Sustainable
Energy & Fuels
COMMUNICATION
One-pot synthesis of ordered nanoporous
Cite this: Sustainable Energy Fuels,
amorphous H-Zn-aluminosilicate for catalysis of
2018, 2, 1693 bulky molecules†
Received 26th March 2018 Jitendra Diwakar,ab Nagabhatla Viswanadham,
Accepted 5th June 2018
Adarsh Kumarac and Sandeep K. Saxenab
Published on 05 June 2018. Downloaded on 4/26/2019 7:14:44 AM.
DOI: 10.1039/c8se00150b
rsc.li/sustainable-energy
We are reporting a simple one-pot synthesis method of nanoporous
H-zinc-aluminosilicate (HZnAlSi) from a Na-free chemical mixture.
The material exhibits strong acidity required to catalyse bulky
molecular reactions generally restricted in micro-porous zeolites. The
material also exhibits superior catalytic properties giving as high as
99% glycerol conversion in glycerol acetylation, with stability and
reusability.
In the present scenario which calls for cleaner fuel and chem-
icals, the demand for green processes is increasing for indus-
trial applications.1 For catalytic processes, the trend is to switch
over from liquid to solid acid catalysed processes that have the
advantages of ease of catalyst separation, ease of catalyst
handling, being economical and avoiding additional process
steps involved in product separation.2 Aluminosilicates are one
such material that have potential catalytic applications by virtue
of their having valence differences to create the acid sites.
Generally, an aluminosilicate (AlSi) is an inorganic polymer
which consists of aluminium and silicon along with oxygen
atoms. They are found in the earth’s crust in many forms such
as zeolite, kaolinite, clay etc.3 Due to their natural abundance
and stability, aluminosilicates have attracted much attention
for their wide application, especially in the area of catalysis for
decades.4–6 The advantage lies in the exible and tunable cata-
lytic properties that include acidity, surface area, pore size etc.
during pre- as well as post-synthesis processes.7,8 This material
has a further advantage of being suitable for loading a variety of
metal atoms for performing acid, redox and base catalytic
a
Academy of Scientic and Innovative Research (AcSIR) at CSIR-Indian Institute of
Petroleum, Dehradun-248005, Uttarakhand, India
b
Conversions & Catalysis Processes Division, Indian Institute of Petroleum, Council of
Scientic and Industrial Research, Dehradun-248005, India. E-mail: nvish@iip.res.in;
Fax: +91-135-2525702; Tel: +91-135-2525856
c
Biofuel Division, Indian Institute of Petroleum, Council of Scientic and Industrial
Research, Dehradun-248005, India
† Electronic supplementary information (ESI) available: Experimental details,
SEM, EDX, TEM, XRD etc. See DOI: 10.1039/c8se00150b
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*ab Saurabh Kumar,ab
reactions.9,10 Functionalization of AlSi with Zn was observed to
improve the catalytic properties by modifying the acidity and
providing additional dehydrogenation properties.11 Zinc func-
tionalized zeolites such as Zn/ZSM-5 have been successfully
applied for hydrocarbon conversion, but the narrow micropores
limit the bulky catalytic reactions. Hence synthesizing ZnAlSi
with larger pores is an interesting approach. The nanoporous
aluminosilicates are generally synthesized by using bulky
organic templates such as micelles, polymers and macro
molecular adducts. Triethanolamine (TEA),12 polystyrene,13 cit-
ric acid,14 and CTAB alone or in combination with a beta zeolite
precursor15 have been successfully employed to synthesize
nanoporous aluminosilicates. However, these methods involve
the use of costly templates and cumbersome procedures, and
simple and effective methods for the synthesis of nanoporous
aluminosilicates are in demand. Achieving stable zinc alumi-
nosilicates is another challenge as the synthesis of zinc alumi-
nosilicate (ZnAlSi) having all the zinc in its integral framework
is not easy since Zn is too reactive to form zinc oxide (ZnO) on
the surface of AlSi.16,17 In order to have ZnO-free ZnAlSi for
catalytic applications, the focus is on the synthesis of such
materials along with the creation of nanopores to facilitate
bulky molecular reactions such as those with bulky fossil and
bio-derived feedstocks for the production of fuels and ne
chemicals. The main objective of the present study is to achieve
direct synthesis of H–Zn–aluminosilicates possessing nano-
pores from a simple single step method so as to avoid addi-
tional treatments with ammonia followed by calcination that
may cause instability to the Zn in the structure.
Glycerol is one of the low-value bio-derived feeds available
for value addition. Recently biodiesel production and its
demand have increased signicantly, which leads to the
formation of a large number of by-products, especially glycerol,
in the biodiesel industry.18,19 According to the OECD report, the
global production of biodiesel is estimated to reach 42 billion
liters by 2020, from which 10 wt% of glycerol will be formed.20
So glycerol is an easily available low-cost feedstock that can be
used for the synthesis of a variety of value-added chemicals.21
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Glycerol can be converted into acetals, ketals, esters, and
carbonates, which have huge applications as fuel additives,
solvents and many others.22 Acetylation of glycerol using
appropriate acylation agents has gained attention due to the
formation of important chemicals i.e. monoacetin (MA), diac-
etin (DA) and triacetin (TA).23 TA and DA have wide application
in the eld of petrochemicals, and they can be used as bio-
additives for gasoline and biodiesel, which improves properties
such as cetane number, anti-knocking, anti-freezing and
viscosity and also lowers the NO emission, whereas MA and DA
are used as raw materials for biodegradable polyester formation
and all acetylation products also have wide application in the
food, cosmetic, and pharmaceutical industries.24,25
The aim of the present study is to develop a promising
catalyst that can effectively convert glycerol into industrially
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important products. The acetalization products of glycerol,
called acetals, require acidity and space availability in the
micro-environment of the catalyst for reaction. Zeolites, a class
of crystalline aluminosilicates, have been proven as well known
industrial catalysts, but the narrow micropores limit their
applications to the present reaction. Hence we aimed our study
at amorphous aluminosilicates and Zn-aluminosilicates pos-
sessing larger nanopores in the present work. Here we synthe-
sized nanoporous HAlSi and HZnAlSi by a simple one-step
method (1.1 Catalyst preparation, ESI†) to obtain an acidic,
framework-interacting Zn containing nanoporous catalyst suit-
able for the processing of bio-originated bulky molecule glyc-
erol. The direct Na-free synthesis of the material provides
a greener way of catalyst preparation by having an advantage of
obtaining the proton form of the catalyst that does not require
any additional NH4-exchange and decomposition treatments to
evolve ammonia gas. Green aspects are also involved in the
process selection where the acetylation of glycerol has been
chosen to produce industrially important and bio-degradable
di- and tri-acetin molecules whose formation is expected to
increase in the larger nanopores of the present catalyst system.26
The presence of Zn is anticipated to alter the acidity and
porosity properties of the catalyst.
The composition of the synthesized samples was analysed by
SEM EDX (Fig. S1, ESI†) and ICP-MS (Table S2 ESI†). The results
conrmed the presence of Al and Si in HAlSi and Al, Si and Zn in
the HZnAlSi catalyst samples respectively. Further, the HZnAlSi
sample was analysed by XPS (Fig. S2 ESI†) and UV spectroscopy.
In XPS the appearance of two peaks at 1024 eV and 1048 eV
conrmed the +2 oxidation state of zinc in the sample
Fig. 1 (A) XPS binding energy of Zn 2p and (B) the UV spectra of
materials.
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(Fig. 1A),27 whereas in the UV spectra HZnAlSi did not show the
adsorption band at 360 nm related to ZnO revealing the absence
of the oxide form of Zn in the sample (Fig. 1B).16,17 Here the UV
adsorption patterns were observed to be similar for both HAlSi
and HZnAlSi samples. This gives indirect evidence to believe
that all the Zn present in HZnAlSi chemically interacted with Al
and Si and did not exist as ZnO. The presence of zinc metal in
the chemical interaction with Si and Al was further conrmed
by EDS mapping (Fig. S3 ESI†). This aspect is further conrmed
by HRTEM.
The structural elucidation of the materials was conducted by
FTIR and Raman spectroscopy methods (Fig. S5 ESI†). The FTIR
spectra of both the samples (Fig. 2A) show a broad band
centered around 3400 cm 1 representing the O–H stretch-
ing.28,29 The band at 850 cm 1 is due to –Si–OH bending, while
that of 1050 cm 1 is related to the Si–O–Al stretching vibration.
A low-intensity band at around 1650 cm 1 related to the
hydration of the samples is also observed in both the spectra.
Overall, the FTIR spectra of the samples indicate the formation
of the alumina-silicate material.
In wide angle XRD the materials show no denite crystalline
nature: while HZnAlSi shows an amorphous nature, HAlSi
shows some bands at about 15–25 2q, indicating its semi-crys-
talline nature. The difference in the wide angle patterns of the
two materials may be due to the presence of Zn and its partic-
ipation in the chemical structure in HZnAlSi during the
hydrothermal synthesis (Fig. 2B).
The morphology and internal structure of the material was
analysed using SEM, TEM and HRTEM images. SEM analysis of
both materials showed a well dened morphology (Fig. S6 ESI†),
and TEM images showed that HZnAlSi has a well dened
uniform particle nature, while the corresponding HAlSi showed
a layer type morphology (Fig. 3A and 4B). In the HRTEM of
HZnAlSi the presence of 50 nm size particles with a spherical
morphology can be clearly seen (Fig. 3C). The HRTEM also
conrms the presence of lattice springs related to zinc metal
which is also support the presence of zinc metal in the chemical
interaction with Si and Al (Fig. 4).
The material also exhibited a porous morphology in HRTEM,
whereas in HAlSi, the pores were not visible even at such a high
resolution, perhaps due to the formation of the multilayered
structure that suppresses the visibility of such pores (Fig. 3D).
However, the nanoporous nature of both the samples was re-
ected in the low angle XRD patterns of the samples, where
both HAlSi and HZnAlSi materials showed a sharp single
Fig. 2 (A) FTIR spectra and (B) wide-angle XRD of the materials.
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Fig. 3 (A & B) TEM, (C & D) HRTEM images of materials.
Fig. 4 HRTEM of HZnAlSi showing lattice springs.
diffraction band at 0.5 2q, representing the nanoporous nature
of these materials (Fig. S7 ESI†).
Detailed studies on the porous nature of these materials
were conducted using N2 adsorption–desorption isotherms
(Fig. 5). The type IV isotherm exhibited by both samples clearly
indicates the presence of nanosized pores in the materials. For
HAlSi, the adsorption of pores started at P/P0 of 0.5 with
a distinct loop formation that shows the lling of pores up to
the P/P0 of 1, representing the distribution of pores with a range
of pore sizes. Unlike this, the HZnAlSi showed a very sharp
adsorption loop between 0.8 and 1.0P/P0, representing the
presence of almost uniformly sized nanopores (Fig. 5A). The
isotherm also gives an indication that the chemical structure of
HZnAlSi is more ordered and organized to create uniform pores.
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Fig. 5 (A) N2 adsorption isotherm and (B) BJH pore size distribution.
This again supports the participation of Zn in the chemical
structure of HZnAlSi through chemical bonding.
This aspect is further analysed using BJH pore size distri-
bution patterns. As shown in Fig. 5B, the pores are distributed
from 5 nm to 40 nm sizes in HAlSi with two distinct populations
at 5 nm and 30 nm. For the corresponding HZnAlSi an
increased nanopore volume with a huge peak at 40 nm was
observed. This observation suggests that not only are the pores
uniformly sized but also the increased pore volume is created in
the material by the presence of Zn. Accordingly, the total pore
volume of HZnAlSi is observed to be 0.70 cm3 g 1, which is
almost double that of HAlSi (0.37 cm3 g 1) (Table S3 ESI†). The
pore volume distribution data in the table also indicate that the
micropore volumes of both the samples are comparable and the
signicant increase in pore volume observed in HZnAlSi is
completely due to the nanopores. Overall the TEM and N2-
sorption analysis revealed that both the materials have a porous
structure but HZnAlSi has a morphology and porosity different
from HAlSi, which can be ascribed to the molecular level
interaction of Zn with Si and Al in the initial synthesis gel used
during the hydrothermal treatment.
The acidity of the materials was determined by temperature
programmed desorption (TPD) of ammonia (Fig. 6). HAlSi
exhibited two distinct desorption peaks at 150  C and 550  C
related to weak and strong acidity, respectively. In the case of
HZnAlSi, the strong acidity peak was not distinct but displayed
a continuous desorption from 300  C to 550  C related to
medium to strong acidity. Since both HZnAlSi and HAlSi have
comparable amounts of Si and Al, the difference in acidity,
especially the acid sites of medium strength created in HZnAlSi,
can be ascribed to the presence of chemically interacting Zn in
this sample. Overall, both the materials exhibited comparable
Fig. 6 Ammonia-TPD of the materials.
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total acidity values, but there are more strong acid sites in the
HAlSi sample (Table S2 ESI†).
The synthesized HAlSi and HZnAlSi materials also show
good thermal stability, as conrmed by TG/DTA analysis (Fig. S8
ESI†). In TGA the weight loss of around 4 wt% that occurred
below 200  C with the corresponding endothermic peak in DTA
reveals the removal of moisture from the materials. Above this
temperature, no considerable weight loss or exothermic peak
was observed up to the studied temperature of 600  C, which
conrms the suitability of the synthesized materials for high
temperature catalytic applications. It is interesting to see that
zinc incorporation does not affect the thermal stability of the
material as HZnAlSi exhibited similar DT/TGA patterns to those
of HAlSi.
Glycerol acetalization is an esterication reaction where the
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three hydroxyl groups in the glycerol act as three alcohol
moieties to individually react with three acetic acid molecules to
form a tri-ester of glycerol. As shown in Scheme S1 (ESI†), the
acid sites on the catalyst can facilitate the reaction between the
–OH group of glycerol and acetic acid to undergo dehydration to
form an ester group.30 Unlike a simple alcohol, the tri-hydroxy
molecule glycerol makes the reaction molecularly bulky, which
requires a larger free-space environment around the active sites,
i.e. acid sites. The acetylation reaction is an acid catalysed
reaction but the acidity should be optimum so as to control the
undesired de-acetylation reactions that lower the selectivity to
bulky products such as di- and tri-acetin.31 Finally, the bulky
molecular acetylation reactions are thermodynamically fav-
oured at lower temperatures and thus the catalyst materials
should possess low-temperature activity to produce the desired
product. Overall, the reaction requires moderate acidity and
reaction space on the catalyst to favour bulky acetal products.
The synthesized materials of the present study exhibiting larger
nanopores and higher acidity have been applied for the glycerol
acetylation reaction that is carried out in a liquid phase batch
reactor, where the reaction temperatures are chosen between
100 and 150  C.32
The studies indeed indicated the promising catalytic func-
tionality of the synthesized materials. Data given in Table 1
indicate that both HAlSi and HZnAlSi are suitable for the effective
production of acetins from glycerol. At the studied reaction
temperatures of >100  C, the catalysts exhibited more than 95%
conversion. At lower reaction temperatures the glycerol conver-
sion is low. On the other hand, higher reaction temperatures
(>120  C) also caused a decrease in the selectivity towards bulky
products DA and TA. A common phenomenon observed is that
a low temperature favoured the formation of bulky products i.e.
DA and TA on both the catalysts. This may be due to the ther-
modynamically favourable branch formation at lower tempera-
tures. At higher temperatures, one of the reactants, acetic acid,
exists in the vapour phase while the other reactant glycerol is in
the liquid phase that may limit the reactivity towards acetin
formation. Another important factor is the equilibrium shi from
the acetylation to de-acetylation reactions favoured at higher
temperatures. The optimum reaction temperature observed for
the catalyst of the present study seems to be 110  C to produce the
desired bulky acetylated products.
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Between HAlSi and HZnAlSi, the later one exhibited signi-
cant TA formation (as high as 83 wt%, entry 12), while the yield
of this particular product is minimal for HAlSi under similar
reaction conditions (12 wt%, entry 3). Upon increasing the
temperature to 120  C, the TA yield decreased along with the
simultaneous formation of DA on the HZnAlSi catalyst (entry
13). This particular feature of HZnAlSi can be ascribed to the
highly porous nature of the HZnAlSi when compared to the
corresponding HAlSi. Since the strong acid sites possessing
a higher heat of adsorption are expected to enhance the de-
acetylation reactions (cracking at the alkyl branch), a medium
strength of acidity seems to be useful for improving the bulky
DA and TA product selectivity. HZnAlSi possessing a higher
number of medium strength acid sites may be responsible for
the formation of higher multiple-branched products in the
present study. HAlSi also exhibited reasonably high conversions
of glycerol but the main product obtained here is less bulky MA.
The difference in the product selectivity of the two catalysts can
be ascribed to the difference in their acid strength. As can be
seen from the TPD patterns, HAlSi exhibits stronger acidity
when compared to HZnAlSi. In other words, strong acid sites in
HAlSi seem to catalyse the reversible de-acetylation of DA and
TA to produce more MA.
Reaction parameters related to the amount of catalyst and
the feed ratio (glycerol : AcOH) were also studied. The stoi-
chiometric equation of glycerol acetalization demands a 1 : 3
mole ratio of glycerol to acetic acid to produce triacetin (TA).
Excess acetic acid ratios are also studied in the present work.
The conversion and product selectivity patterns obtained at
various catalyst amounts and feed ratios indicate the 1 : 6 feed
ratio as the optimum with a catalyst amount of 0.6 g in the
present study.33
Stability of the active sites against leaching was also studied.
For this, the spent catalyst was removed from the reaction
mixture, washed with ethanol, dried and reused for the fresh
run. Data given in entries 8, 9 and 17, 18 clearly indicate the
comparable performance of the catalysts and their stable
performance in reusability studies. This stability aspect of the
catalysts was also checked by the characterization of the spent
catalysts. As shown Fig. S9 and S10 ESI† the spent catalyst
exhibited a comparable morphology in SEM and TEM. The FTIR
spectra indicated the structural stability while the stability of
acid sites was conrmed from ammonia TPD experiments. As
shown in Fig. S11 and S12 ESI,† the spent catalysts exhibited
structure and acidity properties comparable with those of the
corresponding fresh ones, conrming the catalyst stability
against leaching. The SEM-EDX analysis of the spent catalyst
also shows a comparable elemental composition of HZnAlSi
(Fig. S13 ESI†).
A comparison of the performance of the present catalysts
with those of reported is given in Table S1 (ESI†). The glycerol
conversions are almost more than 90% for all the catalysts but
the selectivity towards mono-, di- and tri-acetin are different for
these catalysts. The selectivity towards bulky tri-acetin is limited
for most of the catalysts reported except for A15 (entry 9 in Table
S1 ESI†). This may be either due to the space constraints around
the active sites or due to the occurrence of reversible de-
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Table 1 Performance of the catalyst systems towards glycerol acetylation

Product yield (wt%)

Conversion of
S. no. Catalyst Temp ( C) Ratios (glycerol : AcOH) Ratios (feed : catalyst) glycerol (%) Monoacetin Diacetin Triacetin

1 HAlSi 110 1:3 13.3 85.3 73.4 11.9 —

2 " 100 1:6 22.16 27.3 23.4 3.9 —
3 " 110 " " 96.4 76.4 7.9 12.0
4 " 120 " " 99.9 59.9 40.0 —
5 " 150 " " 99.9 99.1 0.9 —
6 " 110 1:6 44.33 99.9 78.0 21.9 —
7a " 110 " " 98.4 72.8 25.6 —
8b " 110 1:6 22.16 99.9 76.2 23.7 —
9c " 110 " " 99.8 65.9 33.9 —
10 HZnAlSi 110 1:3 13.3 91.2 67.8 6.4 17.0
11 " 100 1:6 22.16 38.2 28.6 9.6 —
12 " 110 " " 99.9 16.5 — 83.4
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13 " 120 " " 99.8 5.8 76.2 17.8

14 " 150 " " 85.3 79.4 5.9 —
15 " 110 1:6 44.33 99.9 82.7 17.2 —
16a " 110 " " 99.9 84.3 15.6 —
17b " 110 1:6 22.16 99.9 58.3 — 41.6
18c " 110 " " 99.9 55.7 — 44.2
a
Performance of the catalyst aer three hours of reaction time. b Regenerated catalyst performance. c Aer ve reaction cycles.

acetylation reactions. HAlSi of the present study also exhibited
an inferior selectivity to the formation of tri-acetin. On the other
hand, signicant formation of tri-acetin was observed on the
corresponding HZnAlSi catalyst of the present study. Since the
difference in properties of the two catalysts is mainly in terms of
porosity and strong acidity, these factors seem to be responsible
for the difference in product selectivity. Acid sites are active
sites for both acetylation and deacetylation reactions and hence
the presence of moderate acidity may be suitable for favouring
the formation of the acetylation product by minimizing the
reversible reaction. Between the two catalysts studied in the
present work, HZnAlSi possessing more porosity and moderate
acidity could produce more bulky acetylation (tri-acetin) prod-
ucts. It is interesting to see that the cumulative yield of DA and
TA turned out to be as high as 94 wt% on the HZnAlSi catalyst,
which is useful for industrial applications.
Overall, the studies indicated that the formation of TA and
DA is favoured by nanoporous HZnAlSi possessing moderate
acidity at low reaction temperatures by virtue of favoured reac-
tion equilibrium towards acetylation reaction to produce
industrially important (bio-degradable fuel additive) bulky tri-
acetin for green applications.26
Conclusions
In summary, a single-step method was successfully developed
for the synthesis of nanoporous HAlSi and HZnAlSi materials
from a Na-free gel mixture. The new concept of avoiding the use
of NaOH to directly obtain the H-form HZnAlSi has been real-
ized to reduce the additional steps and time involved in the
traditional synthesis methods i.e. ion exchange of the Na-form
to obtain the NH4-form of the material and its calcination to
produce the H-form in the nal step. The alkalinity required for
establishing the chemical interaction between Si and Al has
been achieved by the presence of TMAOH and TPAOH structure-
directing agents. The present method is simple and reproduc-
ible for the production of thermally stable materials suitable for
catalytic applications involving organic transformations. The
HZnAlSi synthesized by a simple one-pot Na-free synthesis
exhibited excellent textural properties such as large surface
area, high pore volume, nanoporosity, moderate acidity, high
temperature thermal stability and reusability. Since glycerol is
a by-product obtained from bio-fuel production, present cata-
lyst systems have potential application for the value addition of
glycerol through the production of important oxygenated
compounds acetins. Though there are several glycerol conver-
sion reactions, value addition through acetin production is
important as there is no oxygen removal involved in the process.
Further, bulky di- and tri-acetin formation facilitated by nano-
porous HZnAlSi of the present study is useful for wide industrial
application.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
The authors are thankful to the director, IIP, for his encour-
agement. JD is thankful to CSIR-New Delhi for awarding a junior
research fellowship. We are thankful to XRD, IR, and SEM
analysis groups at IIP for analysis.

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Notes and references
1 C. J. Clarke, W. Tu, O. Levers, A. Bro and J. P. Hallett, Chem.
Rev., 2018, 118, 747.
2 F. Su and Y. Guo, Green Chem., 2014, 16, 2934.
3 C. Ning, M. Xu, D. C. W. Hui, C. S. K. Lin and G. McKay,
Chem. Eng. J., 2017, 311, 37.
4 P. Djinović, T. Tomše, J. Grdadolnik, Š. Božič, B. Erjavec,
M. Zabilskiy and A. Pintar, Catal. Today, 2015, 258, 648.
5 M. Zendehdel, M. Ali, H. Behyar and Z. Mortezaei,
Microporous Mesoporous Mater., 2018, 266, 83.
6 M. Peng, D. Chen, J. Qiu, X. Jiang and C. Zhu, Opt. Mater.,
2007, 29, 556.
7 E. R. Cooper, C. D. Andrews, P. S. Wheatley, P. B. Webb,
P. Wormald and R. E. Morris, Nature, 2004, 430, 1012.
Published on 05 June 2018. Downloaded on 4/26/2019 7:14:44 AM.
8 D. López, L. J. Giraldo, J. P. Salazar, D. M. Zapata,
D. C. Ortega, C. A. Franco and F. B. Cortés, Catalysts, 2017,
7, 319.
9 P. Gao, S. Li, X. Bu, S. Dang, Z. Liu, H. Wang, L. Zhong,
M. Qiu, C. Yang, J. Cai, W. Wei and Y. Sun, Nat. Chem.,
2017, 9, 1019.
10 J. E. Samad, J. Blanchard, C. Sayag, C. Louis and
J. R. Regalbuto, J. Catal., 2016, 342, 213.
11 N. Musselwhite, K. Na, K. Sabyrov, S. Alayoglu and
G. A. Somorjai, J. Am. Chem. Soc., 2015, 137, 10231.
12 J. Zhou, Z. Hua, J. Zhao, Z. Gao, S. Zeng and J. Shi, J. Mater.
Chem., 2010, 20, 6764.
13 G. Zhu, S. Qiu, O. Terasaki and Y. Wei, J. Am. Chem. Soc.,
2001, 123, 7723.
14 L. Xu, S. Wu, J. Guan, Y. Ma, K. Song, H. Xu, C. Xu, Z. Wang
and Q. Kan, Catal. Commun., 2008, 9, 1970.
15 Y. Li, J. Shi, Z. Hua, H. Chen, M. Ruan and D. Yan, Nano Lett.,
2003, 3, 609.
16 S. Sogukkanli, K. Iyoki, S. P. Elangovan, K. Itabashi,
N. Koike, M. Takano, Y. Kubota and T. Okubo, Microporous
Mesoporous Mater., 2017, 257, 272.
1698 | Sustainable Energy Fuels, 2018, 2, 1693–1698
View Article Online
Communication
17 N. Koike, W. Chaikittisilp, K. Iyoki, Y. Yanaba, T. Yoshikawa,
S. P. Elangovan, K. Itabashi and T. Okubo, Dalton Trans.,
2017, 46, 10837.
18 N. Bordoloi, R. Narzari, R. S. Chutia, T. Bhaskar and
R. Kataki, Bioresour. Technol., 2015, 178, 83.
19 C. H. Lam, A. J. Bloomeld and P. T. Anastas, Green Chem.,
2017, 19, 1958.
20 P. U. Okoye, A. Z. Abdullah and B. H. Hameed, Fuel, 2017,
209, 538.
21 A. Shaei, H. Rastegari, H. S. Ghaziaskar and M. Yalpani,
Biofuel Res. J., 2017, 13, 565.
22 N. J. Venkatesha, Y. S. Bhat and B. S. Jai Prakash, RSC Adv.,
2016, 6, 45819.
23 B. O. Dalla Costa, H. P. Decolatti, M. S. Legnoverde and
C. A. Querini, Catal. Today, 2017, 289, 222.
24 A. Behr, J. Eilting, K. Irawadi, J. Leschinski and F. Lindner,
Green Chem., 2008, 10, 13.
25 Y. Sun, J. Hu, S. An, Q. Zhang, Y. Guo, D. Song and Q. Shang,
Fuel, 2017, 207, 136.
26 X. Liu, H. Ma, Y. Wu, C. Wang, M. Yang and U. Welz-
biermann, Green Chem., 2011, 13, 697–701.
27 S. S. Mali, H. Kim, W. Y. Jang, H. S. Park, P. S. Patil and
C. K. Hong, ACS Sustainable Chem. Eng., 2013, 1, 1207.
28 A. Coloma, F. J. Rodrı́guez, J. E. Bruna, A. Guarda and
M. J. Galotto, J. Chil. Chem. Soc., 2014, 59, 2409.
29 M. Bartoszek, R. Eckelt, C. Jäger, H. Kosslick, A. Pawlik and
A. Schulz, J. Mater. Sci., 2009, 44, 6629.
30 A. Pankajakshan, S. M. Pudi and P. Biswas, Int. J. Chem.
Kinet., 2017, 50, 98–111.
31 L. Zhou, E. Al-zaini and A. A. Adesina, Fuel, 2013, 103, 617–
625.
32 M. S. Khayoon, S. Triwahyono, B. H. Hameed and A. A. Jalil,
Chem. Eng. J., 2014, 243, 473–484.
33 M. Balaraju, P. Nikhitha, K. Jagadeeswaraiah, K. Srilatha,
P. S. S. Prasad and N. Lingaiah, Fuel Process. Technol.,
2010, 91, 249–253.
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