The Enhanced Catalytic Performance and Stability of Ordered Mesoporous Carbon Supported Nano-Gold with High Structural Integrity for Glycerol Oxidation

Article abstract of DOI:10.1002/tcr.201800109

Ordered mesoporous carbon (OMC) supported gold nanoparticles of size 3–4 nm having uniform dispersion were synthesized by sol-immobilization method. OMCs such as CMK-3 and NCCR-56 with high surface area and uniform pore size were obtained, respectively, using ordered mesoporous silicas such as SBA-15 and IITM-56 as hard templates, respectively. The resulting OMC supported monodispersed nano-gold, i. e., Au/CMK-3 and Au/NCCR-56, exhibited excellent performance as mild-oxidizing catalysts for oxidation of glycerol with high hydrothermal stability. Further, unlike activated carbon supported nano-gold catalysts (Au/AC), the OMC supported nano-gold catalysts, i. e., Au/CMK-3 and Au/NCCR-56, show no aggregation of active species even after recycling. Thus, in the case of Au/CMK-3 and Au/NCCR-56, both the fresh and regenerated catalysts showed excellent performane for the chosen reaction owing to an enhanced textural integrity of the catalysts and that with remarkable selectivity towards glyceric acid. The significance of the OMC supports in maintaining the dispersion of gold nanoparticles is explicit from this study, and that the activity of Au/AC catalyst is considerably decreased (～50 %) upon recycling as a result of agglomeration of the active gold nanoparticles over the disordered amorphous carbon matrix.

Full text of DOI:10.1002/tcr.201800109

Personal Account
DOI: 10.1002/tcr.201800109
The Enhanced Catalytic Performance and
Stability of Ordered Mesoporous Carbon
Supported Nano-gold with High
Structural Integrity for Glycerol
Oxidation
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C H E M I C A L
R E C O R D
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[
a]
[a, b, c]
Palle R. Murthy and Parasuraman Selvam*
rd
Dedicated to Dr. M. Lakshmi Kantam on the occasion of her 63 birthday
Chem. Rec. 2018, 18, 1–14
© 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Wiley Online Library
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Abstract: Ordered mesoporous carbon (OMC) supported gold nanoparticles of size 3–4 nm
having uniform dispersion were synthesized by sol-immobilization method. OMCs such as
CMK-3 and NCCR-56 with high surface area and uniform pore size were obtained, respectively,
using ordered mesoporous silicas such as SBA-15 and IITM-56 as hard templates, respectively.
The resulting OMC supported monodispersed nano-gold, i.e., Au/CMK-3 and Au/NCCR-56,
exhibited excellent performance as mild-oxidizing catalysts for oxidation of glycerol with high
hydrothermal stability. Further, unlike activated carbon supported nano-gold catalysts (Au/AC),
the OMC supported nano-gold catalysts, i.e., Au/CMK-3 and Au/NCCR-56, show no
aggregation of active species even after recycling. Thus, in the case of Au/CMK-3 and Au/
NCCR-56, both the fresh and regenerated catalysts showed excellent performane for the chosen
reaction owing to an enhanced textural integrity of the catalysts and that with remarkable
selectivity towards glyceric acid. The significance of the OMC supports in maintaining the
dispersion of gold nanoparticles is explicit from this study, and that the activity of Au/AC catalyst
is considerably decreased (~50%) upon recycling as a result of agglomeration of the active gold
nanoparticles over the disordered amorphous carbon matrix.
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Keywords: Glycerol oxidation, Glyceric acid, Nano-Gold, Ordered mesoporous carbon, CMK-
3, Activated carbon.
production. Owing to the high functionality, glycerol can be
used in synthesizing different value-added chemicals through
oxidation, hydrogenolysis, dehydration, etherification, ester-
1
. Introduction
Supported gold catalysts are used in oxidation and hydro-
genation reactions. They are predominantly employed in
alcohol oxidation especially glycerol oxidation reaction
(Scheme 1) as glycerol, a by-product of transesterification
reaction in the production of bio-diesel, is one of the
important bio-refinery feedstock. The glycerol availability
will increase sharply due to an increase in bio-diesel
[
1]
[4]
ification, pyrolysis, polymerization, etc. Glyceric acid is one
of the major oxidation products of glycerol and has extensive
applications in variety of biological activities like liver
stimulant and cholesterolytic activity, base material for func-
[
2]
[3]
[5]
tional surfactants and monomer for oligoesters or polymers.
Therefore, it is important to control the oxidation process in
order to obtain this valuable and desired product. Supported
gold nanoparticles are showing promising results for glycerol
oxidation compared to several other noble metal nano-
[
6]
particles. Nano-gold exhibits superior activity for selective
oxidation of organic molecules due to the higher fraction of
[
7]
surface atoms with low coordination numbers
when
compared to bulk gold which has filled d band and high
activation energy barrier. In order to increase stability and
avoid aggregation, gold nanoparticles are dispersed on high
[
8]
surface area carbon or metal oxide supports. Ordered
porous carbon with uniform pore structure and high surface
area is considered as most attractive support in view with its
[9]
Scheme 1. Products obtained by the oxidation of glycerol.
[
7a]
stability and chemical inertness.
In general, ordered mesoporous carbons (OMC) are
prepared by soft and hard-templating method, primarily
[a] Dr. P. R. Murthy, Prof. Dr. P. Selvam
National Centre for Catalysis Research and Department of
Chemistry
[
10]
using surfactant-templated silica frameworks
and the
Indian Institute of Technology Madras
Chennai 600 036 (India)
E-mail: selvam@iitm.ac.in
process depends on the action of carbonizing carbon
precursors inside the pores of silica. Specifically, OMC like
CMK-1 and CMK-3 have been produced by carbonizing the
organic precursor inside the pores of MCM-48 and SBA-15,
[b] Prof. Dr. P. Selvam
School of Chemical Engineerning and Analytical Science
The University of Manchester
[
5,7]
respectively.
In the case of noble metal nanoparticles
Manchester M13 9PL (United Kingdom)
supported on OMCs show profound applications in catalysis,
electrochemistry and fine-chemical synthesis. In this regard,
platinum supported on OMCs were widely studied for direct
[c] Prof. Dr. P. Selvam
Department of Chemical and Process Engineering
University of Surrey, Guildford
[
11]
Surrey GU2 7XH (United Kingdom)
methanol fuel cell applications while gold supported on
Chem. Rec. 2018, 18, 1–14
© 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Wiley Online Library
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OMCs were mostly used in organic transformations. In
this context, we have synthesized OMCs such as CMK-3 and
NCCR-56 using SBA-15 and IITM-56 as hard-templates,
respectively. These OMCs were then employed as supports
for gold nanoparticles, and the resulting supported nano-gold
catalysts, viz., Au/CMK-3 and Au/NCCR-56, were utilized
for glycerol oxidation reaction. The uniform pore size of the
OMC supports are mainly responsible for stabilizing the
nanoparticles and hence the recyclability of the catalyst is also
examined. In addition, the efficiency of these catalysts was
also evaluated in relation to the popularly known catalysts
such as activated carbon supported gold catalysts, Au/AC.
polyvinyl alcohol (PVA, average MW 14,000, CDH),
glycerol (99.5%, Rankem), glyceric acid (95.0%, Aldrich).
2.2. Synthesis of OMSs
SBA-15: Ordered mesoporous silica, SBA-15 was prepared by
adding tetraethoxysilane (TEOS) into the hydrochloric acid
solution of triblock co-polymer P123. The molar composi-
tion was 1 TEOS: 0.017 P123: 5.9 HCl: 193 H O. The
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mixture was stirred at 408C for 20 h, followed by hydro-
thermal treatment at 1008C for 48 h. The solid product
obtained was filtered and dried overnight at 808C followed
by calcination at 5508C for 6 h in the presence of air
[
13]
atmosphere.
2. Experimental
IITM-56: The ordered mesoporous silicate, referred as
IITM-56, was synthesized adopting a previously reported
2.1. Starting Materials
[
14]
method. The molar gel composition was 1 TEOS: 0.15
The chemicals used in this study are of analytical grade:
Pluronic P-123, Brij-56, tetraethyl orthosilicate (TEOS,
98.0%, Sigma Aldrich), methanol (99.9%), hydrofluoric
acid (Merck) and sulphuric acid (98.0%, Merck), sodium
tetrachloroaurate (III) dihydrate (99.0%, Sigma Aldrich) and
activated carbon from SD fine chemicals, sodium borohy-
dride (95.0%, SRL), tri-sodium citrate (99.0% SRL) and
Brij-56: 11.30 HCl: 119 H O. In a typical synthesis, 4.0 g of
2
Brij 56 was added to 20 mL of water and the solution was
stirred at 508C until a clear solution was obtained. There-
after, 80 mL of 2 M HCl was added to the solution and
further stirred for 2 h. Then, 8.3 g of (TEOS) was added and
stirred at 508C for 24 h. The resulting mixture was the
transferred to an autoclave and hydrothermally treated at
1008C for 24 h. Obtained precipitate was filtered, washed,
Dr. Palle Ramana Murthy obtained MSc
degree in Chemistry from Andhra Univer-
sity, Visakhapatnam, India, and PhD in
Catalysis from the Indian Institute of
Technology (IIT) -Madras, Chennai, In-
dia. The research work presented here was
carried out at the National Center for
Catalysis Research (NCCR), IIT-Madras.
His research interests include supported
catalyst systems and their applications in
biomass conversion and selective oxidation
processes.
was also a Visiting Associate Professor in
the School of Chemical Engineering, The
University of Queensland, Brisbane, Aus-
tralia, and an Eminent International Visit-
ing Professor in the School of Science and
Health, Western Sydney University, Pen-
rith, Australia. Prior to these, Prof. Selvam
was a Post-Doctoral Research Associate in
the Department of Condensed Matter
Physics, and Laboratory of X-ray Crystal-
lography, University of Geneva, Geneva,
Switzerland. His research interests are in
the areas of solid state and surface
chemistry with an emphasis on nano-
structured materials and their applications
in heterogeneous catalysis as well as energy
conversion, strorage and environmental
remediation processess. Prof. Selvam has
filed about 20 patents and published over
Prof. Dr. Parasuraman Selvam is cur-
rently Head, National Center for Catalysis
Research, and Professor in the Department
of Chemistry, IIT-Madras, Chennai, India;
Adjunct Faculty, School of Chemical En-
gineering and Analytical Science, The
University of Manchester, Manchester,
U.K., and Department of Chemical and
Process Engineering, University of Surrey,
Guildford, U.K. Earlier, Prof. Selvam was
a Faculty at IIT-Bombay, Mumbai, India,
and Tohoku University, Sendai, Japan. He
3
00 original research papers in peer-
reviewed journals and conference proceed-
ings. https://www.iitm.ac.in/info/fac/sel-
vam
Chem. Rec. 2018, 18, 1–14
© 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Wiley Online Library
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dried at 608C for 6 h and calcined at 5508C for 1 h in
nitrogen followed by 5 h in air atmosphere at a heating rate
of 18C/min in order to obtain surfactant free OMS, i.e.,
IITM-56.
tor with a Ni-filtered Cu Ka radiation source (l=1.5406 A)
operating at 40 kV and 40 mA. Low (0.5–78) and high angle
(10–808) diffraction patterns were recorded separately with a
scanning rate of 0.58 and 18min respectively. The crystallite
size was calculated by X-ray line broadening using Scherrer
method d=K l/ (b cosq) where, d is the crystallite size in nm,
K is the numerical (crystallite shape) constant (K=0.89), l is
À1
2.3. Synthesis of OMCs
˚
CMK-3 and NCCR-56: Ordered mesoporous carbons CMK-
the wavelength of radiation used (l=1.5405 A), b is full
3 and NCCR-56 were prepared as per the reported
width at half maximum (FWHM) in radians and q is the
Bragg diffraction angle in degrees, at the peak maximum.
Transmission Electron Microscope (TEM) analysis of the
carbon material was performed on Philips CM12 Trans-
mission Electron Microscope with EDAX attachment.
Nitrogen adsorption-desorption isotherms were obtained
at 77 K on Micrometrics ASAP 2020 Porosimetry system.
The specific surface area of the samples were calculated
according to the Brunauer-Emmett-Teller (BET) method,
and pore size distribution curves were obtained from the
analysis of nitrogen desorption isotherms using Barrett-
Joyner-Halenda (BJH) method for mesoporous materials and
HorvathÀKawazoe (HK) method for microporous AC. FT-IR
spectra of various mesoporous silica and carbon samples were
recorded on Bruker Tensor 27 FT-IR spectrometer with
[
13a,15]
[14]
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procedure.
Initially, IITM-56
was added to an
acidified sucrose solution obtained by dissolving suitable
amount of sucrose and H SO in water. The mixture was
2
4
dried at 1008C for 6 h followed by drying at 1608C for 6 h.
The impregnation step was repeated at this stage. Prior to
impregnating sucrose solution, the silica template was dried
in vacuum at 1008C for 30 min. The dark black colored
sample obtained was carbonized at 9008C under nitrogen
flow for 6 h with heating rate of 58C/min. The silica template
was removed by dissolving in dil. HF. Similarly, CMK-3 was
prepared using SBA-15 as hard template. The resulting
carbon materials were washed with ethanol and dried at
1208C for 6 h and systematically characterized by various
analytical and spectroscopic techniques.
À1
4 cm resolution and 100 scans in the mid IR (600–
4000 cm ) region using the KBr pellet technique. FT-Raman
À1
2.4. Preparation of Au/OMC and Au/AC
spectra of various samples were recorded using Bruker Multi
RAM FT-Raman spectrometer attached with a Nd:YAG
diode pumped laser (1064 nm) as the excitation source having
an output power of 1 W and liquid nitrogen cooled
germanium detector.
The gold content in the calatyst was analysed using
Inductively Coupled Plasma Optical Emission Spectrometer
(ICP-OES, Perkin Elmer Optima Model 5300 DV) after
calibration with standard solution containing known metal
content. XPS measurements were performed with an
Omicron Nanotechnology spectrometer with hemispherical
analyzer. The monochromatized Mg Ka X-ray source (E=
1253.6 eV) was operated at 15 kV and 20 mA. For the narrow
scans, the analyzer pass energy of 25 eV was applied. The base
Gold nanoparticles were immobilized on carbons(OMC and
AC) via the formation of a gold-sol and subsequent
[16]
deposition of the sol onto the carbon support. Initially,
PVA (2% w/w, 0.706 mL) was added to the NaAuCl .2H O
4
2
À4
(140 mL, 5310 M) solution, which was subsequently
reduced by the addition of NaBH (2.88 mL; 0.1 M). The
4
resulting colloid (acidified at pH 2 by sulphuric acid) was
immobilized by adding carbon (1.4 g)under vigorous stirring
in order to have a final metal loading of 1 wt%
(0.608 mmol%). After 2 h, the slurry was filtered off and the
catalyst was thoroughly washed with distilled water to remove
residual chlorine present, if any. The catalyst was dried for
5 h at 1208C and used for characterization and catalytic
evaluation. The size effect of the Au nanoparticles with
varying particle size were prepared and subsequently sup-
À10
pressure in the analysis chamber is 5310 torr.
ported on activated carbon (AC) by varying the NaAuCl
concentration from 5310 to 5310 M whilst NaBH4
4
2.6. Catalytic Evaluation
À4
À3
and PVA are kept constant.
All the prepared catalysts were tested for glycerol oxidation
reaction. Glycerol, NaOH (glycerol/NaOH=4 mol/mol) and
the supported nano-gold catalyst (glycerol/metal=500 mol/
mol) were dispersed in 10 mL of distilled water and kept in
autoclave (Parr, 100 mL). Initially, the reactor was pressurized
2.5. Characterization
UV-VIS spectra of Au-sols were performed on Jasco V-530.
UV-Visible spectrophotometer in H O between 200 and
with 7 bar O and thermostated at the 608C. After the
2
2
800 nm, in a quartz cuvette with a scan rate of 200 nm per
min. Diffraction patterns were recorded using a Bruker D8
Focus Advance diffractometer equipped with LynxEye detec-
reaction mixture was allowed for 5 h the collected products
were analysed by HPLC with refractive index (RI) detector.
Reactant and products were separated on an ion-exclusion
Chem. Rec. 2018, 18, 1–14
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column (Alltech OA-1000 organic acid) heated at 808C with
reflections in the diffraction patterns suggest the formation of
long-range ordered porous materials. As expected, the main
reflections of the carbon replicas were found to systematically
shift towards higher-angle in comparison with that of their
corresponding silica counterparts, indicating a reduction in
the size of the unit cell (Table 1). On the other hand, the
broadening of the reflections observed, in particular, for the
mesoporous carbons signifies the presence of disordered pore
structure as compared to the mesoporous silica structures.
À1
0.5 mLmin of H SO (0.0004 M) as the eluent. Products
2
4
were recognized by comparison with authentic samples.
Conversion is defined as the ratio of moles of glycerol
converted to moles of glycerol initially charged. Selectivity
towards a specific product is given as the ratio of moles of
specific product to the total moles of glycerol. Carbon balance
is defined as the ratio of moles of carbon in all products to
that in the converted glycerol. Conversion, selectivity and
carbon balance are expressed in mole percentage. Turnover
frequency (TOF) is defined as the number of molecules of
glycerol converted per active site per second.
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Table 1. Structural and textural properties of OMS and OMC.
a
b
Material
a
(
h
w
S
Vp
D
BJH
D
TEM
0
BET
2
À1
3
À1
nm) (nm) (m g ) (cm g ) (nm) (nm)
3. Results and Discussion
SBA-15
CMK-3
Au/CMK-3
IITM-56
NCCR-56
Au/NCCR-
10.08 3.58 663
9.77 5.47 1080
9.93 5.73 1032
5.94 2.14 772
5.10 1.90 1367
4.88 1.58 1243
1.10
1.26
1.17
1.00
1.40
1.30
6.5
4.3
4.2
3.8
3.2 2.9
3.3 3.3
6.6
4.5
4.3
3.6
3.1. OMC
Figure 1 shows the low angle XRD patterns of mesoporous
carbon products such as CMK-3, NCCR-56 and those of the
ordered mesoprous silica (OMS) templates SBA-15 and
IITM-56, respectively. The ordered porous carbons, viz.,
CMK-3 and NCCR-56, obtained from the silica templates
such as SBA-15 and IITM-56, respectively have exhibited
well resolved peaks which are typical of highly ordered 2D
5
6
AC
Au/AC
—
—
—
—
1080
1049
0.80
0.79
1.3
1.4
—
—
a
2
Average unit cell parameter calculated using 1/d =4/3
2
2
2
b
(h +hk+k /a ). Wall thickness, h
=a
ÀDBJH
.
w
0
[14–15]
hexagonal mesoporous structures.
An intense reflection
representing (100) crystal plane of 2D-hexagonal structure is
observed for both silica templates as well as the corresponding
mesoporous carbons indicating proper replication of 2D-
hexagonal porous structures. The appearances of well defined
The N adsorption-desorption isotherms and pore size
2
distribution of OMSs (SBA-15, IITM-56) and corresponding
OMCs (CMK-3, NCCR-56) are shown in Figure 2. The
textural parameters of the materials are given in Table 1. Both
OMS and OMC exhibited type-IV isotherms with H1
hysteresis loop indicating the mesoporous characteristics. The
mean pore size of CMK-3 and NCCR-56 are 4.3 nm and
3.3 nm respectively which are lower than their corresponding
silica templates; the distinct, narrow pore-size distribution
reveals the retention of mesoporous structure with uniform
pores.
Figure 3 depicts the FT-IR spectra of SBA-15 and CMK-
3, which reveal signatures of the various functional groups
present at the surface of the ordered mesoporous silica and
carbon. The stretching and bending mode of OÀH are seen
À1
as broad signals in the range 3100–3800 cm and at
À1
1633 cm respectively. The signal corresponding to asym-
2
metric and symmetric CÀH stretching vibrations of sp -type
À1
carbon are observed at 2985 and 2879 cm . On the other
hand, the signals related to asymmetric, symmetric CÀH
3
stretching and bending vibrations of sp -type carbon are seen
À1
À1
at 2950, 2828 cm and at 1355 cm respectively. The
presence of C=C and CÀC bonds of aromatic rings is
À1
supported by the bands at 1520 and 1410 cm , respectively.
The broad signal in the range 1150–1300 cm is assigned to
À1
Figure 1. XRD patterns of SBA-15; CMK-3; IITM-56; NCCR-56.
CÀO stretching and OÀH bending modes of alcoholic,
Chem. Rec. 2018, 18, 1–14
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Figure 4. FT-IR spectra of: (a) IITM-56; (b) NCCR-56. Insets: correspond-
ing functional groups of NCCR-56.
Figure 2. (A) N sorption isotherms and (B) Pore size distribution.
2
Figure 5. FT-Raman spectrum of CMK-3.
phenolic, and carboxylic groups. Stretching vibration of C=O
À1
gives rise to a band at 1730 cm . The complete removal of
silica from the ordered mesoporous carbons is substantiated
À1
by the absence of a band at 1100 cm arising due to
symmetric vibration of SiÀOÀSi. Similar vibrational charac-
teristics are observed in case of IITM-56 and NCCR-56 and
the spectra are shown Figure 4.
Figure 5 shows the FT-Raman spectrum of CMK-3 which
À1
À1
exhibits two distinct signals at 1296 cm and 1586 cm
Figure 3. FT-IR spectra of: (a) SBA-15; (b) CMK-3. Insets: corresponding
functional groups of CMK-3.
corresponding to D1-band and G-band, respectively. Figure 6
shows the FT-Raman spectrum of NCCR-56, in which two
À1
À1
distinct signals at 1287 cm and 1587 cm corresponding to
Chem. Rec. 2018, 18, 1–14
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3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
Figure 6. FT-Raman spectrum of NCCR-56.
Figure 7. XP spectrum of CMK-3.
D1-band and G-band, respectively are observed. The
presence of broad D1-band corresponding to a graphitic
lattice vibration mode with A1g symmetry in the spectra
indicate the possible disordered arrangement of carbon in the
pore walls leading to the loss of hexagonal symmetry of the
[17]
graphitic framework structure. Furthermore the D2 band
for both the carbons corresponds to a defective graphitic
lattice mode with E2g symmetry. The intensity of G band is
more in case of CMK-3 sample; So it is expected that the
intensity of D2 band will be more intense in case of CMK-3
À1
sample. The prominent D3 band at around 1470 cm
originates from the amorphous carbon fraction contributed
largely by the walls of mesoporous carbon CMK-3 and
À1
NCCR-56. The band at ~1180 cm in Raman spectra of
both the mesoporous CMK-3 and NCCR-56 carbon could
be attributed to diamond like carbons with significant
3
fraction of sp bonds.
On the other hand, the relative integrated area of the D1-
band and G-band (A /A ) of CMK-3 is 2.97 and NCCR-56
Figure 8. XP spectrum of NCCR-56.
D1
G
is 2.73, indicating that the mesoporous carbon is composed
of folded graphene sheets with a small degree of graphitiza-
tion and high degree of disordered surface. Further, the
integrated peak intensity ratio of the D- and G-bands is used
to quantify the changes in-plane crystallite sizes (L ) which is
[
20]
groups such as CÀOH, C=O and COOH, respectively.
[18]
Similar observations are made in case of NCCR-56 and
spectrum is presented in Figure 8.
a
128 nm and 146.4 nm respectively for CMK-3 and NCCR-
56.
3.2. Catalytic Stability of Au/OMC
XPS is a surface technique which provides valuable
information on the chemical composition, electronic state
and oxidation state of the elements that exist in the few
The surface area of OMC samples has been slightly decreased
after Au loading because the Au nanoparticles are within the
pores of OMCs (see Table 1). The XRD patterns of Au/OMC
and regenerated (second cycle) catalysts after the catalytic
reaction are shown in the Figure 9 and 10. A strong reflection
of (111) plane corresponding to face-centered cubic (FCC)
lattice of gold was observed for all gold nanoparticles
immobilized on carbon. However the broad features of (111)
plane reveals that the Au metallic clusters are of nano-size and
[19]
uppermost layers of the surface. C (1 s) XP spectrum of
CMK-3 (Figure 7) features an intense peak at 284.4 eV which
could be attributed to both amorphous/disordered (diamond-
like) and graphitic carbons, in agreement with FT-IR data,
the bands (deconvoluted) at 286.0, 287.2 and 288.8 eV are
attributed to the presence of oxygen-containing functional
Chem. Rec. 2018, 18, 1–14
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9
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3
3
3
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3
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4
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4
4
4
4
4
4
4
4
5
5
5
Figure 11. TEM images of: (a) SBA-15; (b) CMK-3; (c) Au/CMK-3; (d)
Au/CMK-3 recycled. Inset: Gold particle size distribution.
Figure 9. XRD patterns of: (a) Au/CMK-3 (fresh), (b) Au/CMK-3
(recycled), and (c) CMK-3.
carbon samples CMK-3 and NCCR-56 (Figure 11b and 12b)
reveal that the structures of these mesoporous carbons are
[
15]
exactly inverse replica of their silica counterparts. Further,
the micrographs of Au/CMK-3 and Au/NCCR-56 sample
(Figure 11c and 12c) reveal an excellent dispersion of gold
nanoparticles with a narrow particle size distribution which is
ably supported by the histogram (inset). These micrographs
clearly illustrate the uniform grafting of Au particles onto the
mesoporous channels of carbon supports. In case of Au/
CMK-3 and Au/NCCR-56 catalysts, the particle size
remained significantly unchanged even after regeneration
(second cycle) which demonstrates the role of mesoporous
network in preventing the aggregation of gold nanoparticles
during the reaction (Figure 11d and 12d).
The surface oxidation states of the Au nanoparticles
[
21]
dispersed over the carbon support is determined by XPS.
XP spectrum of Au supported CMK-3 in 4f region is shown
in the Figure 13. The gold nanoparticles grafted over the
mesoporous carbon supports gave rise to peaks at a binding
energy of 83.9 and 87.6 eV corresponding to Au 4f7/2 and the
Au 4f5/2 electrons respectively. The intense component of the
deconvoluted signal of Au 4f , observed at 83.9 eV is
Figure 10. XRD patterns of: (a) Au/NCCR-56 (fresh), (b) Au/NCCR-56
(recycled), and (c) NCCR-56.
7/2
0
possibly well dispersed over the carbon support. The
crystallite sizes are calculated by using the Scherrer equation
and they are well correlated with TEM data which is given in
Table 3. In the case of Au/CMK-3 and Au/NCCR-56 catalyst
the intensity of the peak corresponding to the plane (111)
remained unchanged, even after regeneration (second cycle)
which reinstates the presence of monodispersed and uniform
gold particles even after the reaction (Figure 9b & 10b).
The corresponding gold loaded carbon samples are shown
in Figures 11 and 12. SBA-15 and IITM-56 (Figure 11a and
12a) exhibit well ordered mesoporous channels and the
attributed to metallic (Au ) whereas the component at
+
85.0 eV is due to non-metallic gold (Au ) and a weak signal
+
3
at 86.5 eV represents the presence of Au . Similar trend has
been observed for Au 4f5/2 signal as the peak component at
0
87.6 eV is due to metallic Au whereas the component at
88.7 eV and a weak signal at 90.2 eV are attributed to non-
+
+3
metallic (Au ) and Au respectively. The electronic charac-
teristics of Au/NCCR-56 resembled as that of Au/CMK-3
and the spectrum is given in Figure 14. But from the area of
the deconvolution peaks (Table S3) we have observed that
Chem. Rec. 2018, 18, 1–14
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8

P e r s o n a l A c c o u n t
T H E C H E M I C A L R E C O R D
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
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9
0
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7
8
9
0
1
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
Figure 14. XP spectrum of Au/NCCR-56.
Figure 12. TEM images of: (a) IITM-56; (b) NCCR-56; (c) Au/NCCR-56;
Table 2. Structural and spectral properties of Au/AC.
(d) Au/NCCR-56 recycled. Inset: Gold nanoparticles size distribution.
a
Catalyst
Structural data Particle size (nm)
UV-VIS c
b
Au/a (nm)
XRD TEM
lmax (nm)
0
À4
À4
À3
À3
À3
5
6
1
310
310
310
M
M
M
M
M
0.4082
0.4074
0.4072
0.4069
0.4068
4.5
6.7
8.8
10.9
12.8
4.1Æ1.1
511
515
520
7.0Æ1.6
8.9Æ2.6
3310
310
11.1Æ3.0 526
5
13.0Æ5.0 532
a
1 wt% Au/AC prepared using various concentration of gold sol;
a=d3(h +l +k ) ; Au-sol.
b
2
2
2 1/2 c
increase with the particle size as a function of the precursor
concentration. Figure 15 depicts XRD patterns of various AC
supported gold catalysts. All the samples exhibit typical
reflections corresponding to the gold nanoparticles present on
the AC support. The characteristic reflections corresponding
to FCC gold clearly indicate the quality of the samples.
However, the broad featured reveal that the metallic gold
clusters are of nano-size and possibly dispersed well over the
carbon-support. The size of particles were calculated using
the Scherrer equation by considering the full width at half
maximum of the intense (111) reflection, and agree reason-
ably well with the particle size values obtained from TEM
(see Figure 16).
Figures 16 illustrate the TEM bright field images of Au-
NSP and Au/AC samples. It can be seen from these images
that good dispersion of gold nanoparticles with a narrow
particle size distribution is achieved. The average crystallite
size obtained by TEM is in close agreement with the values
calculated from the XRD data (Table 2). The selected area
Figure 13. XP spectrum of Au/CMK-3.
more amount of gold present on the surface of Au/NCCR-56
catalysts than on Au/CMK-3.
3.3. Catalytic Instability of Au/AC
As shown in Table 2, the Au absorption bands of all samples
shifted from 511 to 532 nm suggesting that the monotonic
Chem. Rec. 2018, 18, 1–14
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6
7
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9
0
1
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3
4
5
6
7
8
9
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2
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7
8
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7
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3
4
5
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7
8
9
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1
2
Stability studies: TEM images of Au-NSP before and after
the reaction were shown in Figure 17. It can be seen from this
figure that before the reaction, the gold-sol comprises of
uniform nanoparticles while, after reaction, they get agglom-
erated. Figure 18 shows UV-VIS spectra of Au-NSP recorded
before and after the reaction. It can be seen from this figure
that the SPR band is red-shifted for the used sample, i.e., the
band appear at 557 nm as against 511 nm for the fresh
sample. It is, therefore, clear that the nanoparticles agglom-
erated during the glycerol oxidation reaction in agreement
with TEM images (cf. Figure 17).
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
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3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
Figure 15. XRD patterns of 1 wt% Au/AC catalyst prepared using different
À4
À4
À3
NaAuCl concentration (M): (a) 5310 ; (b) 6310 ; (c) 1310 ; (d) 33
4
À3
À3
10 ; (e) 5310 ; (f) AC.
Figure 17. TEM images of Au-NSP: (a) Before reaction; (b) After reaction.
Inset: particle size distribution.
Figure 18. UV-VIS spectra of Au-NSP: (a) Before; (b) After reaction.
A similar observation can also be noticed for the Activated
carbon-supported samples. For example, the diffraction
pattern of regenerated catalyst, viz., Au/AC (Figure 19b),
shows sharper reflection indicating increased size of the gold
(see also Table 3). This is well supported by TEM micrographs
(Figure 20b), i.e., fresh catalyst shows excellent dispersion
with a narrow particle size distribution while the regenerated
catalyst shows larger sizes due to agglomeration.
À4
Figure 16. TEM image of: (a) Au-NSP, 5310 M NaAuCl4); (b) Au/AC;
c) single Au particle; (d) SAED of Au. Inset: gold particle size distribution.
(
electron diffraction pattern shown in Figure 16d also con-
firmes the highly (single) crystalline nature of the gold with
lattice constant of ~0.4 nm.
Chem. Rec. 2018, 18, 1–14
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T H E C H E M I C A L R E C O R D
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2
3.4. Catalytic Activity
Size-dependent activity: The oxidation of glycerol was carried
out over AC-supported gold nanoparticles with varied sizes.
In this reaction, glyceric acid was obtained as major product
along with by-products such as glycolic acid, tartronic acid
and oxalic acid. The effect of gold nanoparticle size on the
glycerol conversion and selectivity of the glyceric acid product
is illustrated in Figure 21. The impact of the size on the
reactivity can clearly be noticed and that it can also be
observed that upon increasing the size of the gold particle
size, the glycerol conversion monotonically decreases and that
glyceric acid selectivity remain nearly constant. The former
could be attributed to the reduction in the surface active
gold, i.e., with an increase in size, the surface-to-volume ratio
decreases and therefore the lower activity.
Regeneration studies: The catalytic activities of OMC and
AC supported Au catalysts are tested for the glycerol
oxidation and the results are presented in Table 3. During the
reaction along with the glyceric acid which is the desired
product, other oxidation products such as tartronic acid,
glycolic acid and oxalic acid are also formed. The porous
nature of the support also influence the selectivity of glyceric
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
Figure 19. XRD patterns of Au/AC: (a) Fresh; (b) Recycled.
[
22]
acid according to the report of Rodrigues et al. and that
these liquid products accounted for majority of the carbon
balance (93%) for reactions with Au/CMK-3 and Au/
NCCR-56 catalysts. CO2 might be the gaseous product
formed (not identified in the present case) during the reaction
[
23]
[24]
according to the reports of Liu et al. and Zhao et al. The
carbon balance noted in the present work is agreement with
that observed for the oxidation of glycerol using gold
Figure 20. TEM images of Au/AC: (a) Fresh; (b) Recycled. Inset: particle size
distribution.
[
25]
catalyst.
All the mesoporous carbon supported Au catalysts exhibit
an excellent performance under similar reaction conditions
and exhibited higher TOF when compared to that supported
on AC. The regenerated catalysts (second cycle) of OMCs
a
Table 3. Catalytic activity of carbon-supported nano-gold.
b
c
Catalyst
d (nm)
Au
X
Selectivity (mol%)
TOF
(h )
Carbon balance
(mol%)
À1
XRD
TEM
(wt%)
(mol%)
A
B
C
D
E
Au/CMK-3
Fresh
Recycled
Au/NCCR-56
Fresh
4.2
4.8
3.9Æ1.3
4.1Æ1.3
0.52
–
82
84
71
70
8
10
15
14
5
6
1
–
96
–
92.9
92.8
3.2
5.3
3.1Æ0.9
5.1Æ1.8
0.52
–
84
84
70
71
7
6
17
16
4
5
2
2
99
–
93.3
93.2
Recycled
Au/AC
Fresh
Recycled
4.5
23.0
4.1Æ1.1
0.58
–
88
48
72
76
7
3
13
11
7
10
1
–
92
–
93.3
93.0
35 Æ11
a
Reaction conditions: Glycerol=0.3 M; glycerol/Au=500 mol/mol; glycerol/NaOH=4 mol/mol; water=10 mL; T=608C; pO =7 atm;
t=5 h. ICP-OES data. TOF calculated by using TEM results. X=Glycerol conversion; A – Glyceric acid; B – Tartronic acid; C – Glycolic
acid; D – Oxalic acid; E=Others.
2
b
c
Chem. Rec. 2018, 18, 1–14
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P e r s o n a l A c c o u n t
T H E C H E M I C A L R E C O R D
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3
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5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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1
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3
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5
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7
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5
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8
9
0
1
2
uted to the key role of ordered porous structure of carbons in
maintaining the dispersion of nanoparticles by enclosing
them well within the pores. The study further reiterates the
importance of ordered pore structure in the supported
catalysts systems, in particular, for a favorable mass transfer of
reactants and products.
Acknowledgements
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
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3
3
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4
4
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5
5
The authors thank Department of Science and Technology
(DST), New Delhi for funding NCCR, IIT-Madras. We are
also grateful to Professor B. Viswanathan for kind support
and constant encouragement. This work is partially supported
by a grant-in-aid for the scientific research by the Ministry of
New and Renewable Energy (MNRE) under Grant No.
103/140/2008-NT.
Figure 21. Effect of the size of gold nanospheres on the oxidation of glycerol
over Au/AC catalysts. Reaction conditions: Glycerol=0.3 M, glycerol/Au=
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Manuscript received: November 5, 2018
Version of record online: && &&, &&&&
Chem. Rec. 2018, 18, 1–14
© 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Wiley Online Library
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PERSONAL ACCOUNT
High quality ordered mesoporous
carbons such as CMK-3 and NCCR-56
were successfully synthesized and charac-
terized. These materials were used as
supports for gold nano-particles and
confined inside the pores with narrow
size distribution. Their high catalytic
stability on activity has been tested for
the selective (liquid-phase) oxidation of
glycerol.
Dr. P. R. Murthy, Prof. Dr. P. Selvam*
1 – 14
The Enhanced Catalytic Performance
and Stability of Ordered Mesoporous
Carbon Supported Nano-gold with
High Structural Integrity for Glycerol
Oxidation
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