepare and investigate Au nanocatalysts without any support to
assess the activity of pure Au without support effects, the application of gold nanoparticles (Au NPs) in
solution as catalysts for oxidation reactions is scarce, mainly due to aggregation issues that induce low
reproducibility in the results. So far, Kulikova et al. [20] has disclosed the use of Au NPs stabilized by
a 1-dodecanethiol monolayer to catalyze the aerobic oxidation of cyclohexene to produce cyclohexene
oxide (11%), alkyl hydroperoxide (84%), and allyl ketone (5%).
It is known that catalytic properties of metal NPs are size- and shape-dependent [21,22]; therefore,
the ability to control sizes and morphologies of the Au NPs is an important issue in nanomaterial
science. In this work, cetyltrimethylammonium chloride (CTAC)-stabilized Au nanotriangles (Au NTs)
were synthetized by a seed-mediated approach and “face-blocking” growth mechanism [23].
The above CTAC-stabilized Au NTs were tested for the microwave (MW)-assisted oxidation
of neat cyclohexane to ketone and alcohol (KA) oil under mild conditions using a “green” oxidant
(aqueous tert-butylhydroperoxide, TBHP), in contrast to the current inefficient industrial harsher
conditions [18,24]. To our knowledge, this is the first time that the successful use of Au NTs for the
oxidation of cyclohexane is disclosed.

2. Materials and Methods

All solvents and reagents were obtained from the commercial sources and were used without
further purification.
Cetyltrimethylammonium chloride-stabilized gold nanotriangles (CTAC-stabilized Au NTs) were
synthetized following a three-step (seed preparation, growth and shaping) procedure previously
described in the literature [23]. Briefly, first Au seeds were synthesized by the standard CTAC/NaBH4
procedure; then a “growing solution” (CTAC, HAuCl4 and NaI onto Milli-Q water) and a “shaping
solution” (CTAC, HAuCl4 and NaI) were prepared. Ascorbic acid was added to both solutions and
were manually stirred until they become colorless (AuIII → AuI ). Consequently, 250 µL of seeds were
added to solution 1 and manually stirred. Right after, 3.2 mL of solution 1 were added to solution
and left to react in the dark during 1 h at room temperature. Finally, to induce flocculation of Au NTs,
cetyltrimethylammonium bromide (CTAB) was added until the desired concentration of CTAC+CTAB
was reached. The solution was left overnight to flocculate the gold nanotriangles.
Scanning electron microscope (SEM) JEOL 7001F with Oxford light elements, energy dispersive
(EDX) detector and electron backscatter diffraction (EBSD) detector (JEOL, Tokyo, Japan) was used to
characterize the size distribution and morphology of Au triangles.
Transmission Electron Microscopy (TEM) measurements were carried out on a Transmission
Electron Microscope Hitachi 8100 with ThermoNoran light elements EDX detector and digital image
acquisition (Hitachi, Tokyo, Japan).
UV-visible spectroscopic measurements of CTAC-stabilized Au NTs aqueous solutions were
performed on a PerkinElmer Lambda 750 UV-visible spectrophotometer (PerkinElmer, Inc., Waltham,
MA, USA), using a 1 cm path length quartz cuvette.
The catalytic oxidation reactions of cyclohexane were performed in an Anton Paar Microwave
300 reactor (Anton Paar GmbH, Graz, Austria) fitted with a rotational system and an infra-red (IR)
temperature detector, in G10 borosilicate glass tubes.
In a typical experiment, were introduced in a 10 mL Pyrex tube a desired volume of Au NTs
solution, 5.00 mmol of cyclohexane and 50 µL of nitromethane (as internal standard). The additive
(if any) was added and the reaction started by adding TBHP (70% aqueous solution, 10.0 mmol) in
one portion. The mixture was irradiated with 10 W and stirred (650 rpm) at the desired temperature
(30–70 ◦ C) and reaction time (1–6 h). After the reaction, the obtained mixture was cooled to room
temperature and centrifuged. A sample (4 µL) was taken from the organic phase and analyzed by gas
chromatography (GC) upon the addition of an excess of PPh3 to reduce cyclohexyl hydroperoxide
to cyclohexanol, following a method developed by Shul’pin [25,26]. For the experiments using air
Appl. Sci. 2018, 8, 2655 3 of 11

Appl. Sci. 2018,

as oxidant, 8, x FOR PEERpressure
atmospheric REVIEW was used, and the other reaction conditions are the same 3 as
of 12
the
stated before.
experiments using air as oxidant, atmospheric pressure was used, and the other reaction conditions
GC measurements were performed in a FISONS Instruments GC 8000 series gas chromatograph
are the same as the stated before.
with a flame ionization (FID) detector and a capillary column (DB-WAX, column length: 30 m; internal
GC measurements were performed in a FISONS Instruments GC 8000 series gas
diameter: 0.32 mm) and the Jasco-Borwin v. 1.50 software (Jasco, Tokyo, Japan) using helium as the
chromatograph with a flame ionization (FID) detector and a capillary column (DB-WAX, column
carrier gas. The temperature of injection was 240 ◦ C. The initial temperature was kept at 100 ◦ C
length: 30 m; internal diameter: 0.32 mm) and the Jasco-Borwin v. 1.50 software (Jasco, Tokyo, Japan)
forusing
1 min, then as increased ◦ C/min until 180 ◦ C and maintained at this temperature for 1 min.
10gas.
helium the carrier The temperature of injection was 240 °C. The initial temperature was
GC-MS
kept atanalyses
100 °C for were executed
1 min, in a Perkin
then increased Elmer Clarus
10 °C/min until 180600°CCand
instrument
maintained (Heat as the
this carrier gas).
temperature
Theforionization
1 min. GC-MS analyses were executed in a Perkin Elmer Clarus 600 C instrument (He using
voltage was 70 eV. GC was conducted in the temperature-programming mode, as thean
SGE BPX5 column (30 m × 0.25 mm × 0.25 µm). All products formed were
carrier gas). The ionization voltage was 70 eV. GC was conducted in the temperature-programming identified by comparison
of their
mode, retention
using antimes
SGE BPX5confirmed
columnwith those ofmm×0.25
(30 m×0.25 commercially
µm). All available
productssamples. Blank
formed were experiments
identified by
were also carried
comparison out, retention
of their and it was confirmed
times confirmed thatwith
in the absence
those of the Au available
of commercially NTs almost no oxidation
samples. Blank
products (only up
experiments were to also
1.2%,carried
see Table
out, 1)andwere obtained.
it was confirmedReaction
that inproducts mass
the absence spectra
of the werealmost
Au NTs compared
no
oxidation products
to fragmentation (onlyobtained
patterns up to 1.2%, fromseetheTable
NIST1)(National
were obtained. Reaction
Institute products
of Standards mass
and spectra
Technology)
were compared
spectral library stored to fragmentation
in the computer patterns
softwareobtained
of thefrom
massthe NIST (National Institute of Standards
spectrometer.
and Technology) spectral library stored in the computer software of the mass spectrometer.
3. Results
3. Results
Cetyltrimethylammonium chloride-stabilized gold nanotriangles (CTAC-stabilized Au NTs) were
Cetyltrimethylammonium
synthetized by a 3 steps procedure chloride-stabilized gold nanotriangles
[23]: seed preparation, growth and(CTAC-stabilized
shaping (see Scheme Au NTs)
1 and
were synthetized by
Materials and Methods section). a 3 steps procedure [23]: seed preparation, growth and shaping (see Scheme 1
and Materials and Methods section).
“Face-blocking” growth, i.e., directed growth upon selective adsorption of surfactants to
“Face-blocking”
most-favorable growth, was
facets (capping), i.e., directed
chosen asgrowth
growthupon selectiveBy
mechanism. adsorption of surfactants to
this “surfactant-templating”,
most-favorable
an initial shape yieldedfacetsabove
(capping),
50% was chosen
can be as growth
achieved mechanism.
by firstly generatingBy this
CTAC “surfactant-templating”,
capped single-twinned
an initial shape yielded above 50% can be achieved by firstly generating CTAC capped
seeds (<10 nm) and then fast seed adding to a growth solution using ascorbic acid, yielding
single-twinned seeds (<10 nm) and then fast seed adding to a growth solution using ascorbic acid,
nanotriangles of 60–150 nm upon depletion-induced purification. The synthesis process yielded
yielding nanotriangles of 60–150 nm upon depletion-induced purification. The synthesis process
mostly triangles, although hexagons and small polyhedral particles are scarcely detected.
yielded mostly triangles, although hexagons and small polyhedral particles are scarcely detected.

Scheme1.1.Preparation
Scheme Preparation of
of gold
gold nanotriangles.
nanotriangles.
 Appl. Sci. 2018, 8, 2655 4 of 11
Appl.Sci.
Appl. Sci.2018,
2018,8,
8,xxFOR
FORPEER
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REVIEW 44 of
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12

Characterization
Characterization by by TEM
by TEM
TEM andand SEM
and SEM confirm
confirm aaa regular
SEM confirm regular triangular
regular triangular shape
triangular shape
shape of of the
the synthetized
of the synthetized
Characterization synthetized
CTAC-stabilized
CTAC-stabilized Au
Au NTs
NTs (Figure
(Figure 1).
1). High-resolution
High-resolution TEM
TEM show
show nearly
nearly 60%
60% of
of the
the total
total nanoparticle
nanoparticle
CTAC-stabilized Au NTs (Figure 1). High-resolution TEM show nearly 60% of the total nanoparticle
population are
population are gold
are gold triangles
gold triangles and
triangles and confirmed
and confirmed
confirmed thethe {111}
the {111} nature
{111} nature of
nature of the
of the planar
the planar facets
planar facets of
facets of the
of the nanotriangles
the nanotriangles
nanotriangles
population
(Figure 1a)
(Figure 1a) which
1a) which are
which are very
are very uniform
very uniform
uniform inin size
in size distribution
size distribution and
distribution and exhibit
and exhibit an
exhibit anedge
an edge length
edge length of
length of ± 3 nm
7171±3
of nm
(Figure 71±3 nm
(Figure 1b)
(Figure 1b) and
1b) and heights
and heights up
heights up to
up to 40
to 40nm.
40 nm. Additional
nm. Additional TEM
Additional TEM images
TEM images and
images and histogram
and histogram of
histogram of Au
of AuNTs
Au NTs are
NTs are depicted in
are depicted
depicted
(Figure
Figure S1 S1
in Figure
Figure of Supplementary
of Supplementary
Supplementary Information.
Information.
in S1 of Information.

(a)
(a) (b)
(b)
Figure 1.
Figure 1.
Figure TEM(a)
1. TEM
TEM (a)and
(a) and SEM
and SEM (b)
SEM (b) images
(b) images of
images of the
of the obtained
the obtained CTAC-stabilized
obtained CTAC-stabilized Au
CTAC-stabilized Au NTs.
Au NTs.
NTs.

The catalytic
The catalytic
The performance
catalytic performance
performance of of the
of the CTAC-stabilized
the CTAC-stabilized
CTAC-stabilized gold gold nanotriangles
gold nanotriangles
nanotriangles was, was, for the
was, for
for the first
the first time,
first time,
time,
evaluated
evaluated for
evaluated for the
for the cyclohexane
the cyclohexane oxidation,
cyclohexane oxidation,
oxidation, inin terms
in terms of
terms of products
of products yield,
products yield, turnover
yield, turnover number
turnover number (TON,
number (TON, moles
(TON, moles
molesof
KA oil per mole of catalyst) or frequency (TOF, h − 1 , TON/reaction time), catalyst amount, and type of
of KA
of KA oil
oil per
per mole
mole ofof catalyst)
catalyst) oror frequency
frequency (TOF,
(TOF, hh−1,, TON/reaction
−1 TON/reaction time),
time), catalyst
catalyst amount,
amount, and and type
type
oxidant
of used
oxidant (see
used Table
(see 1
Table and
1 Figures
and Figures
of oxidant used (see Table 1 and Figures 2–5). 2–5).
2–5).
The
The Au
The Au
Au NTsNTs
NTs show
show an
show an effective
an effective performance
effective performance as
performance as catalysts
as catalysts for
catalysts for the
for the MW-assisted
the MW-assisted oxidation
MW-assisted oxidation
oxidation of of
of
cyclohexane,
cyclohexane, with
cyclohexane, with aqueous
with aqueous tert-butylhydroperoxide
aqueous tert-butylhydroperoxide
tert-butylhydroperoxide (TBHP), (TBHP), to
(TBHP), to KA
to KA oil,
KA oil, through
oil, through the
through the formation
the formation
formation of of
of
cyclohexyl hydroperoxide
cyclohexyl hydroperoxide
cyclohexyl (primary
hydroperoxide (primary product),
(primary product), under
product), under
under mildmild conditions
mild conditions (Scheme
conditions (Scheme 2).
(Scheme 2).2).

Scheme 2.
Scheme Oxidation of
2. Oxidation of cyclohexane
cyclohexane with
with peroxide, catalyzed by
peroxide, catalyzed
catalyzed by Au
Au NTs.
NTs.

Importantly, the
Importantly, the
Importantly, cyclic
the cyclic KA
cyclic KA oil
KA oil are
oil are the
are the only
the only products
only products detected
products detected
detected byby gas
by gas chromatographic
gas chromatographic analysis,
chromatographic analysis,
analysis,
confirming the high selectivity of the catalytic oxidative system (please see Table 1). This achieved high
confirming the
confirming the high
high selectivity
selectivity of
of the
the catalytic
catalytic oxidative
oxidative system
system (please
(please see
see Table
Table 1).
1). This
This achieved
achieved
selectivity (100% selectivity for the conditions of entry 4, Table 1) is of utmost economic importance
high selectivity
high selectivity (100%
(100% selectivity
selectivity for
for the conditions
conditions of of entry
entry 4,4, Table
Table 1)1) is
is of
of utmost
utmost economic
economic
since it avoids costly separation steps in the
the KA oil production process. In addition, the mild conditions
importance
importance
used since itit avoids
since
also contribute avoids costly separation
costly separation
for a sustainability steps in
steps
enhancement in the
the KAcatalytic
KA
of the oil production
oil production
process.process. In
process. In addition,
addition, the
the
mild conditions
mild conditions used
used also
also contribute
contribute for
for aa sustainability
sustainability enhancement
enhancement of
of the
the catalytic
catalytic process.
process.

Table 1.
Table 1. Selected
Selected data
dataaa for
for the
the MW-assisted
MW-assisted oxidation
oxidation of
of cyclohexane
cyclohexane to
to KA
KA oil
oil catalyzed
catalyzed by
by Au
Au NTs.
NTs.

Catalyst
Catalyst Yield/% cc
Yield/%
TT Time
Time Conversion
Conversion Selectivity
Selectivity Total
Total Total
Total
Entry
Entry amount
amount Additive
Additive
/°C
/°C /h
/h /%bb
/% CyO (K)
CyO (K) CyOH
CyOH (A)
(A) Total
Total /% dd
/% TON ee
TON TOF/h−1−1 ff
TOF/h
/µmol
/µmol
Appl. Sci. 2018, 8, 2655 5 of 11

Table 1. Selected data a for the MW-assisted oxidation of cyclohexane to KA oil catalyzed by Au NTs.

Catalyst Yield/% c
Total
Entry Amount/ T/◦ C Time/h Additive Conversion/% b CyO CyOH Selectivity/% d Total TON e
Total TOF/h−1 f
µmol (K) (A)
1 5 50 3 — 3.9 3.5 — 3.5 90 35 12
2 10 50 3 — 6.3 5.7 — 5.7 90 29 10
3 20 50 3 — 13.9 13.1 — 13.1 94 33 11
4 30 50 3 — 14.2 14.2 — 14.2 100 24 8
5 5 50 3 HNO3 1.9 1.7 — 1.7 89 17 6
6 10 50 3 HNO3 3.4 3.1 — 3.1 91 16 5
7 20 50 3 HNO3 12.8 10.3 1.9 12.2 95 31 10
8 20 50 3 H2 SO4 3.5 3.3 — 3.3 94 8 3
9 20 30 3 — 5.4 4.7 — 4.7 87 12 4
10 20 70 3 — 14.2 12.3 1.6 13.9 98 35 12
11 20 50 1 — 2.6 2.5 — 2.5 96 6 6
12 20 50 6 — 14.9 11.3 3.1 14.4 97 36 6
13 — 50 3 — 1.5 1.2 — 1.2 80 — —
14 g 20 50 3 — 6.9 6.7 — 6.7 97 17 6
15 g 20 50 3 HNO3 6.2 5.9 — 5.9 95 15 5
16 h 20 50 3 — — — — — — — —
a Reaction conditions, unless stated otherwise: MW (10 W), CyH (5.0 mmol), TBHP (70% aq. solution, 10.0 mmol),
n(additive)/n(substrate) = 4. b Based on gas chromatography (GC) analysis, after treatment with PPh3 . c Molar yield
(%) based on substrate, that is, moles of products (cyclohexanol and cyclohexanone) per 100 moles of cyclohexane.
d Moles of cyclohexanol and cyclohexanone per mole of converted cyclohexane. e TON = Total turnover number

(moles of cyclohexanol + cyclohexanone per mole of catalyst). f TOF (h−1 ) = TON/time. g H2 O2 (30% aq. solution,
10.0 mmol). h Using air as oxidant.

The best catalytic conditions consisted of using 20 µmol of catalyst and TBHP (70% aq. solution)
as oxidant under MW irradiation at 50 ◦ C for 3 h (Table 1 and Figures 2–5).
In fact, the amount of catalyst plays a significant role, as shown in Figure 2. The increase from
e.g., 10 to 20 µmol of Au NTs in the reaction medium increases the yield from 5.7 to 13.1%.
The ratio of Au NTs surface to volume per mole of catalyst was determined for the different
amounts of catalyst used and is presented in Table 2. Calculations were performed using the
Equations S1 and S2 (see Supplementary Information) for the area and volume of an equilateral
triangle, respectively.

Table 2. Au NTs surface/volume ratio per mole of catalyst used for the MW-assisted cyclohexane
oxidation to KA oil.

Catalyst Amount/µmol Au NTs Surface/Volume Ratio/×10−4 nm−1 µmol−1

5 50
10 25
20 13
30 8

The influence of the TON affected by the surface to volume ratio, on the total yield of products was
determined (see Figure S2 of Supplementary Information), and it was found to exhibit a considerable
dependence of the catalyst amount.
Moreover, the presence of nitric acid (a commonly used cyclohexane oxidation promotor [27,28])
has a slight inhibitory effect on the catalytic activity of CTAC-stabilized Au NTs as depicted in
Figure 2 and entries 5–7 or 15 of Table 1. However, sulfuric acid has a much stronger inhibitory
effect than nitric acid (compare entries 8 and 7 of Table 1) reducing the obtained KA oil yield to
3.3% and 12.2%, respectively. Possibly, the inhibiting effect observed is due to the cationic surfactant
cetyltrimethylammonium chloride (CTAC) when combined with H2 SO4 . The complete dissociation of
the acids occurs and the pKa of the formed species is higher for sulfuric acid (HSO4 ; pKa = 1.92) than
for nitric acid (weak conjugated base NO3 − ). This higher value of pH of the reaction mixture probably
promotes the decomposition of TBHP.
Appl. Sci. 2018,
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Figure
Figure 2.
2. Effect of the Au NTs amount on the total yield of cyclohexanol and cyclohexanone obtained
Effect of the Au NTs amount on the total yield of cyclohexanol and cyclohexanone obtained
by
by MW-assisted oxidation
MW-assisted oxidation of cyclohexane with TBHP
TBHP during
during 33 h at 50 °C
◦ C using
using (---)
(—) or without
without (⎯)
(—)
of cyclohexane with TBHP during h at 50 °C using (---) or without (⎯)
nitric acid.
nitric acid.

The
The catalytic
catalytic activity
activity of
of the
the Au
Au NTs
NTs is
is also
also sensitive
sensitive to
to the
the reaction
reaction temperature
temperature and
and time
time of
of MW
MW
The catalytic activity of the Au NTs is also sensitive to the reaction temperature and time of MW
irradiation,
irradiation, as depicted
as depicted inin Figures
Figures 33 and
and 4,
4, respectively.
respectively.
irradiation, as depicted in Figures 3 and 4, respectively.

ºC
ºC
3. Influence
Figure 3.
Figure Influenceofofthethe
reaction temperature
reaction on the
temperature onyield of KAof
the yield oilKA
achieved by the Au
oil achieved byNTs
thecatalyzed
Au NTs
Figure 3. Influence
cyclohexane of with
oxidation the reaction
TBHP temperature
under MW on the for
irradiation yield
3 of KA oil achieved by the Au NTs
h.
catalyzed cyclohexane oxidation with TBHP under MW irradiation for 3 h.
catalyzed cyclohexane oxidation with TBHP under MW irradiation for 3 h.
The attempts to perform the aerobic catalytic oxidation using the above optimized conditions
(20 µmol of Au NTs, 3 h of MW irradiation at 50 ◦ C) failed (see entry 16 of Table 1 and Figure 5).
As expected, molecular oxygen is harder to activate than a peroxide compound. Moreover, as presented
in Table 3, the pressure when using air as oxidant is much lower than that generated by hydrogen
peroxide or TBHP.
In addition, the use of the greener hydrogen peroxide (30% aq. solution) oxidant leads to a
significant reduction of the KA oil produced (Figure 5). The auto-oxidation of hydrogen peroxide
 Appl. Sci. 2018, 8, 2655 7 of 11

under the optimized conditions for TBHP is known, leading to decrease in the conversion of substrates.
Decomposition of H2 O2 also prohibits its use at temperatures above 50 ◦ C.
The maximum
Appl. Sci. pressure
2018, 8, x FOR inside the reactor for the different oxidants is shown in Table 73.of 12
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Figure 4. Dependence on the reaction time of the yield of KA oil attained by the Au NTs catalyzed
oxidation of cyclohexane with TBHP under MW irradiation at 50 °C.

The attempts to perform the aerobic catalytic oxidation using the above optimized conditions
(20 µmol of Au NTs, 3 h of MW irradiation at 50 °C) failed (see entry 16 of Table 1 and Figure 5). As
expected, molecular oxygen is harder to activate than a peroxide compound. Moreover, as presented
in Table 3, the pressure when using air as oxidant is much lower than that generated by hydrogen
peroxide or TBHP.
In addition, the use of the greener hydrogen peroxide (30% aq. solution) oxidant leads to a
significant reduction of the KA oil produced (Figure 5). The auto-oxidation of hydrogen peroxide
under the optimized conditions for TBHP is known, leading to decrease in the conversion of
substrates. Decomposition of H2O2 also prohibits its use at temperatures above 50 °C.
The maximum
Figure
Figure pressure
4. Dependence
4. Dependence inside
onon
the
the the reactor
reaction
reactiontime offor
time of thethe
the different
yield
yield ofofKA oxidants
KAoiloil byisby
attained
attained shown
the the AuinNTs
Au NTs Table 3.
catalyzed
catalyzed
oxidation of cyclohexane with TBHP ◦
oxidation of cyclohexane with TBHPunder
underMWMW irradiation
irradiation atat5050°C.C.
Table 3. MW reactor maximum pressure for the oxidation of cyclohexane to cyclohexanol and
Table 3. MW reactor maximum pressure for the oxidation of cyclohexane to cyclohexanol and
The attempts
cyclohexanone to perform
catalyzed by Authe aerobic catalytic oxidation using the above optimized conditions
NTs.
cyclohexanone catalyzed by Au NTs.
(20 µmol of Au NTs, 3 h of MW irradiation at 50 °C) failed (see entry 16 of Table 1 and Figure 5). As
expected, molecular oxygenMW-reaction
MW-Reaction
conditions
is harder to activate Pressure/atm
than a peroxide
Conditions compound. Moreover, as presented
Pressure/atm
Control
in Table 3, the pressure when using(without catalyst)
air as oxidant is much lower 1.3 than that generated by hydrogen
peroxide or TBHP. Control (without
TBHP catalyst) 5.31.3
TBHP 5.3
In addition, the use of the greener HH2OOhydrogen
2 peroxide (30% 5.65.6aq. solution) oxidant leads to a
2 2
significant reduction of the KA oil producedair
air (Figure 5). The auto-oxidation
1.01.0 of hydrogen peroxide
under the optimized conditions for TBHP is known, leading to decrease in the conversion of
substrates. Decomposition of H2O2 also prohibits its use at temperatures above 50 °C.
The maximum pressure inside 14 the reactor for the different oxidants is shown in Table 3.
No additive
Table 3. MW reactor maximum12 pressure for the oxidationNitric
of cyclohexane to cyclohexanol and
acid
cyclohexanone catalyzed by Au NTs.
10
KA oil yield / %

MW-reaction conditions Pressure/atm

Control
8 (without catalyst) 1.3
TBHP 5.3
6 H2O2 5.6
air 1.0
4

2 14
No additive
0 12
Nitric acid
H 2O 2
H2O2 TBHP O2
O2
10
KA oil yield / %

Figure 5. Influence of the oxidant type on the yield of cyclohexanol and cyclohexanone achieved by
8
the Au NTs catalyzed oxidation of cyclohexane under MW irradiation for 3 h at 50 ◦ C.
6
Even using the very low MW irradiation power of 10 W, a favorable effect was observed for the
4
present catalytic system, as reported for other oxidative systems [28–32]. For example, only 2% of
product, under the same conditions2of those presented in entry 4 of Table 1 but using an oil-bath as
heating source (entry 4, Table 4), was obtained. The accelerating effect of microwave-assisted reactions
0
results mainly from (i) the selective absorption
H 2O 2
H2O2 of the radiation
TBHP O2
O2 by polar compounds, (ii) the local
Appl. Sci. 2018, 8, 2655 8 of 11

overheating (“hot-spot” effect), and (iii) the non-thermal effects such as influence on the pre-exponential
factor A in the Arrhenius equation [33].

Table 4. Selected data a for the oxidation of cyclohexane to cyclohexanol and cyclohexanone during 3 h
at 50 ◦ C using conventional heating.

Catalyst Yield/% b
Entry Additive Total TON c Conversion/%
Amount/µmol CyO (K) CyOH (A) Total
1 5 — 0.2 — 0.2 2 0.5
2 10 — 0.3 — 0.3 2 0.6
3 20 — 0.5 — 0.5 1 0.9
4 30 — 2.0 — 2.0 3 2
5 5 HNO3 0.6 — 0.6 6 0.8
6d 20 — 0.2 — 0.2 1 0.3
7d 20 HNO3 0.3 — 0.3 1 0.3
8e 20 — — — — — —
a Reaction conditions, unless stated otherwise: CyH (5.0 mmol), TBHP (70% aq. solution, 10.0 mmol),
n(additive)/n(substrate) = 4. b Based on gas chromatography (GC) analysis, after treatment with PPh3 ; molar yield
(%) based on substrate, that is, moles of products (cyclohexanol and cyclohexanone) per 100 mol of cyclohexane.
c TON = Total turnover number (moles of cyclohexanol + cyclohexanone per mole of catalyst). d H O (30% aq.
2 2
solution, 10.0 mmol). e Using air as oxidant.

It is also worth to notice that the attained maximum yield value in the present study is also
higher than the reported [34] for the currently industrial (commercial) process with the advantage of
being much more selective (100% selectivity was obtained, see entry 4 of Table 1) and obtained under
mild conditions.
The stability of the gold nanotriangles in the oxidative reaction medium was assessed by UV-vis
spectrophotometry, through the localized surface plasmonic resonance (LSPR) of the AuNTs before
and after the reaction. As depicted in Figure 6, after the catalytic reaction, only a very small λmax
shift from 533 nm (before the reaction) to 536 nm (after the reaction) of the LSPR was detected. As a
common rule, bigger nanoparticles, as well as more complex morphologies, lead to longer red-shifted
absorptions in the LSPR and therefore no significant aggregation of the Au NTs appears to occur
duringAppl.
theSci.
catalytic
2018, 8, x reaction.
FOR PEER REVIEW 9 of 12

0.50

0.45

0.40
Initial
0.35 After reaction
Abs

0.30

0.25

0.20

0.15

0.10

0.05

0.00
400 500 600 700

λ /nm

Figure 6. Absorption spectra (400 – 700 nm) of the Au NTs before and after the catalytic
Figure 6. Absorption spectra (400 – 700 nm) of the Au NTs before and after the catalytic oxidation
oxidation reaction.
reaction.

By analogy with reported mechanisms for different types of Mn/n-1 metal systems [6,7,35], the
proposed mechanism for the present Au NTs/TBHP system follows (reactions (1)–(9), Scheme 3).
 400 500 600 700

λ /nm

Figure
Appl. Sci. 2018,6.
8, Absorption
2655 spectra (400 – 700 nm) of the Au NTs before and after the catalytic oxidation9 of 11
reaction.

By analogy with reported

reported mechanisms
mechanisms for
fordifferent
differenttypes
typesofofMM n/n−1 metal systems [6,7,35],
n/n-1 metal systems [6,7,35], the
the proposed mechanism for the present Au NTs/TBHP system follows (reactions
proposed mechanism for the present Au NTs/TBHP system follows (reactions (1)–(9), (1)–(9), Scheme
Scheme 3). 3).

Scheme 3. Suggested mechanism for cyclohexane oxidation catalyzed by Au NTs.

NTs.

Firstly,
Firstly,Au-catalyzed
Au-catalyzed decomposition
decomposition of TBHP occurs,
of TBHP leading
occurs, to ROO
leading toand
ROOROand
radicals
RO upon oxidation
radicals upon
by n
Au or reduction n− 1
by reduction
A according
oxidation by Au or n by Ato reactions
n-1 according (1)to
and (2), respectively.
reactions (1) and Then, H-abstractionThen,
(2), respectively. from
CyH by RO leads
H-abstraction from to CyH
the formation
by RO leadsof cyclohexyl radical (Cy)
to the formation (reaction (3)).
of cyclohexyl CyOO
radical (Cy)is formed
(reactionby(3)).
the
reaction of Cy with dioxygen (reaction (4)), and CyOOH can then be formed
CyOO is formed by the reaction of Cy with dioxygen (reaction (4)), and CyOOH can then be formed upon H-abstraction from
TBHP by CyOO (reaction
upon H-abstraction from (5)).
TBHP Au-assisted decomposition
by CyOO (reaction of CyOOHdecomposition
(5)). Au-assisted to CyOO and CyO (reactions
of CyOOH to
(6)
CyOO and and
(7)) leads to the formation
CyO (reactions (6) andof(7))
theleads
desired products:
to the cyclohexanol
formation (CyOH)
of the desired and cyclohexanone
products: cyclohexanol
(Cy − H =O),
(CyOH) andaccording to reactions
cyclohexanone (8) and
(Cy−H=O), (9)).
according to reactions (8) and (9)).
This work created the possibility of using non-supported gold nanoparticles towards cyclohexane
This under
oxidation work mildcreated the possibility
conditions of using
using peroxide non-supported
as oxidant. gold nanoparticles
The combination of suitable Autowards
NPs,
cyclohexane oxidation under mild conditions using peroxide as oxidant.
such as CTAC-stabilized Au NTs, and well-adjusted reaction parameters (in particular, the use of The combination of
suitable
MW Au NPs,can
irradiation) such
leadasto CTAC-stabilized
highly selective and Au efficient
NTs, and well-adjusted
catalytic reaction
systems with parameters
significance (in
for the
development of a sustainable process for cyclohexane oxidation to KA oil.
In fact, the following advantages of using Au NTs instead of spherical Au NPs can be considered:
(i) for the same diameter, triangular nanoplates present more gold atoms at the nanoparticle surface
when compared with nanospheres and circular nanoplates; (ii) despite being stable, gold nanotriangles
are less stable than small gold nanospheres and therefore easier to separate from solution by
centrifugation (expensive and not an easy-to-scale process), which can be important for reusing
these materials at an industrial level; and (iii) anisotropic materials such as nanotriangles present
hot-spots that can concentrate the energy. This can be important to favor the reaction.

Supplementary Materials: The following are available online at http://www.mdpi.com/2076-3417/8/12/2655/

s1, Figure S1: Additional Transmission Electron Microscopy (TEM) images (a) and (b) and histogram (c) of Au
NTs, Figure S1: Dependence of turnover number (TON) affected by the surface to volume ratio, on the total yield
of products.
Author Contributions: Conceptualization, A.P.C.R. and R.P.O.-S.; methodology, I.A.S.M.; formal analysis, A.P.C.R.
and R.P.O.-S.; investigation, A.P.C.R., I.A.S.M. and R.P.O.-S.; writing—original draft preparation, L.M.D.R.S.M.;
writing—review and editing, L.M.D.R.S.M.; supervision, L.M.D.R.S.M. and D.M.F.P.; project administration,
L.M.D.R.S.M.; funding acquisition, L.M.D.R.S.M.
Funding: This research was funded by the Fundação para a Ciência e a Tecnologia (FCT), Portugal:
projects UID/QUI/00100/2013, UID/BIO/04565/2013 and PTDC/QEQ-ERQ/1648/2014 and fellowships
SFRH/BPD/90883/2012 to APCR and PD/BD/116850/2016 to RP Oliveira-Silva. Funding received by
IBB-Institute for Bioengineering and Biosciences from Programa Operacional Regional de Lisboa 2020 (Project N.
007317) is also acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.
Appl. Sci. 2018, 8, 2655 10 of 11

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