Received: 7 April 2021 Revised: 25 June 2021 Accepted: 29 June 2021

DOI: 10.1002/cjce.24284

ARTICLE

Catalytic transesterification of glycerol with dimethyl

carbonate to glycerol carbonate with Co3O4 nanoparticle
incorporated MCM-41 derived from rice husk

Shivali Arora1 | Vijayalakshmi Gosu1 | Verraboina Subbaramaiah1 |

Tian C. Zhang2

1
Department of Chemical Engineering,
Malaviya National Institute of Technology
Abstract
Jaipur, Jaipur, India A rice husk-derived MCM-41 catalyst has been synthesized, and active metal
2
Department of Civil & Environmental Co3O4 nanoparticles were incorporated. The synthesized MCM-41 derived
Engineering, University of Nebraska-
from rice husk exhibited highly ordered p6mm hexagonal symmetry. The cata-
Lincoln, Omaha, Nebraska, USA
lytic activity of the prepared catalyst was investigated for glycerol carbonate
Correspondence (GLc) synthesis through transesterification of glycerol (GLy) with dimethyl
Vijayalakshmi Gosu and Verraboina
Subbaramaiah, Department of Chemical
carbonate (DMC). Experimentally, it was found that 5 wt.% cobalt incorpo-
Engineering, Malaviya National Institute rated MCM-41 activated at 400
C showed a higher yield of GLc, 60.2%, due to
of Technology Jaipur, 302017, India. its optimum basicity. Approximately, 98.7 ± 1.2% GLy conversion and 94.1
Email: vlakshmi.chem@mnit.ac.in and
vsr.chem@mnit.ac.in ± 0.7% GLc yield was achieved with the batch reactor at adjusted conditions: a
molar ratio of DMC-to-glycerol = 3, catalyst dosage = 6 wt.% (based on glyc-
Funding information
erol mass), reaction temperature = 90
C, and reaction time = 2 h. The trans-
Ministry of Education; Science and
Engineering Research Board, Grant/ esterification reaction kinetics were also studied using the ODE 15s tool in
Award Numbers: ECR/2015/000085, MATLAB. The catalyst’s activation energy was calculated as 58.2 ± 2.4 kJ/mol.
Dated 20.08.2016
KEYWORDS
glycerol carbonate, MCM-41, nanoparticles, rice husk, transesterification

1 | INTRODUCTION
Recently, renewable fuels have received significant atten-
tion to meet the present demand. Among the various
renewable fuels, biodiesel is a potential alternative
source. However, every 100 kg biodiesel production gen-
erates nearly 10 kg of glycerol (GLy) as a by-product.
Effective utilization of this by-product GLy could
enhance the sustainability of the biodiesel industry.
Besides, an abundant quantity of GLy may hamper mar-
ket prices that have dropped drastically since 2006.[1]
Numerous ventures have been explored for the valori-
zation of GLy into several value-added chemicals, such
as, glycidol, glycerol carbonate (GLc), propanediol, and
polyamides. Among them, GLc has received significant
attention due to its high boiling point, low toxicity, and
biodegradability. It can be used as a novel solvent, surfac-
tant, electrolyte in a lithium-ion battery, and monomer
for polymers. Many researchers have paid attention to
GLc synthesis. The exploration of state-of-the-art technol-
ogy is an important challenge for the industrial-scale syn-
thesis of GLc. Up to now, several methods have been
adopted in the literature to make GLc using GLy as
feedstock with various reactants: (i) CO2, (ii) urea,
(iii) CO, (iv) phosgene, and (v) ethylene or dimethyl
carbonate (DMC).[2] However, the lowest conversion of
GLy was obtained with CO2, since the reaction is ther-
modynamically limited. In the case of urea, ammonia
formed as a by-product, which needs to be removed
under vacuum.

Can J Chem Eng. 2021;1–16. wileyonlinelibrary.com/journal/cjce © 2021 Canadian Society for Chemical Engineering. 1
2 ARORA ET AL.
In contrast, CO and phosgene as reactant are toxic.
Among various synthesizing routes, the trans-
esterification of GLy with DMC is an environmentally
benign and industrially feasible route to produce GLc.[3]
However, without the aid of any suitable catalyst, GLy
and DMC are immiscible, forming a biphasic mixture
with a negligible conversion of GLy.[4]
The transesterification reaction needs a basic site cat-
alyst to accelerate the rate of reaction.[5] Homogeneous
basic catalysts such as NaOH, KOH, K2CO3, and MgO
have been used; such catalysts have provided excellent
results in GLc yield.[6] However, the separation and
regeneration of catalyst from the product mixture were
poor. In this view, several methods were adopted for het-
erogenizing homogeneous catalysts to overcome the
problems mentioned above. A heterogeneous catalyst can
be easily separated from the product mixture, reused,
and barely corrodes the reactor. Researchers have utilized
various catalysts, such as Ca/La,[7] Mg/Al/Zr,[8] Li/ZnO,[9]
and Mg/Ce[10] as basic heterogeneous catalysts for tailoring
the transesterification reaction. However, these catalysts
have certain limitations. For instance, Li/ZnO exhibits poor
reusability due to active species leaching during the reac-
tion. Similarly, hydrotalcite requires a long reaction time
and a high DMC-to-GLy molar ratio to achieve a high
conversion of GLy.[11] In sequence, these catalysts possess
low surface area due to the non-utilization of the highly
porous catalyst support. Thus, an environmentally benign,
reusable, inexpensive, and non-toxic solid-base catalyst
needs to be explored for the synthesis of GLc.
Mesoporous catalysts incorporated with active metal
oxide species have fascinated researchers due to their
excellent catalytic activity, high surface area, and easy to
tailor pore length and pore diameter to enhance the reac-
tion. Among the various mesoporous support materials,
mesoporous silica has received rapid attention in mate-
rial science and catalysis due to its uniform channels,
high surface area, adjustable pore sizes, and high thermal
stability.[6] MCM-41 is a mesoporous silica material with
a two-dimensional hexagonal array of mesopores and a
large pore size. MCM-41 can be synthesized using various
silica sources, including aerosol, n-alkyl amines, n-
alkoxysilanes, TEOS, and water glass. However, purely
siliceous MCM-41 has relatively low catalytic activity due
to the chemically inert silicate framework; besides, these
silica precursors are expensive and may eventually
increase the process cost.[12]
Some researchers have attempted a more economical
approach using various waste resources: coal fly ash, rice
husk, kaolin, red mud, and so on to make catalysts.[2,5,6]
Utilization of waste resources is a highly motivated
recycling technique which reduces waste management
costs.[13] Approximately 120 MTPA of rice paddy are
produced, especially in India, of which around 24 MTPA
of rice husk are produced by the rice milling industry.[14]
During rice husk combustion, approximately 14–25 wt.%
of ash is generated, which contains silica as high as 90%
to 97% and has been confirmed to be ideal silica due to
its significant portion of silica oxide. [15,16] Several other
agricultural sources or biomasses such as rice straw,
sugarcane bagasse, bamboo culm, bamboo leaf, corn-
cob, and banana leaf were also employed as silica
sources.[17]
Nanoparticles of metal and metal oxides have been an
indispensable area of research for the last few decades
owing to their high-performance catalytic activity and
good interaction with support material. Among various
metal oxides, Co3O4 nanoparticles were found to be a
promising catalyst due to their small Co-O bond
energy.[18] In several instances, unsupported metal oxide
nanoparticles are not stable because of the high surface-
area-to-volume ratio. Generally, nano-metal oxides are
supported onto porous materials to inhibit the agglomer-
ation and to enhance the recovery. The catalytic perfor-
mance of support material enhances upon introduction
of oxides of nanoparticles through synergistic effects or
metal-support interactions. Hence, in the present study,
Co3O4 nanoparticles are introduced upon stable support
material, such as MCM-41.
In this study, rice husk was used as a silica precursor
for the synthesis of mesoporous catalysts (MCM-41). The
basic sites of the catalyst were boosted by varying active
metal loading and calcination temperature. Batch experi-
ments were conducted to maximize yield and conversion
by adjusting influencing conditions. The stability of the
prepared catalyst was investigated through a reusability
study. The reaction’s apparent activation energy was cal-
culated with the reaction’s kinetic data using the ODE
15s tool in MATLAB.
2 | MATERIALS AND METHODS
2.1 | Materials
Rice husk was obtained from a rice mill in Agra, India. Cobalt
nitrate hexahydrate (Co[NO3]2.6H2O) was acquired from
CDH Fine Chemicals, New Delhi, India. Tetraethyl amine
(TEA) was purchased from Avra Chemicals, Hyderabad,
India. Cetyltrimethylammonium bromide (CTAB), nitric acid,
phenolphthalein, 2, 4-nitroaniline, sodium hydroxide pellets,
and bromothymol blue were procured from Fisher Scientific,
India. Methanol was supplied by Qualichem Fine Chemicals,
Mumbai, India. Ethanol was bought from Merck, India.
Glycerol, dimethyl carbonate, and acetic acid were obtained
from Loba Chemie, Mumbai, India.
ARORA ET AL.
2.2 | Preparation of catalyst
In this study, the catalyst was prepared by adopting a
two-step process: (i) synthesis of catalyst support material
followed by (ii) impregnation of Co3O4 nanoparticles on
the synthesized support material. Initially, the catalyst
support material, MCM-41, was prepared using rice husk
as a silica source.[6,19] Rice husk was cleaned with water,
dried, and acid-treated with 1 mol/L nitric acid to remove
adhered dust and other impurities. The acid-treated
material was placed in a furnace at 700
C to obtain silica
fuse. Then, 10 g of white silica fuse was dissolved in
500 ml of sodium hydroxide solution (1 mol/L) for 18 h
to acquire a sodium silicate solution. Then, 9.8 g of sur-
factant (CTAB) was dissolved in 50ml of distilled water,
and 400 ml of sodium silicate was added dropwise into
it. Under continuous stirring, the pH of the solution was
adjusted to 11 using 1 mol/L acetic acid and was con-
stantly stirred for 6 h. The obtained solution was trans-
ferred into a polypropylene bottle and placed into a hot
air oven at 100
C for 72 h. The formed precipitate (gel)
was filtered and washed with ethanol (99%); the washed
gel was dried in an oven at 100
C for 24 h. The dried
white powder was kept in a furnace at 550
C to remove
the surfactant material (CTAB). The calcined product
was designated as MCM-41.
In the second step, cobalt nanoparticles were pre-
pared using a surfactant method.[20] The synthesized
nanoparticles were then introduced on MCM-41. In a
typical procedure, cobalt nitrate hexahydrate was mixed
with CTAB in a molar ratio of 5, followed by heating at
75
C for 0.5 h. Thereafter, triethylamine (TEA) was used
as a reducing agent with a molar ratio of 0.5 (Co:TEA) by
dropwise addition with continuous stirring. During the
acquisition of TEA, dark brown particles appeared due to
the formation of cobalt nanoparticles. Then, the prepared
MCM-41 was added into the dark brown solution and
aged for 10 h under total reflux condition. The resultant
solution was centrifuged and filtered with a Whatman fil-
ter paper. Finally, the filtrate was washed with ethanol,
dried in an oven at 100
C, and then placed in a muffle
furnace for calcination at 450
C for 2 h. Different samples
of catalysts were prepared and titled as Co/MCM-41 (x%, T),
where x% and T refers to the weight percentage of cobalt
loading and calcination temperature of the prepared catalyst
in
C, respectively.
2.3 | Catalyst characterization
The stability of the bare and cobalt-loaded MCM-41 cata-
lyst was analyzed on a PerkinElmer STA-6000
3
(Massachusetts, USA) under nitrogen atmosphere with a
heating rate of 20
C/min from room temperature
(25
C) to 900
C. X-ray data of the bare MCM-41 and
cobalt species-loaded MCM-41 was attained on PAN-
alytical X’Pert Pro equipment. To obtain the X-ray
diffraction (XRD) pattern, the equipment was oper-
ated at 40 kV, 40 mA, where Cu Kα was used as the
target source between the range of 2θ = 10–90
. In
the same way, the small-angle powder scattering was
measured over the 2θ region of 2–10
. The average
crystal size of a particle was calculated using the
Scherrer equation:
0:9 λ
τ¼ ð1Þ
βcosθ
where τ is the average crystallite size (nm), λ is the X-ray
wavelength at 1.54 nm, β is the full width at half-
maximum (FWHM), and θ is Bragg’s angle.[20]
A PerkinElmer Fourier transform spectrophotom-
eter was used to record the Fourier transform infrared
(FTIR) spectrum of prepared samples in the region of
4000–400 cm 1 . Before analysis, a translucent circu-
lar pellet of catalyst and KBr was prepared and ana-
lyzed. The textural properties of the catalyst were
studied on a Quantachrome NovaWin (Version 11.05,
USA). The impurities of the catalyst were degassed at
350
C for 4 h before analysis. The surface area of the
catalyst support and cobalt-loaded support material
was calculated using the BET method, whereas the
pore volume and diameter were calculated using the
BJH method. The morphology of the catalyst was stud-
ied through an FEI Nova NanoSEM 450. Energy-
dispersive X-ray spectroscopy (EDX) was done to
determine the dispersion of active metal on the sup-
port material. The basic strength of the prepared cata-
lyst was calculated by adopting the Hammett
indicator method with phenolphthalein (H_ = 9.3),
2,4-dinitroaniline (H_ = 15), and bromothymol blue
(H_ = 7.8) as indicators. The method adopted for the
quantification of basic sites was as described by Arora
et al.[21] Firstly, the catalyst was added to a solution
containing methanol and indicator and left for 2 h. If
colour change was observed, the catalyst was consid-
ered as stronger than the indicator; otherwise, it was
weaker than the indicator. To quantify the number of
basic sites, the solution was titrated with benzoic acid.
The samples’ internal morphology was studied on a
Tecnai G2 20 S-Twin (FEI, Netherlands) apparatus.
The X-ray photoelectron spectroscopy (XPS) spectra
were recorded on a Scienta Omicron spectrometer
using Al Kα source.
4 ARORA ET AL.

2.4 | Transesterification reaction of GLy GLc moles produced, GLc selectivity, time, and GLy
with dimethyl carbonate molecular mass, respectively.

The procedure adopted for the transesterification of GLy

to GLc was similar to that described by Arora et al.[21] 3 | RESULTS A ND DISCUSSION
Typically, required amount of GLy and DMC was
charged in round-bottom flask and heated until the 3.1 | Catalyst characterization
desired temperature was attained. The required catalyst
was added into the reaction mixture and the reaction was Figure 1A shows the wide-angle XRD profiles of cobalt
proceeded for 2 h. The product was quantified by gas nanoparticles, rice husk, acid treated rice husk, rice husk
chromatography using pyridine as internal solvent. In all ash, MCM-41, and Co-loaded MCM-41. The existence of
the calculations, GLy was assumed as a limiting reactant. the broad hump at 2θ = 23
in all the samples except
The GLy conversion, GLc yield, and selectivity, as well as Co3O4 and rice husk ash may be attributed to the amor-
turn over frequency (TOF), were calculated using the fol- phous nature of silica. The characteristic peaks of cobalt
lowing formulas, respectively: oxide (Co3O4) nanoparticles are located at 2θ = 19.06
,
31.32
, 36.91
, 44.87
, 59.39
, 65.28
, and 77.39
. This


GLyinitial GLyunreacted illustrates its crystalline behaviour. The average crystal-
XGLy ¼  100 ð2Þ
GLyinitial line size was calculated based on the Co3O4 diffraction
peak (311), using Equation (1) and was about ~32.94 nm.

 The current work is in good agreement with Zhu
GLcproduced
YGLc ¼  100 ð3Þ et al.,[22] who calculated the crystallite size of spinel
GLyinitial
Co3O4 particles prepared from hydrothermal treatment
to be 35.4 nm.


YGLc Rice husk, acid-treated rice husk, and rice husk ash
SGLc ¼  100 ð4Þ samples’ XRD profiles are depicted in Figure 1A. Rice
XGLy
husk and acid-treated rice husk samples’ observed peak

 at 27.4
[23] was attributed to partially crystallized carbon
GLyinitial  XGLy  MGLy from cellulose; upon calcination, the peak disappeared.
TOF ¼  100
100  mass of catalyst used for reaction  t Rice husk ash sample (silica fuse) exhibited a broad
ð5Þ hump around 22
, characteristic of amorphous silica.[24]
Thus, it confirmed that calcination of acid-treated rice
where XGLy, GLyinitial, GLyunreacted, YGLc, GLcproduced, husk removes carbon impurities present in it and the
SGLc, t, and MGLy, represent GLy conversion, moles of carbon will not interfere during the synthesizing process
GLy in feed (initial), GLy moles in product, GLc yield, of MCM-41.

FIGURE 1 X-ray diffraction (XRD) profile: (A) wide and (B) small-angle profile
ARORA ET AL.
The presence of strong peaks at 36.91
, which corre-
spond to Co3O4, justifies the incorporation of Co3O4
nanoparticles into the MCM-41 framework. The strength
of the peak at 36.91
increased with an increase in the
loading amount of cobalt in the channels of MCM-41.
The small-angle X-ray scattering profile of bare MCM-41
and Co/MCM-41 is displayed in Figure 1B. The planes
(100), (110), (200), and (210) are ascribed to the hexago-
nal space group p6mm.[6] The intensity of the major peak
at the (100) plane was noticeable even after loading a higher
percentage of cobalt oxide nanoparticles, indicating that
MCM-41 has a high degree of hexagonal organization in
the mesoporous region. At a higher concentration of cobalt
species in MCM-41, the peak strength decreased owing to
distortion of the porous hexagonal structure of MCM-41.
Furthermore, the Co/MCM-41 samples’ peaks were
observed broadening compared to the parent MCM-41 due
to the reduction of inter-planar d-spacing from 3.28–2.81 nm.
It may be due to the incorporation of Co3O4 nanoparticles in
the channels of MCM-41. The present results obtained were
in good agreement with the previous reports by Sikarwar
et al.[6] and Huo et al.[25]
Thermogravimetric analysis (TGA) was performed to
confirm the calcination temperature of the rice husk and
acid-treated rice husk. TGA curves of rice husk and acid-
treated rice husk showed a similar pattern (Figure 2A).
Thermal decomposition of hemicellulose and cellulose
was observed with a temperature range of 250–370
C.
Firstly, hemicellulose was decomposed and then cellulose
decomposed in temperature ranging from 150–275
C and
275–350
C, respectively. When the temperature was
raised from 360 to 650
C, losses in lignin content of the
rice husk were observed. A higher temperature was
FIGURE 2 (A) Thermogravimetric analysis (TGA) profile and (B) Fourier transform infrared (FTIR) spectra of MCM-41 and
Co/MCM-41
5
applied to decompose lignin present in the husk as it is
the most stable aromatic polymer of rice husk.[26,27]
The remaining weight of the sample after 650
C was
silica ash. Based upon TGA results, 700
C was selected as
calcination temperature to get the silica fuse from acid-
treated rice husk, which was further used for the synthesis of
MCM-41.
The devolatilization spectrum of MCM-41 and
Co/MCM-41 (5%, 400
C) is presented in the inset of
Figure 2A. From Figure 2A, two weight-loss zones were
perceived in the TGA. The first weight loss zone was
observed below ~300
C, indicating the loss of water mol-
ecules present in the pores of the MCM-41 framework.[11]
Furthermore, the second weight loss zone observed in
the range of ~300–565
C might be due to the burning of
left-over CTAB molecules. No further losses were
witnessed upon an increase in the temperature until
800
C, justifying the support material’s stability. Simi-
larly, in the spectra of Co/MCM-41 (5%, 400
C), the first
weight loss zone was up to 300
C, similar to the parent
MCM-41, and occurred owing to the loss of adsorbed
water molecule in the catalyst pores. The second weight-
loss region in the range of 550–850
C might be due to the
decomposition of metal nitrate into oxides, which is
responsible for accelerating the transesterification
reaction.
The FTIR spectra of washed rice husk, acid-treated
rice husk, rice husk ash, MCM-41, and cobalt impreg-
nated MCM-41 in the fingerprint region of 4000–
400 cm1 is presented in Figure 2B. The FTIR spectra of
washed and acid-treated rice husk possess similar func-
tional groups. In all the spectra, the intense broadband at
3434 cm1 represents an adsorbed molecule or O-H
6 ARORA ET AL.
hydroxyl group, and the band at 2922 cm1 is ascribed to
stretching vibrations of C-H2/C-H.[19] The characteristic
bands at 1733 cm1 and 1447 cm1 are designated to the
carbonyl group of C=O and –CH2 group, respec-
tively.[28,29] The band at 1059 cm1 represents symmetric
stretching vibrations of the alkyl alcohol group. The
small vibrations at ~802, ~673, and ~465 cm1 might be
due to silicon atoms attached to the oxygen in the rice
husk.[27,30] After calcination of rice husk, all the peaks
related to organic compounds were lost due to the com-
bustion of organic matter (mainly cellulose, hemicellu-
lose, and lignin). In the spectra of rice husk ash, a peak
appears at 1632 cm1 owing to stretching vibration of the
O-H group or absorbed water encapsulated in the struc-
ture of silica. The strong band at 1107 cm1 is ascribed to
the structural siloxane (Si-O-Si) bond, representing the
formation of amorphous silica after calcination.[28]
The vibrational modes near 808 and 467 cm1 which
intensified after calcination is assigned to the formation
of the Si-O bond.[31,32]
MCM-41 synthesized from rice husk ash exhibits a
strong band at 1096.96 cm1 associated with the asym-
metric stretching of the Si-O-Si bond, whereas the band
at 803 cm1 was attributed to symmetric and bending
vibration of Si-O-Si.[6,28] Similar to rice husk ash, the
band at 467 cm1 in MCM-41 and cobalt-loaded MCM-41
was assigned to the tetrahedral bending mode of Si-O.[25]
The band at 1636.28 cm1 may be attributed to Si-OH
stretching vibration of a physically adsorbed water mole-
cule.[18] In the IR spectra of all the samples of Co-loaded
MCM-41, the additional bands at 583.88 and 669.80 cm1
appeared owing to the absorption band of Co3+-O
stretching mode and Co2+-O stretching vibrations of
cobalt oxide nanoparticles in the framework of MCM-
41.[29] The peaks were barely visible when the loading
concentration of Co nanoparticles was less than 5 wt.
%, while the peak intensity increased with an increase
in loading amount to 10 wt.%, suggesting that the
active metal was successfully incorporated on the sup-
port material.
Purwaningsih et al.[33] investigated the rice husk ash
composition using EDX analysis. They found a major
portion of rice husk ash was silica and oxygen, and a
minor portion was Na, Al, Fe, carbon, and so on. Acid
treatment of rice husk effectively removes organic matter
and other metal impurities. Kamari and Ghorbani[34] and
Bakar et al.[27] investigated the rice husk ash composition
using X-ray fluorescence (XRF). The acid treatment
removes metallic impurities from rice husk and signifi-
cantly improves the purity of silica,[27,35,36] which serves
as a precursor for the synthesis of MCM-41.
The morphology of Co3O4 nanoparticles, MCM-41,
and Co/MCM-41 (5%, 400
C) was investigated through
SEM, and results are shown in Figure 3. Figure 3A repre-
sents the cobalt nanoparticles having a flower-like struc-
ture with small nanorods of a size around 32.34 nm,
which was found by taking an average of around
100 nanoparticles using ImageJ software.[20] The surface
pictograph of MCM-41 revealed that the material com-
prised unevenly distributed spheroidal-shape particles
(Figure 3C).[37] However, cobalt nanoparticles-loaded
MCM-41 (Figure 3E) have no significant difference in
morphology, but a slightly thin film was observed on the
support. The EDX results show the presence of Si and O
in a major portion of bare MCM-41, but cobalt-loaded
MCM-41 samples confirm Co species besides Si and
O. From the SEM and EDX results, it can be confirmed
that cobalt species were successfully dispersed on
MCM-41.
The nitrogen adsorption–desorption isotherms of
MCM-41 and Co/MCM-41 (5%, 400
C), and their
corresponding pore size distributions are displayed in
Figure 4A,B. Both the samples exhibit typical type IV iso-
therms with the H1 hysteresis loop, which signifies the
presence of cylindrical mesopores structure, presumably
due to the typical structure of MCM-41 according to
IUPAC nomenclature. The stability of liquid nitrogen
meniscus in the material’s narrow pores may be the plau-
sible cause of the formation of such a hysteresis loop.[25]
Moreover, the pore structure of MCM-41 remained
undamaged even after cobalt nanoparticles were incorpo-
rated into its framework. The pore size distribution of
both samples illustrates the uniform distribution with the
average pore size being in the range of 3–4 nm that corre-
sponds to the ordered structure of cylindrical pores
(Figure 4B).[38] As seen from the isotherm, monolayer
adsorption of nitrogen to the walls of MCM-41 and
cobalt-loaded MCM-41 takes place at a relative pressure
below 0.25, mainly due to structural pore filling.
Moreover, the multilayer adsorption on the particle’s
outer surface was evidenced in the relative pressure range
between 0.3–1.0. The isotherm is steeper in the relative
pressure range of 0.8–1.0, which may be assigned to capil-
lary condensation in inter-particulate secondary pores.[39]
The surface area and pore volume of MCM-41 decreased
slightly with the incorporation of active metal (Co/MCM-41)
from 532 to 490 m2/g and 0.506 to 0.453 cm3/g, respec-
tively. Impregnation of cobalt nanoparticles on the
MCM-41 framework may not cause any substantial
changes in average pore diameter, which decreased
slightly from 3.653 to 3.627 nm.
Figure 5 depicts the transmission electron microscopy
(TEM) image of MCM-41 and Co/MCM-41 (5%, 400
C).
A highly ordered two-dimensional honey-type pore struc-
ture formed from series or parallel lines was observed in
the image (Figure 5A) when an electron beam was
ARORA ET AL. 7

F I G U R E 3 Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis of (A) SEM image of Co3O4, (B) EDX of
Co3O4, (C) SEM image of MCM-41, (D) EDX of MCM-41, (E) SEM image of Co/MCM-41 (5%, 400
C), and (F) EDX of Co/MCM-41
(5%, 400
C)
8 ARORA ET AL.

FIGURE 4 (A) Nitrogen adsorption–desorption isotherm and (B) pore size distribution of MCM-41 and Co/MCM-41 (5%, 400
C)

F I G U R E 5 High-resolution image
of MCM-41 (A) along the pore and
(B) perpendicular to the pore;
Co/MCM41 (5%, 400
C) (C) along the
pore and (D) perpendicular to the pore
with the insert being the corresponding
particle

directed in the direction along with the pores of MCM-41
framework. Furthermore, the TEM images were also taken
by orienting the electron beam in the direction perpendicular
to the pores, which displays the channels and structure of
the MCM-41 (Figure 5B). From the micrographs, it can be
believed that MCM-41 possesses a highly ordered hexagonal
array of long-range silicate tubes.[25] Cobalt-loaded MCM-41
also showed a long-range hexagonal pore structure similar to
MCM-41 (Figure 5C). Some dark particles were observed in
Co/MCM-41, which may correspond to the dispersion of
cobalt nanoparticles on MCM-41. A clear honey-comb struc-
ture was observed in the TEM image of Co/MCM-41
(5%, 400
C), showing that MCM-41 retains its structure upon
the loading of active metal into its framework elucidating
complete dispersion of cobalt nanoparticles in the structure
of MCM-41 (Figure 5D).
ARORA ET AL.
F I G U R E 6 Full-range X-ray photoelectron spectroscopy (XPS) spectrum of (A) MCM-41, (B) full-range XPS spectrum of Co/MCM-41
(5%, 400
C), (C) C 1s, (D) O 1s, (E) Si 2p, and (F) Co 2p
The details of surface composition and chemical state
linkage present in surface layers were studied in the
range 5–10 nm through the solid sample XPS spectra.
The XPS spectra of MCM-41 and Co/MCM-41
(5%, 400
C) are depicted in Figure 6. The major photo-
electron lines of C 1s, O 1s, and Si 2p were detected in
both the spectra; also, Co species were identified in
Co/MCM-41. The obtained findings are compatible with
the results of SEM–EDX. However, the deconvoluted
spectra of individual elements of MCM-41 are not shown
in Figure 6. The photoelectron spectra of cobalt-loaded
9
MCM-41 was analyzed to confirm its interaction with sil-
ica and carbon. Curve fitting was performed by assuming
the Gaussian-Lorentzian peak shape after subtracting
from the Shirley baseline. The C 1s XPS spectra of
Co/MCM-41 (5%, 400
C) were deconvoluted into four
major peaks centralized at the binding energy values of
284.06, 284.63, 286.01, and 287.73 eV, and these peaks
may be due to C-C, C=C, C-O, and C=O, respectively, as
shown in Figure 6C.[40,41] The appearance of the C bond
in photoelectron spectra may be due to the surfactant
decomposed in the MCM-41 framework. The spectra of O
10 ARORA ET AL.

F I G U R E 7 Optimization of reaction parameters to maximize yield and conversion: (A) influence of catalyst mass (molar ratio of DMC-
to-GLy: 4, temperature: 80
C, residence time: 2.5 h), (B) influence of molar mass of DMC-to-GLy (catalyst mass: 6 wt.%, temperature: 80
C,
residence time: 2.5 h), (C) influence of reaction temperature (catalyst mass: 6 wt.%, molar ratio of DMC-to-GLy: 3, residence time: 2.5 h),
(D) influence of residence time (catalyst mass: 6 wt.%, molar ratio of DMC-to-GLy: 3, temperature: 90
C), and (E) reusability study (catalyst
mass: 6 wt.%, molar mass of DMC-to-GLy: 3, reaction temperature: 90
C, residence time: 2 h)

1s were deconvoluted into three characteristic peaks: 531.13,
532.20, and 532.69 eV; these deconvoluted peaks may be due
to the presence of Co3O4, C-O, and Si-O-Si, respectively
(Figure 6D). The deconvoluted Si 2p spectra reveal the exis-
tence of peaks at a binding energy of 102.32, 103.00, and
103.51 eV due to the presence of Si-C, SiO2, and Si-O, respec-
tively (Figure 6E).[42,43]
Apart from the silicate peaks, the XPS spectra of cobalt
was deconvoluted into four peaks at binding energy, 781.08,
782.89, 786.88, and 797.43 eV, indicating the existence of
different states of cobalt on MCM-41. Furthermore, the for-
mation of clear spin-orbit doublets located at around 781.08
and 782.89 eV was due to the contribution of Co3+ associ-
ated to Co 2p3/2 oxidation states (Figure 6F), respectively.[44]
The shake-up satellite peaks positioned at 786.88 and
797.43 eV strongly correspond to Co2+ species. The occur-
rence of different oxidation states might be due to the inter-
action of Co3+ with the pore walls of silicate followed by its
reduction into Co2+ by -OH during calcination to remove
surfactant.[45]
ARORA ET AL. 11

TABLE 1 Effect of basicity, yield, and conversion by varying calcination temperature and active metal loading

Basicity Basic Yield of Conversion

Catalyst (mmol/g) strength GLc (%) ±SE of GLy (%) ±SE TOF ±SE
MCM-41 5.0 H_ ≤ 7.2 4.8 0.5 5.0 0.4 0.3 0.0
Co/MCM-41(2%, 500
C) 7.1 7.2 ≤ H_ ≤9.8 19.1 1.8 19.2 2.2 1.2 0.1
Co/MCM-41(5%, 500
C) 8.2 7.2 ≤ H_ ≤9.8 40.2 2.2 42.0 1.7 2.8 0.2


Co/MCM-41(7%, 500 C) 9.2 7.2 ≤ H_ ≤9.8 32.5 1.9 35.8 2.9 2.3 0.1


Co/MCM-41(10%, 500 C) 9.8 9.8 ≤ H_ ≤15 16.6 0.5 17.2 0.6 1.1 0.1
Co/MCM-41(5%, 200
C) 5.8 H_ ≤7.8 11.3 1.5 11.5 1.8 0.7 0.0


Co/MCM-41(5%, 300 C) 6.5 7.2 ≤ H_ ≤9.8 25.1 3.3 25.7 2.9 1.7 0.2


Co/MCM-41(5%, 400 C) 8.7 7.2 ≤ H_ ≤9.8 60.2 2.6 63.8 1.9 4.2 0.0


Co/MCM-41(5%, 500 C) a
8.0 7.2 ≤ H_ ≤9.8 81.6 1.6 86.7 2.7 5.7 0.1

Note: Reaction condition for calcination temperature and active metal loading was conducted with a DMC-to-GLy molar ratio of 4, catalyst dose of 4 wt.%
(based on GLy mass), reaction temperature of 80
C, and reaction time of 2.5 h.
a
Regeneration study was conducted at optimized conditions: DMC-to-GLY molar ratio of 3, catalyst dosage of 6 wt.% (based on GLy mass), reaction
temperature of 90
C, and reaction time of 2 h.

During impregnation, cobalt nanoparticles coordinate
with the hydroxyl group. The aqueous cobalt complex
interacts with the surface silanol group of support mate-
rial. The surface silanol group possesses amphoteric
character and can exist in the form of SiOH, SiO species,
the cationic exchange between the negatively charged sil-
ica and the positively charged cobalt ions is the
predominating process, resulting in the formation of
surface-bound Co3O4, Co2+, and Co-silicate like species
with the support material.[46–48] The existence of these
bonds is verified by XRD profile (Figure 1A), FTIR spec-
tra (Figure 2B), and XPS spectrum of cobalt (Figure 6F).
3.2 | Catalyst activity
Synthesized catalyst catalytic activity has been evaluated
to maximize the yield and selectivity of GLc. The proper-
ties of basicity and basic strength of catalyst highly
influenced the transesterification reaction. The batch
transesterification results (Figure 7A–E) revealed that
GLc selectivity had not fluctuated significantly, indicating
that Co/MCM-41 has high selectivity for the conversion
of GLy into GLc without any by-product formation. This
may be due to the prepared Co/MCM-41 catalyst having
moderate basic strength (7.2 < H_ < 15) and high basicity
(5–10 mmol/g). Das and Mohanty[2] reported that high
selective GLc demands moderate basic strength and
strong basic sites of the catalyst. This might be the reason
why the catalyst developed in this study marked the high
selectivity. In addition, the TOF has been calculated and
presented (Figure 7A–D) for readers to obtain a thorough
understanding. TOF directly depends on the moles of
GLc yield as well as the moles of GLy conversion.
3.2.1 | Effect of active metal loading and
calcination temperature on GLc yield
The presence of basic sites on the catalyst surface
enhances the transesterification reaction. It has been
reported that these basic sites strongly depend on active
metal loading as well as calcination temperature. Trans-
esterification of GLy into GLc with the absence of cata-
lysts did not occur. In sequence, unloaded MCM-41
showed negligible conversion of GLy (~5% conversion),
and this may be due to a lack of basic sites.[49] In this
study, cobalt species (2–10 wt.%) on the MCM-41 frame-
work showed better catalytic activity than bare MCM-41
due to improvement of basic sites on the catalyst surface
(see Table 1). All the experiments were conducted thrice,
and the standard error (SE) of each parameter was calcu-
lated as shown in Figure 7. The GLy conversion and GLc
yield increased from 19.2 ± 2.2% to 42.1 ± 1.7% and 19.1
± 1.8% to 40.2 ± 2.2%, respectively, with an increase in
active metal cobalt from 2 to 5 wt.% on the MCM-41
framework. The positive trend may be due to the basic
site concentration’s escalation from 7.1 to 8.7 mmol/g
(shown in Table 1). However, the GLy conversion, TOF,
GLc yield, and selectivity showed a negative trend with a
further increase in active metal cobalt from 7 to 10 wt.%,
despite an increase in basic site concentration to
9.8 mmol/g. This may be due to multilayer dispersion of
active metal at higher active metal loading on support,
12
which leads to decreased surface area by blockage/filling
of pores with an active metal, and the reactant species
may not access active sites to participate in the reaction.
Calcination temperature strongly influences the surface
properties of metal oxides and the geometry of the support.
The catalytic activity of 5 wt.% Co/MCM-41 catalyst cal-
cined at different temperatures from 200–500
C for 2.5 h
was used in the transesterification reaction for GLc synthe-
sis (Table 1). It was perceived that an increase in the calci-
nation temperature from 200 to 400
C, the basicity of the
catalyst, TOF, GLy conversion, GLc yield, and selectivity
showed a positive trend. This might be due to an improve-
ment in basic site concentration from 5.8 to 8.7 mmol/g,
which leads to higher catalytic activity on GLy conversion
from 11.5 ± 1.8% to 63.8 ± 1.9%, respectively. However, at a
lower calcination temperature (200
C), the catalyst may
possess lower basic sites due to the incomplete decomposi-
tion of cobalt nitrate into oxides. But, at a higher calcination
temperature, cobalt nitrate converted into its oxide forms
(Co3O4), which were responsible for enhancing the basic
site, and thus, leading to higher catalytic activity for the
conversion of GLy. Parameswaram et al.[50] addressed that
the number of oxide ions present on the catalyst surface
was responsible for an increase in the basicity and basic
F I G U R E 8 Comparative plots showing simulated and experimental concentration of GLy and GLc at (A) 70, (B) 80, (C) 90, and
(D) 100
C (DMC-to-GLy molar ratio of 3, Co/MCM-41 [5%, 400
C], catalyst dose of 6 wt.%)
ARORA ET AL.
sites of the catalyst. With a further increase in calcination
temperature from 400 to 500
C, the GLy conversion
declined. At higher calcination temperature, sintering and
agglomeration of particles on the active surface take place,
which leads to the decline of basic sites.[2] From the TGA
and XPS study, it was found that a trace amount of surface
directing agent was left over within the framework of
MCM-41. The surface directing agent, CTAB, exhibits the
weak basicity dispersed inside the mesoporous channel,
which is in favour of the transesterification reaction. Mori
et al.[51] investigated the effect of residual templates with
the MCM-41 framework. It was found that residual tem-
plates (CTAB) within the MCM-41 exhibit superior cata-
lytic activity than conventionally calcined catalyst
without templates. This may be due to enhancement of
basicity of the catalyst through surfactant and it is the
prime factor for the transesterification reaction.
3.2.2 | Influence of reaction conditions
The yield of GLc and conversion of GLy were optimized
upon studying the effect of catalyst dosage, molar ratio of
reactants, reaction time, and temperature.
ARORA ET AL. 13

TABLE 2 Equilibrium constants for the conversion of GLy to GLc at different reaction temperatures
Temperature k3 a ra  1004 Ea
(
C) K1 ±SE K2 ±SE (min1) ±SE K4 ±SE K5 ±SE (min1) ±SE  1005 (kJ/mol) ±SE

70 2.6830 0.2341 2.8041 0.5623 0.0892 0.0045 2.6463 0.4559 2.6580 0.3652 1.3697 3.5635 58.2 2.4

80 2.7112 0.1653 2.8454 0.4896 0.1943 0.0395 2.6158 0.5236 2.5480 0.2362 1.0468 2.2895

90 2.7305 0.3631 2.9577 0.5231 0.4282 0.0651 2.5592 0.2651 2.4238 0.1542 0.2220 0.4865

100 2.7146 0.3562 2.9369 0.3581 0.4191 0.040 58 2.5471 0.3725 2.4138 0.2158 0.2350 0.1576

a
Reaction rate constant.

The effect of catalyst dose concerning GLy mass has
been investigated to enhance the reaction rate, keeping
other reaction parameters constant (i.e., the DMC to GLy
molar ratio = 4, reaction temperature = 80
C, and the
reaction time = 2.5 h). Results are summarized in
Figure 7A, increasing the catalyst concentration from
1 to 6 wt.% (concerning the GLy mass), the GLy conver-
sion, GLc yield, and TOF were increased from 30.5
± 0.7% to 75.8 ± 1.5%, 29.9 ± 1.2% to 71.3 ± 0.5%, and
2.0 ± 0.1 to 5.0 ± 0.2 h1, respectively. The positive trend
might be attributed to the increase in active/basic sites
with an increase in catalyst mass, which maximizes the
GLc yield.[52] A decline in yield of GLc was witnessed
when the catalyst concentration increased from 6 to 8 wt.
% in the reaction mixture. This might be because the
agglomeration of the particles at higher catalyst loading
hinders the accessibility of the reactants to the active sites
of catalyst, and thereby stabilizes the conversion of GLy.
Algoufi et al.[52] reported that increasing catalyst mass
beyond a threshold value would induce sufficient
mass transfer resistance.
The influence of reactant mass (the DMC-to-GLy
molar ratio) was investigated in the range of 1–7 under
constant reaction conditions (Reaction time = 2.5 h, reac-
tion temperature = 80
C, and catalyst dose = 6 wt.%)
(Figure 7B). The GLc yield, GLy conversion, and TOF
showed a positive trend from 57.9 ± 1.1% to 78.7 ± 2.6%,
58.6 ± 2.9% to 80.9 ± 1.5%, and 3.9 ± 0.09 to 4.5
± 0.2 h1, respectively, with an increase of DMC-to-GLy
molar ratio from 1 to 3. This may be due to a shift of
equilibrium towards the forward direction when increas-
ing the reactant molar ratios. However, a further increase
in the DMC-to-GLy molar ratio from 3 to 7 would reduce
the conversion, yield, and TOF because dilution of cata-
lyst concentration in the reaction mixture occurred when
the DMC was added in a large amount. The observed
trends are in good agreement with the studies on catalyst
mass effect.[9]
The experiments have been conducted at different
temperatures to investigate the critical importance of
reaction temperature in the transesterification reaction
for the synthesis of GLc. Figure 7C demonstrates the
influence of reaction temperature ranging from 70–
100
C, with a constant catalyst dose of 6 wt.%, a DMC-to-
GLy molar ratio of 3, and reaction time of 2.5 h on GLc
yield. The experimental results exhibited a gradual
improvement in GLc yield, TOF, and GLy conversion
from 50.7 ± 2.2% to 91.3 ± 0.9%, 3.4 ± 0.4 to 6.5
± 0.4 h1, and 51.4 ± 1.2% to 98.4 ± 1.1%, respectively, as
the reaction temperature increased from 70 to 90
C. This
might be because, at higher temperatures, the kinetic
energy of the liquid mixture increases, resulting in a
decrease in the reactant molecules’ viscosity, which leads
to the improvement in miscibility, thus enhancing the
yield and conversion.[53] However, a decrease in the
selectivity of GLc was observed with a further increase of
temperature from 90 to 100
C. The decline of yield could
be attributed to the decomposition of the formed mole-
cule into other by-products due to opening of the GLc
ring on excess available basic sites on the surface of the
catalyst.[7]
The effect of reaction time was investigated to maxi-
mize the GLc yield with a set of experiments conducted
at the optimized conditions at a regular time interval of
0.5–2.5 h (Figure 7D). Both the GLy conversion and GLc
yield increased with an increase in reaction time. In the
reaction time of 0.5 h, 63.3 ± 2.5% GLc yield and 64.5
± 1.5% GLy conversion were observed. The GLc yield
and GLy conversion rose to 94.1 ± 0.7% and 98.7
± 1.2%, respectively, when the reaction time was pre-
ceded to 2 h. The minor increase in GLy conversion
and a slight decrease in GLc yield were observed with
an increase in the reaction time from 2 to 2.5 h, owing
to decarboxylation of GLc into glycidol on the active
sites of the catalyst upon prolonging the reaction
time.[53] Though glycidol quantification was moni-
tored, glycidol was not identified. This may be because
of the low concentration of glycidol present in the reac-
tion mixture. Hence, the reaction time of 2 h was taken
as an optimized time to conduct the transesterification
of GLy into GLc.
3.3 | Reusability and catalyst
stability test
The feasibility of heterogeneous catalysts in an industrial
application needs to meet the reusability criteria without
14
rapid deactivation. By considering this, the reusability of
Co/MCM-41 was investigated via reuse experiments
(Figure 7E). The method implemented to reuse the spent
catalyst was the same as that in Arora et al.[21] without
adopting any regeneration technique. Spent catalyst was
washed with methanol, dried, and reused in the subsequent
reaction. Results concluded that cobalt impregnated MCM-
41 could be used for four cycles without sustainable loss in
its activity. After the fourth cycle of reusability, the GLc yield
and GLy conversion declined slightly from 94.1 ± 0.7% to
~81.6 ± 1.6% and 98.7 ± 1.2% to 86.7 ± 2.7%, respectively.
This declining trend may be due to loss of basic sites and
leaching of active metal (last line of Table 1). After the fourth
cycle, the spent catalysts were separated, dried, and then
used to investigate their surface chemistry and crystallinity
using FTIR and XRD. It was seen from the spectra that the
intensity of the peak of active metal decreased in XRD and
FTIR profiles of the spent catalysts, which might be responsi-
ble for the loss in activity of the catalyst.[54]
3.4 | Green parameters
The present study’s greener approach and eco-friendly
nature were quantitatively accessed by the E-factor and
process mass intensity using Equations (6) and (7). The
lower the E-factor, the lower the waste generated during
the process. Thereby the process is considered eco-
friendly for the environment:
Total waste ðgÞ
E  factor ¼
Product ðgÞ
where total waste = total mass of material used in the
process  total mass of product formed:
Total mass used in the process ðgÞ
PMI ¼
Mass of final product ðgÞ
Since methanol is the only major by-product of trans-
esterification of GLy into GLc, which could be further
used in the biodiesel production plant, the recoverability
of solvent and reusability of catalyst were not considered
while calculating the values of these parameters. E-fac-
tor = 1.1 and PMI = 2.1 were calculated for the produc-
tion of GLc, showing the minimum waste generated
during the process.
3.5 | Reaction kinetics
In order to get an in-depth understanding of heteroge-
neous catalytic reactions, it is essential to evaluate its
ARORA ET AL.
chemical reaction kinetics. The catalytic transesterification
reaction of GLy with DMC follows three significant steps:
(i) adsorption of reactants (GLy and DMC), (ii) the surface
reaction between GLy and DMC molecules on the active
site, and (iii) desorption of products and unconverted reac-
tants from the active site (GLc and methanol). To describe
the possible dual site catalytic process, the Langmuir-Hin-
shelwood-Hougen-Watson (LHHW) model was used.[55]
The kinetic model Equation (8) was adopted as developed
by Arora et al.[21] for GLy and DMC transesterification. The
elucidated derivation of Equation (8) is provided in the
Supporting Information (SI, Appendix S1):
dCGLy k0 CGLy
¼ 2 ;
dt
1 þ KGLy CGLy þ KGLy CGLy þ KCGLc þ KCMM ð8Þ
GLc
k0 ¼ kSR KGLy KDMC CDMC C2t
The parity plot between the experimental data and simu-
lated data of GLc and GLy is shown (Figure S1A,B in SI,
Appendix S1), and an excellent fit with an error of 20%
and 10%, respectively, was witnessed. Equation (8) was
solved to compute different rate constants of the reaction
using stiff integrators-ODE 15s from MATLAB. All the
parameters were taken in the range of positive real num-
bers. For each run, the value of the concentration of each
species was passed to the objective function, Equation (9),
and the best value was selected based on the value pro-
vided by the ‘Fmincon’ function.
The concentrations of GLy and GLc (simulated and
ð6Þ
experimental) were compared. The graphs are shown in
Figure 8A–D. From the results, it can be concluded that
the model shows an excellent fit between the experimen-
tal and simulated data of GLy and GLc. The criteria for
the determination of rate constant were that the value of
the sum of squares (SSE), root mean square error
ð7Þ
(RMSE), and chi-square (χ2) should tend to 0, while the
coefficient of determination (R2) should be close to
1. The mathematical formula used for the calculation of
SSE, RMSE, χ2, and R2 is provided in the SI[56]:
N 
X 2  2 
f¼ CiGLy,exp  CiGLy,pred þ CiGLc,exp  CiGLc,pred
i¼1
ð9Þ
The values of statistical parameters are presented in the
SI, which shows that SSE, RMSE, and χ2 tend to nearly
zero. In contrast, the higher values of the R2 approxi-
mately incline to 1, illustrating a good fit with the model.
The values of equilibrium constants at temperatures
between 70–100
C is shown in Table 2. When the
ARORA ET AL.
reaction was conducted at higher temperatures, the reac-
tion rate increased due to the movement of reaction
equilibrium towards a forward direction. It can be easily
perceived from the table that the apparent reaction rate
constant increases with the rise in reaction temperature
from 70 to 90
C, signifying that the concentration of
GLy and GLc attains equilibrium rapidly with the
increase in reaction temperature. The transesterification
reaction activation energy was calculated from the
Arrhenius plot and found to be 58.2 ± 2.4 kJ/mol.
4 | C ON C L U S I ON S
The present study successfully utilized agricultural waste
(rice husk) to prepare a mesoporous structure catalyst for
the valorization of GLy obtained from the biodiesel
industry. Synthesized catalyst portrays well-defined hex-
agonal structure exhibiting high thermal stability up to
800
C. The surface area and pore volume of Co/MCM-41
(5%, 400
C) declined compared with bare MCM-41 from
532 to 490 m2/g and 0.506 to 0.453 cm3/g, respectively.
Basic sites on the catalyst surface significantly influenced
the catalyst’s activity towards GLc yield. The catalyst
developed sustained its activities for transesterification
reactions up to the fourth cycle without any regenera-
tion. The value of K1, K2, K3, K4, and kˈ in the devel-
oped differential equation was solved through
MATLAB’s ODE 15s tool. The activation energy was
found to be 58.2 ± 2.4 kJ/mol. The obtained E-factor
value shows that the process is environmentally
friendly and green.
ACK NO WLE DGE MEN TS
This work was supported by Department of Science and
Technology, Government of India through Early Career
Research grant (ECR/2015/000085, dated 20 August
2016). Ms. Shivali Arora would like to thank Malaviya
National Institute of Technology, and the Department of
Higher Education, Ministry of Education, Government of
India for the award of a fellowship.
P EE R R EV IE W
The peer review history for this article is available at
https://publons.com/publon/10.1002/cjce.24284.
DATA AVAILABILITY STATEMENT
All data included in this study are available upon request
by contact with the corresponding author.
ORCID
Vijayalakshmi Gosu https://orcid.org/0000-0001-6510-
9873
15
Verraboina Subbaramaiah https://orcid.org/0000-0003-
4457-6725
RE FER EN CES
[1] Y. T. Algoufi, G. Kabir, B. H. Hameed, J. Taiwan Inst.
Chem. E. 2017, 70, 179.
[2] B. Das, K. Mohanty, Journal of Environmental Chemical
Engineering 2019, 7, 102888.
[3] M. A. Do Nascimento, L. E. Gotardo, R. A. C. Le~ao, A. M. De
Castro, R. O. M. A. De Souza, I. Itabaiana, ACS Omega 2019,
4, 860.
[4] P. U. Okoye, A. Z. Abdullah, B. H. Hameed, J. Taiwan Inst.
Chem. E. 2016, 68, 51.
[5] S. Arora, V. Gosu, U. K. A. Kumar, V. Subbaramaiah, Int.
J. Chem. React. Eng. 2020, 18, 1.
[6] P. Sikarwar, U. K. A. Kumar, V. Gosu, V. Subbaramaiah,
Journal of Environmental Chemical Engineering 2018, 6, 1736.
[7] P. Kumar, P. With, V. C. Srivastava, R. Gläser, I. M. Mishra,
Ind. Eng. Chem. Res. 2015, 54, 12543.
[8] M. Malyaadri, K. Jagadeeswaraiah, P. S. Sai Prasad, N.
Lingaiah, Appl. Catal. A-Gen. 2011, 401, 153.
[9] X. Song, Y. Wu, F. Cai, D. Pan, G. Xiao, Appl. Catal. A-Gen.
2017, 532, 77.
[10] G. Parameswaram, P. S. N. Rao, A. Srivani, G. N. Rao, N.
Lingaiah, Molecular Catalysis 2018, 451, 135.
[11] P. Liu, M. Derchi, E. J. M. Hensen, Appl. Catal. A-Gen. 2013,
467, 124.
[12] D. Li, H. Min, X. Jiang, X. Ran, L. Zou, J. Fan, J. Colloid Interf.
Sci. 2013, 404, 42.
[13] M. J. Hülsey, H. Yang, N. Yan, ACS Sustain. Chem. Eng. 2018,
6, 5694.
[14] A. Gidde, M. R. Jivani, in Proc. of the Int. Conf. on Cleaner Tech-
nologies and Environmental Management, PEC, Pondicherry,
India 2007, p. 586.
[15] F. W. Chang, M. S. Kuo, M. T. Tsay, M. C. Hsieh, Appl. Catal.
A-Gen. 2003, 247, 309.
[16] H. B. Dizaji, T. Zeng, I. Hartmann, D. Enke, T. Schliermann,
V. Lenz, M. Bidabadi, Appl. Sci. 2019, 9, 1.
[17] N. Sapawe, N. Surayah Osman, M. Zulkhairi Zakaria, S.
Amirul Shahab Syed Mohamad Fikry, M. Amir Mat Aris,
Mater. Today-Proc. 2018, 5, 21861.
[18] H. M. A. Hassan, M. A. Betiha, R. F. M. Elshaarawy, M. Samy
El-Shall, Appl. Surf. Sci. 2017, 402, 99.
[19] M. Bhagiyalakshmi, L. J. Yun, R. Anuradha, H. T. Jang,
J. Porous Mat. 2010, 17, 475.
[20] M. Salavati-Niasari, F. Davar, M. Mazaheri, M. Shaterian,
J. Magn. Magn. Mater. 2008, 320, 575.
[21] S. Arora, V. Gosu, V. Subbaramaiah, Molecular Catalysis 2020,
496, 111188.
[22] Z. Zhu, G. Lu, Z. Zhang, Y. Guo, Y. Guo, Y. Wang, ACS Catal.
2013, 3, 1154.
[23] R. V. Krishnarao, M. M. Godkhindi, Ceram. Int. 1992, 18, 243.
[24] R. V. Krishnarao, M. M. Godkhindi, P. G. I. Mukunda, M.
Chakraborty, J. Am. Ceram. Soc. 1991, 74(11), 2869.
[25] C. Huo, J. Ouyang, H. Yang, Sci. Rep. 2015, 4, 1.
[26] W. Roschat, T. Siritanon, B. Yoosuk, V. Promarak, Energ.
Convers. Manage. 2016, 119, 453.
[27] R. A. Bakar, R. Yahya, S. N. Gan, Procedia Chem. 2016,
19, 189.
16
[28] S. Arora, V. Gosu, U. K. A. Kumar, V. Subbaramaiah, J. Clean.
Prod. 2021, 295, 126437.
[29] K. Tang, X. Hong, Energ. Fuel. 2016, 30, 4619.
[30] T. H. Liou, S. J. Wu, J. Hazard. Mater. 2009, 171, 693.
[31] D. An, Y. Guo, Y. Zhu, Z. Wang, Chem. Eng. J. 2010, 162, 509.
[32] F. Adam, K. Kandasamy, S. Balakrishnan, J. Colloid Interf. Sci.
2006, 304, 137.
[33] H. Purwaningsih, S. Raharjo, V. M. Pratiwi, D. Susanti, A.
Purniawan, Mater. Sci. Forum 2019, 964, 88.
[34] S. Kamari, F. Ghorbani, Biomass Conversion and Biorefinery
2020, https://doi.org/10.1007/s13399-020-00637-w.
[35] T. Sirisoontornpanit, A. Wongkoblap, S. Junpirom, Key Eng.
Mater. 2017, 729, 24.
[36] K. Kordatos, A. Ntziouni, L. Iliadis, V. Kasselouri-Rigopoulou,
J. Mater. Cycles Waste 2013, 15, 571.
[37] B. M. Abu-Zied, M. M. Alam, A. M. Asiri, W. Schwieger,
M. M. Rahman, Colloid. Surface. A 2019, 562, 161.
[38] G. V. Mamontov, A. S. Gorbunova, E. V. Vyshegorodtseva, V. I.
Zaikovskii, O. V. Vodyankina, Catal. Today 2019, 333, 245.
[39] V. Subbaramaiah, V. C. Srivastava, I. D. Mall, Ind. Eng. Chem.
Res. 2013, 52, 9021.
[40] Y. Li, J. Liu, D. He, Appl. Catal. A-Gen. 2018, 564, 234.
[41] P. Sikarwar, U. K. A. Kumar, V. Gosu, V. Subbaramaiah,
J. Chem. Eng. Data 2018, 63, 2975.
[42] R. Gostynski, R. Fraser, M. Landman, E. Erasmus, J.
Conradie, J. Organomet. Chem. 2017, 836–837, 62.
[43] F. J. Grunthaner, P. J. Grunthaner, R. P. Vasquez, B. F. Lewis,
J. Maserjian, J. Vac. Sci. Technol. 1979, 16, 1443.
[44] B. Solsona, E. Ayl on, R. Murillo, A. M. Mastral, A. Monzonís,
S. Agouram, T. E. Davies, S. H. Taylor, T. Garcia, J. Hazard.
Mater. 2011, 187, 544.
[45] S. Shen, J. Chen, R. T. Koodali, Y. Hu, Q. Xiao, J. Zhou, X.
Wang, L. Guo, Appl. Catal. B-Environ. 2014, 150–151, 138.
ARORA ET AL.
 Szegedi, M. Popova, C. Minchev, J. Mater. Sci. 2009, 44,
[46] A.
6710.
[47] E. Van Steen, G. S. Sewell, R. A. Makhothe, C. Micklethwaite, H.
Manstein, M. De Lange, C. T. O’Connor, J. Catal. 1996, 162, 220.
[48] S. Madadi, J. Y. Bergeron, S. Kaliaguine, Catal. Sci. Technol.
2021, 11, 594.
[49] K. Lanjekar, V. K. Rathod, Journal of Environmental Chemical
Engineering 2013, 1, 1231.
[50] G. Parameswaram, M. Srinivas, B. Hari Babu, P. S. Sai Prasad,
N. Lingaiah, Catal. Sci. Technol. 2013, 3, 3242.
[51] H. Mori, K. Takuya, Y. Ikurumi, S. Yamashita, Chem.
Commun. 2013, 49, 10468.
[52] Y. T. Algoufi, U. G. Akpan, G. Kabir, M. Asif, B. H. Hameed,
Energ. Convers. Manage. 2017, 138, 183.
[53] Y. T. Algoufi, B. H. Hameed, Fuel Process. Technol. 2014, 126, 5.
[54] S. Wang, J. Wang, P. Sun, L. Xu, P. U. Okoye, S. Li, L. Zhang,
A. Guo, J. Zhang, A. Zhang, J. Clean. Prod. 2019, 211, 330.
[55] P. Devi, U. Das, A. K. Dalai, Chem. Eng. J. 2018, 346, 477.
[56] H. A. Hamid, R. Yunus, U. Rashid, T. S. Y. Choong, A. H.
Al-Muhtaseb, Chem. Eng. J. 2012, 200-202, 532.
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How to cite this article: S. Arora, V. Gosu,
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