Materials Science for Energy Technologies 1 (2018) 11–21

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Materials Science for Energy Technologies

CHINESE ROOTS
GLOBAL IMPACT
journal homepage: www.keaipublishing.com/en/journals/materials-science-for-energy-technologies

Engineered nanoporous materials mediated heterogeneous catalysts and

their implications in biodiesel production
Swati Sharma a, Varun Saxena a, Anupriya Baranwal b, Pranjal Chandra b,⇑, Lalit Mohan Pandey a,⇑
a
Bio-Interface & Environmental Engineering Lab, Department of Bioscience and Bioengineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India
b
Laboratory of Bio-Physiosensor and Nanobioengineering, Department of Bioscience and Bioengineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India

a r t i c l e i n f o a b s t r a c t

Article history: World’s energy needs are majorly dependent on the fossil fuels, including petrochemical sources and
Received 18 April 2018 coal. The alternate of these fuels include hydro and nuclear powers. However, all these resources are
Revised 11 May 2018 finite and current rate of consumption indicates the shortening of the fuels and energy in the near future.
Accepted 11 May 2018
Diesel plays a remarkable role in the economy of the developing and developed countries in industry and
Available online 25 May 2018
other sectors being a basic fuel used in transportation. The increasing demand of alternate energy based
on renewable resources and pollution-free production is a major concern these days for environmental-
Keywords:
ists. Biodiesel, in this regard is set to be the best entrant to acquire the desired alternative of conventional
Nanoporous materials
Biodiesel
fuels. The production of biodiesel is carried out through transesterification reaction using edible oil feed-
Transesterification stocks, which is not feasible for developing countries. Hence, utilization of low-grade feedstocks for bio-
Heterogeneous catalyst diesel production is the new clinch for the developing countries. In general, the transesterification
Feedstocks reaction is mediated by catalysts and hence, design of an effective catalyst is the key to produce efficient
Yield and commercially viable biodiesel. In this direction, it is necessary to understand the material chemistry
of catalysts and mechanism of the catalytic transesterification reaction. This review enlightens the basics
of transesterification, role of various process parameters and factors affecting biodiesel production from
different feedstocks. In this review we have discussed various nanoporous heterogeneous catalysts inves-
tigated for biodiesel production and mainly focused on the mechanism involved in transesterification
using heterogeneous catalysts.
Ó 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2. Factors affecting transesterification reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3. Homogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4. Heterogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.1. Heterogeneous acid catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.2. Heterogeneous base catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
5. Mechanism of heterogeneous catalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
7. Challenges and future prospective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

⇑ Corresponding authors.
E-mail addresses: pchandra13@iitg.ernet.in (P. Chandra), lalitpandey@iitg.ernet.in (L.M. Pandey).

https://doi.org/10.1016/j.mset.2018.05.002
2589-2991/Ó 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
12 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21
1. Introduction
Growing concerns about environmental safety and depletion of
fossil fuel reserves have incited extensive research towards finding
substitute fuel sources for conventional fossil fuels. In recent years,
biodiesel, a clean renewable fuel, has garnered commendation
worldwide owing to its biodegradability, similar ignition charac-
teristics to fossil diesel, and less detrimental effects on the environ-
ment [1,2], as its emissions are non-toxic; including lower CO, S,
and other hydrocarbons making it a carbon-neutral fuel. Studies
revealed that biodiesel can lessen total CO2 releases by 78% as com-
pare to the fossil fuels [3–5], which aids towards additional neces-
sity to save the nature from the harmful side effects of the emerged
technologies. The overall biodiesel production across the globe was
8.5 billion gallons in 2016 which is expected to expand 10.3 billion
gallons in the upcoming decade [6]. The Royal Academy of Engi-
neering presented a report on the sustainability of liquid biofuels
explaining the biofuel industry market valued at £262 billion in
2014, with an expected annual growth of 14% per annum by
2020 [7]. The aforementioned factors are helping in the emergence
of the biofuel industry. According to a report of E4tech (UK) for
LBNet, by 2020 the wholesale price of biodiesel may reach up to
€11.7/GJ, higher than that of petrol in Europe. Hence, the current
era demands the practice of sustainable and economical feedstocks
such as nonedible (Jatropha) and used cooking oils, for the eco-
nomic and effective large-scale production of biodiesel [8]. In this
direction, India is producing about 10-250 thousand tons of biodie-
sel per year using non-edible feedstocks and its overall biodiesel
consumption was about 1000 barrels per day in 2014 [9,10]. Fur-
thermore, Government of India has taken the initiative of up to
20% blending of biodiesel in 2017 [11]. According to a report of
Business standard, the Biodiesel Association of India (BDAI), the
total installed capacity of biodiesel production is 12 lakh tons per
annum, with an actual production of 3.5 lac ton per annum in
India, however estimated or potential production is about 27.5
lakh tons per annum. Replacement of conventional diesel by bio-
diesel can save approximately S$1.47 billion foreign currency of
India [12].
Biodiesel chemically is a fatty acid methyl ester, which is
formed by transesterification reaction among the triglycerides (a
major constituent of oils) and alcohols (usually methanol and etha-
nol). The transesterification reaction is reversible in nature and can
be either catalytic or non-catalytic. It involves swapping of R
(alkyl) group of triglyceride’s ester with the Ŕ(alkyl) group of alco-
hol, hence is also termed as alcoholysis (Fig. 1). However, the non-
catalytic reactions are very slow and low yielding processes. Hence,
the transesterification reaction is typically manifested by the cata-
lysts. Briefly, the entire process of transesterification takes place in
three steps: (i) conversion of triglycerides to diglycerides, (ii) con-
version of diglycerides to mono-glycerides and ultimately, (iii)
conversion of mono-glycerides to glycerol along with the forma-
tion of biodiesel [13].
Despite the scientific success in the biodiesel production, it is
still at its infant step in terms of commercial feasibility, due to
Fig. 1. Generalized mechanism of transesterification reaction for biodiesel production.
its inability to meet the world’s present energy demand. Although
various researchers are working to maximize the yield of biodiesel
production, the process is successful only under experimentally
optimized conditions (at pilot scale), which varies solely from geo-
graphic source to source. An accurate cradle to grave valuation is
required to make this process rapid and energy efficient at indus-
trial scale. Design of an effective and efficient heterogeneous cata-
lysts offers a solution for such important problem and hence
researchers have explored various nanoporous catalysts for the
production of biodiesel. In the view of such important develop-
ments, we have discussed the most imperative factors affecting
the transesterification reaction, which eventually leads to the pro-
duction of biodiesel. Majorly, we have focused on the engineered
nanoporous heterogeneous catalysts, their types and applications.
In addition, we have included two comprehensive tables summa-
rizing various heterogeneous catalysts (acidic and basic) used in
the transesterification of edible/non-edible feedstocks, along with
the optimized process parameters and the respective biodiesel pro-
duction yield, which will give the readers an insight into the cur-
rent scenario of biodiesel production. We have also abridged the
properties, drawbacks, and the possible solutions to these draw-
backs for the commercialized production of the biodiesel, citing
various researches with varying degree of successes.
2. Factors affecting transesterification reaction
Fig. 2 shows various factors which govern the transesterifica-
tion reaction which eventually are important for biodiesel produc-
tion. For the effective and commercial production of biodiesel, it is
necessary, to understand the individual role of these factors. In this
section, we have majorly discussed various reaction parameters,
their role in transesterification reaction and their applicability.
There are various grounds, which effects the commercialization
of the biodiesel and its industrial production. These reasons are
also discussed in the following section.
At present, different global regions consume different feedstock
for biodiesel production. For example, US uses Soybean oil, Canada
employs Rapeseed and Canola, Europe uses Sunflower, and Palm oil
dominates in Asia, as feedstock for biodiesel production. The bio-
diesel produced using these edible feedstocks are classified as first
generation biodiesel. However, these expensive feedstocks make
the process less economic for the commercialization of biodiesel
in the developing countries. Hence, recent studies put forward
non-edible oil as an alternative to the edible feedstocks. Many
non-edible plants for example Jatropha, Castor, Neem, Tobacco, Sea
mango, and Mahua, have been explored for the production of bio-
diesel [14–17]. The biodiesel produced using these non-edible
feedstocks are classified as second generation biodiesel. The disad-
vantage with employing non-edible feedstock at commercial scale
involves hectic initial pretreatment and procurement, such as har-
vesting toxic seeds from Jatropha is a cumbersome process [18].
The third generation biodiesel is obtained directly from the bio-
mass (e.g. algae). Depending upon the seasonal and geographic
availability, the feedstock may vary, but it is necessary to
 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21
Fig. 2. Schematic representation of factors involved in the transesterification of oils for biodiesel production.
unanimously standardize the characteristics of feedstock to maxi-
mize the biodiesel yield. These characteristics may include acid
value, saponification value, moisture content, specific density,
pH, and viscosity of feedstocks.
The second ingredient involved in transesterification process is
alcohol. Types of alcohol used in biodiesel production include
methanol, ethanol, propanol, butanol etc. However, it is witnessed
that long-chained alcohol leads to decrease in biodiesel yield. Nye
et al. performed an experiment on the transesterification of used fry-
ing oil using 0.4% KOH at 50 °C employing oil: methanol molar ratio
of 1.3:5 with different solvents i.e. methanol, ethanol and propanol
and the biodiesel yield was obtained as 73.8%, 46.1%, and 31.9%,
respectively [19]. This suggests that the rise in chain length of alco-
hol decreases the yield of biodiesel. Hence, smallest chained metha-
nol being low cost, and highly miscible solvent, ensures its
applicability in transesterification process. Oil to methanol ratio also
plays a critical role in the transesterification reaction. Even though
the stoichiometric ratio of oil: methanol ideally should be 1:3 for
complete transesterification process, it is reported that addition of
methanol in excess amount shifts the reaction towards product (bio-
diesel) formation [20]. However, the problem lies in the optimiza-
tion of the solvent quantity for a spontaneous transesterification
reaction at higher reaction rate. Studies suggested that, the lower
molar ratio of methanol causes an incomplete reaction, whereas its
higher molar ratio decreases the efficiency of separation of the glyc-
erol from the excess methanol and also incurs additional production
cost [21–23]. This happens due to decrease in the overall density of
glycerol, inhibiting its separation from methanol. Hence, it is neces-
sary to optimize the molar ratio of oil: methanol beforehand.
Various reaction conditions such as temperature, time, and mix-
ing/agitation speed also has a decisive effect in the effectiveness of
transesterification reaction. In general, reaction temperature plays
crucial role in decreasing the overall viscosity of oil, thereby
13
increasing its miscibility with methanol [24,25]. Temperature
may enhance the rate as well as the yield of the transesterification
reaction. For example, Baskar et al., obtained the increase in the
yield of biodiesel production from 85% to 95%, with rise in temper-
ature from 40 °C to 55 °C, respectively by using mixture of castor
oil: methanol (1:8), signifying the endothermic nature of transes-
terification process. However, high temperature for transesterifica-
tion reaction, risks the vaporization of methanol, saponification of
triglycerides, as well as decreases the polarity of methanol, hence
causes decrease in the overall biodiesel yield [26]. Hence, opti-
mization of the reaction temperature is the most crucial step of
the transesterification reaction. Likewise, overall reaction time also
regulates the overall conversion of the reactants to products. With
increase in the reaction time, the biodiesel yield enhances until all
the substrate (oil) is consumed. Studies indicated that at room
temperature (25 °C), the reaction time can vary from few mins to
hours [21,27–29]. Moreover, the optimum time of transesterifica-
tion varies with type of feedstock, catalyst type and concentration,
and various other parameters described in above section. Agitation
speed is also, one of the major factors in transesterification reac-
tion which plays a crucial role, when the reactants are immiscible
in nature (e.g. oil and methanol). It should be high enough to break
the barrier of mass transfer between two immiscible liquids. Den-
ser feedstock requires comparatively high agitation rate for signif-
icant biodiesel yield. Studies stated that transesterification using
immiscible catalyst requires higher agitation rate as compared to
the miscible catalyst [30–32]. Apart from high density of feedstock,
as mentioned above, the inability of catalyst to mix properly with
methanol and to form methoxide (transition state product),
required for the biodiesel formation, is also an important reason
for applying high agitation speed. However, studies supported
the contribution of co-solvent in overcoming the oil and water
immiscibility. Principally, in a homogeneous system (where
14 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21
catalyst is miscible in methanol), stirring speed increases the reac-
tion rate, but in case of heterogeneous system (when catalyst is
immiscible in methanol) presence of co-solvent overcomes the
barrier of immiscibility and allows the oil and methanol to come
in contact at standard agitation speed, hence decreases the need
of vigorous mixing, otherwise required. Few co-solvent used in
the transesterification of high-density oil are hexane, ethanol,
tetrahydrofuran, acetone, toluene, diethyl ether, ethyl acetate as
well as chloroform [33–36]. For instance, in a recent study on
transesterification of used cooking oil, acetone (wt.10%) was used
as a co-solvent with methanol utilizing cement as catalyst, yielded
95.5% biodiesel at agitation speed of 300 rpm [37]. In spite of all
the aforementioned factors, catalyst, their concentration and type,
play the key role in transesterification process. In general, catalyst
can be broadly classified as homogeneous catalysts and heteroge-
neous catalyst, based on their ability to mix with solvent and their
physical phase with respect to the reactants. These catalysts are
further classified as acid and base catalysts which are discussed
in details in the next sections.
3. Homogeneous catalysts
Homogeneous catalyst possesses similar physical phase with
that of reactants, i.e. are usually miscible with the reactants, and
are categorized into two forms: homogeneous base and homoge-
neous acid catalysts. Homogeneous base catalysts possess catalysis
rate 4000 times higher than that of an acid catalyst, at mild reac-
tion conditions [38]. However, they can cause soap formation, if the
free fatty acid content of the feedstock is >2%. In a typical base cat-
alyzed transesterification, NaOH and KOH are widely used. Unlike
base catalyst, the homogeneous acid catalyst is insensitive to the
presence of free fatty acids in feedstock oil, hence are mostly appli-
cable for low-grade feedstock. However, their catalysis rate is com-
paratively slower than that of a base catalyst. H2SO4 and HCl have
widely used acid catalyst in the transesterification reaction
[39,40]. Even though, homogeneous catalysts are cheap, easily
available and give better yield at mild reaction conditions, yet the
drawback includes separation of catalyst after reaction from the
product, corrosion of reactor and saponification as side reaction.
These issues are well addressed by the introduction of heteroge-
neous catalyst in the transesterification reaction. We have enlight-
ened an expounded elucidation on heterogeneous catalyst involved
in transesterification process and the entire potential characteristic
that nominates them as lead candidate in this process.
4. Heterogeneous catalysts
A heterogeneous catalyst remains in a separate phase than that of
the reactants. They are also termed as contact catalysts as they func-
tions via adsorbing the reactant entities over their surfaces. In bio-
diesel production (transesterification reaction), heterogeneous
catalyst majorly lies in solid phase, whereas oil and methanol are
in liquid phase. Various heterogeneous catalyst have been investi-
gated for the biodiesel production. It is observed that overall
catalytic activity of these heterogeneous catalysts can be improved
via altering their lattice parameters through elemental doping step.
As discussed above, they catalyze the reaction through adsorption,
and hence, large surface area is required to proceed the transesteri-
fication reaction. Nanocomposites materials, in this contrast have
been proven as the best candidate [41]. Nanoporous materials own
good surface properties for instance, large surface area, nano-
scaled pore size with uniform distribution of pores, required for
transesterification reaction [26,42,43]. These enhanced properties
not only makes them finest entrant for biodiesel production, but
for other applications such as semiconductors [44–46], surface mod-
ification and tissue engineering [47–52], environmental cleanup
[53,54] biomedical applications e.g. drug delivery [55,56], antibacte-
rial activity [57–61], diagnostics [62–66] and energy resources
[67–70]. The heterogeneous catalyst concentration can be tuned
via designing an effective nanocomposite with enhanced surface
properties which includes high surface to volume ratio and uniform
dispersal of nano-pores. Heterogeneous catalyst reduces the cost of
biodiesel production via several ways, in terms of, ease of synthesis,
mild reaction conditions, reusability, regeneration capability and
ease of separation [71]. Based on the presence of acidic or basic sites
on the surface, heterogeneous catalysts are majorly categorized into
two types, as discussed in the following sections.
4.1. Heterogeneous acid catalysts
Acid catalyst is significant in the esterification of low-grade
feedstock which has high free fatty acid contents. In general,
solid-acid catalyst provides positively charged acid site for the
fatty acid content of oil to get adsorbed, initiating transesterifica-
tion reaction between methanol and adsorbed triglyceride, as
shown in Fig. 3. Table 1 lists various heterogeneous acid catalysts
utilized in transesterification of edible/nonedible feedstocks high-
lighting their reaction parameters and obtained biodiesel yield. It
is perceived that acid catalysts are majorly prepared using sulfonic
acid precursor, which provides them high esterification activity for
available free fatty acid content, whereas zirconia and SBA15 act as
carrier support. In a recent study, use of sulfuric carbonization of
biomass waste is employed for solid-acid catalyst preparation.
Presence of various oxygen rich functional groups in the biomass,
acts as major sites for sulfonation to occur thereby increasing the
acidic active sites on the catalyst. Thushari et al. studied sulfonated
coconut meal residue as a catalyst (5% w/w), with overall surface
area of 1.33 m2 g 1, pore volume of 0.31 cm3 g 1, diameter of
13.2 nm, and pore size in the range 2.4–200 nm, respectively.
Transesterification of waste palm oil having acid value:  0.4 mg
KOH g 1, was undertaken using 12:1 M ratio of oil: methanol,
yielding > 92% of biodiesel after 8 h at 65–70 °C reaction conditions
with recyclability up to 4 batches [72]. Recently, sulfonated zirco-
nium phosphate nanosheets (SO3H@ZrP), was also studied with
methanol and oleic acid (9:1) at 65 °C, as a nanoporous catalyst
for transesterification. A comparative study between the catalytic
activity of SO3H@ZrP, H2SO4, and a commercial solid-acid catalyst
AmberlystÒ 15 (all loaded at 5% w/w), has been done, where the
nanoporous catalyst showed 89% conversion of oleic acid, which
was higher than commercial catalyst along with higher recyclabil-
ity up to 5 cycles [73].
Acid catalysts have also been examined for third generation bio-
diesel production. In this regard, Guldhe et al. developed tung-
stated zirconia based heterogenous acid catalyst for biodiesel
production by utilizing S. obliquus lipids as feedstock having
19.72 mg KOH g 1 acid value, and saponification value of 180.35
mg KOH g 1, respectively. They performed a comparative study
between the heterogeneous and homogeneous acid catalyst using
1:12 M ratio of oil: methanol, at temperature of 100 °C resulting
the biodiesel yield of 94.58%. Whereas, the biodiesel yield was
96.68% and 91.7% when homogeneous catalyst (Sulfuric acid) and
enzyme catalysts (Immobilized Pseudomonas fluorescence lipase)
were used, respectively. The solid-acid catalyst exhibited acid
strength (Ho) of 14.6, indicating the high super-acid property.
Lower reaction time and reusability up to 3 batches, reduced
methanol consumption and higher yield ensures the commercial
applicability of the solid-acid catalysts [74].
Heterogenous acid catalysts have been proven as potential can-
didate for producing biodiesel using waste cooking oil. Li et al.
developed a magnetic solid-acid core shell catalyst by immobiliz-
ing (3-aminopropyl) trimethoxysilane over magnetic (Fe3O4) core.
 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21 15

Fig. 3. Schematic representation of transesterification using solid-acid catalyst; AS indicates acid site on catalyst, R1 indicates for alkyl group of fatty acid, and R2 indicates
alkyl group of triglyceride.

Table 1
Performance of heterogeneous acid catalysts in transesterification of edible/nonedible feedstocks for biodiesel production (* stands for Ethanol: Oil ratio).

Feedstocks Nonoporous Catalysts Reaction conditions Biodiesel References

Yield (%)
T (°C) Molar ratio Catalyst loading Time
(M:O)* (W%) (hours)
Palm oil [HSO3-BMIM]HSO4 108 11:1 9.17 6.43 98.93 [76]
Palm oil Sulfonated graphene 100 20:1 10 10 98 [77]
Soybean oil Carbonaceous catalysts 220 12:1* 5 5 93.2 [78]
Macaw palm oil Sulfated niobium oxide 250 120:1* 30 4 >98 [79]
Oleic acid + canola oil Amberlyst-15 120 5:1 2.5 1 >90 [80]
Castor oil Montmorillonite clay 60 12:1 5 5 89.8 [81]
Jatropha oil Montmorillonite clay 110 6:1 5 2.5 98 [81]
Jatropha oil Carbonaceous catalysts 220 12:1 5 5 90.9 [78]
Waste palm oil Sulphonated carbon 65–70 12:1 5 12 92.7 [72]
Waste cottonseed oil CeO2/Li/SBA-15 65 40:1 10 4 >98 [82]
Waste cooking oil Tungsten loaded bovine bone 100 6:1 8 5 98.9 [83]
Used cooking oil Mesoporous silica catalysts containing phosphotungstic acid 70 2:1 26.5 4 93 [84]
Waste cooking oil FeCl3-modified resin 90 10:1 8 2 92 [85]
Waste cooking oil Sulfonated carbon microsphere 110 9.35:1 10 4 89.6 [86]
Waste mustard oil Amberlyst-15 60 8:1 6 0.5 97.13 [87]
Microalgal lipid Chromium-aluminum mixed oxide 80 20:1 15 4 98.28 [88]
Microalgal lipids Tungstated zirconia 100 12:1 15 3 94.5 [74]

The size of the magnetic core was found to be 10 nm, with the
surface area of 245 m2 g 1. The solid acid catalyst had 92 m2 g 1
available surface area. This magnetic solid acid catalyst showed
advantages such as easy accessibility of acidic sites, and ease of
separation along with enhanced waste-oil utilization efficiency.
Strong ionic interactions enhancing the activity and stability was
due to magnetic attraction between particles and the core shell
structure. Under mild reaction conditions at 70 °C, the total yield
from waste cooking oil was found to be 98.9% [75]. Such studies
can lower down the hectic separation process, eventually enhanc-
ing the reusability and time of the overall reaction, which are con-
sidered to be must important factors for the commercialized
production of the biodiesel.
From the various examples enlisted in Table 1, it is perceived
that acid catalysts are mostly employed in case of high acid value,
in order to reduce the soap formation. The solid-acid-catalysts
carry few drawbacks such as; less activity and stability, slower
reaction rate and requirement of high reaction temperature. How-
ever, their ease of separation, non-corrosive nature, lesser down-
stream processing (e.g. washing of biodiesel), and easy
regeneration and reusability makes them an effective candidate
for the transesterification process. Hence, there is a need to
enhance the positive aspects of the solid-acid catalyst, increasing
its stability at high temperature, making its surface more oleophilic
in order to upgrade its insensitivity to moisture content of low
grade feedstock. In addition, the surface area of these solid-
acid catalysts can be enhanced through elemental doping, which
subsequently can provide more number of action sites for the
transesterification reaction. Moreover, the elemental doping may
alter the surface charge of the pristine catalysts, which can be
easily tuned depending upon the acid content of the oil
triglyceride.
4.2. Heterogeneous base catalysts
The transesterification reaction can easily be manifested by
using homogeneous base catalysts such as NaOH and KOH at mild
reaction conditions, yet the separation and reusability are the main
16 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21

drawbacks. In general, solid-base catalysts provide negatively
charged base sites for the methanol to be adsorbed, facilitating
the transesterification reaction [89]. Fig. 4 describes the transester-
ification mechanism in base-catalyzed reaction involving (i)
physical adsorption of methanol to basic site on catalyst, (ii) reac-
tion of fatty acid of triglyceride with methanol, (iii) formation of
methyl esters and glycerol, and (iv) re-availability of basic site on
the catalyst. Overall, the mild reaction conditions, lower time, and
methanol amount required for transesterification reaction using
solid-base catalysts, makes them adequate for their applicability
at commercialized scale. Hence, designing of nanostructured
heterogeneous catalysts with high basic strength, along with effi-
cient reusability is important and has great commercial impor-
tance. In recent studies, alkali metals are pooled with suitable
carrier materials such as alkaline and transition metal oxides, to
maintain the aforementioned properties of solid-base catalysts.
Table 2 includes various examples of the solid-base catalysts used
for biodiesel production and their optimized reaction parameters.
Among the various alkaline base catalyst enlisted, CaO has been
extensively studied due to its high catalytic rate, large abundance,
low production cost and easy availability, however, it undergoes
leaching upon repetitive uses. Other alkaline metal oxide such as;
MgO and SrO also showed similar shortcomings i.e. MgO has poor
basicity whereas SrO has smaller molecular size, in comparison to
CaO. Hence, recent studies are performed with the intention of
enhancing the stability along with surface basicity through the
incorporation of various other metal oxides (ZnO, SiO2, Al2O3 etc.)
[90–92]. In accordance with such study, Yang et al., examined
kinetic study of transesterification using metal oxides viz. ZnO,
Hydrotalcite CH16Al2Mg6O9
4H2O (HT), CaO, Al2O3, MgO, Na2SiO3,
and CaSiO3 using soybean oil as feedstock. The respective surface
properties of the catalysts were as follows: Na2SiO3 (Surface area
and pore diameter 1.40 m2 g 1 and 50.28 nm), CaSiO3 (Surface area
m2 g 1 and pore diameter 45.08 nm), CaO (Surface area m2 g 1 and
pore diameter 24.83 nm), and MgO (Surface area 6.61 m2 g 1, and
pore diameter 10.18 nm), ZnO (Surface area 4.16 m2 g 1, and pore
diameter 35.08 nm), and HT (Surface area 225.20 m2 g 1, and pore
diameter 5.03 nm). Their study revealed that mild conditions such
as 28 °C temperature, 12:1 methanol: oil molar ratio, and time
interval of 9–12 h was required to provide > 95% yield by using
Na2SiO3. However, the yield was decreased from 98.4%, to 98.3%,
87.3% and 70.0% after repeated 4 cycles. Under similar conditions,
the biodiesel yield was 14.2% for CaSiO3, 2% for CaO and <1.1% for
MgO, ZnO and HT. Whereas, CaSiO3 was studied at 28 °C, for 24 h,

Fig. 4. Schematic representation of solid-base catalyzed transesterification process. Image adapted from ‘‘Environment-friendly heterogeneous alkaline-based mixed metal
oxide catalysts for biodiesel production” by Lee et al., 2016, Energies, 9(8): p. 611[89]
 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21 17

Table 2
Performance of heterogeneous base catalysts in transesterification of edible/nonedible feedstocks for biodiesel production.

Feedstocks Nonoporous Catalysts Reaction conditions Biodiesel Yield (%) References

T (°C) Molar ratio Catalyst loading Time (hours)
(M:O) (W%)
Rice bran oil CaO nanocatalyst 65 35:1 0.5 2 93.5 [97]
Soybean oil CaO/activated carbon 69 10:1 2 6 93.01 [98]
Castor oil Nickel doped ZnO 55 8:1 11.07 1 95.2 [26]
White mustard seed oil Powdered quicklime 60 6.1:1 9.8 0.8 95.0 [99]
Soybean oil Cesium impregnated sodium zirconate 65 30:1 1 0.25 98.8 [100]
Linseed oil Calcium oxide 30 9.48:1 15 3 98.08 [36]
Soybean oil Li2TiO3 catalyst 65 24:1 6 2 98.5 [101]
Sunflower oil MgO/MgAl2O4 110 12:1 3 3 95.0 [102]
Soybean oil Cement kiln dust 65 12:1 3.5 6 NR [103]
Silybum marianum L. seed oil Carbon acid catalyst 60 15:1 6 1.25 96.98 [104]
Palm oil Lime derived CaO 65 15:1 6 2 97.0 [105]
Palm oil Rice husk derived sodium silicate 65 12:1 2.5 0.5 97.0 [106]
Palm oil CaO/c-Al2O3 60 15:1 9 3 97.66 [107]
Palm oil Fly ash from wood pellet 60 12:1 9 3 99.92 [107]
Soybean oil MgFe2O4@CaO 70 12:1 1 3 98.3 [108]
Soybean oil Calcined duck eggshell 60 10:1 10 1.3 94.6 [109]
Non-edible Karanja oil Cement waste 60 30:1 2.5 3 76.0 [110]
Jatropha oil Cesium impregnated sodium zirconate 65 15:1 3 1 90.8 [100]
Jatropha oil KOH/calcined waste animal bones 70 9:1 6 3 96.10 [111]
Waste cooking oil Calcium diglyceroxide 62 7.46:1 1.03 0.25 94.86 [27]
Waste olive oil Tio2 nanoparticles 120 30:1 0.2 4 91.2 [112]
Waste cooking oil Cao- ZrO2 65 30:1 10 2 92.1 [113]

using 27:1 M ratio of methanol: oil and catalyst amount of 23% (w/
w) obtaining > 99% of the biodiesel yield [93]. Hence, these cata-
lysts can replace the traditional homogeneous catalysts with the
additional reusability. Similarly, Wang et al., investigated efficiency
of solid-base catalyst prepared using slag of gasified straw
which had surface area of 1.266 m2g 1, and pore volume of
0.01971 cm3g 1, for the transesterification of rapeseed oil. The gasi-
fier included metal oxides such as MgO, SiO2, Al2O3, K2O, CaO, and
FeO. The optimized conditions were found to be 200 °C in the pres-
ence of 20% (w/w) catalyst, 12:1 M ratio of methanol: oil for the
time interval of 8 h, to obtain 95% yield of biodiesel. The catalyst
showed reusability for up to 33 repeats and the biodiesel yield
was found to be >85%. Hence, the gasifier can be concluded as one
of the best fit reusable solid-base catalyst for transesterification
reaction [94].
Sano et al., designed a calcium ferrite dispersed carbon nano-
horn (CNH) as solid-base catalyst (Surface area; 274.4 m2 g 1
CNH) for the transesterification of tricaprylin into methyl capry-
late. Using such CNH, the yield was found to be 95% in 120 min
at 64 °C, which subsequently enhanced the biodiesel yield to
100% within 180 min. The benefit of utilizing the calcium ferrite
lies in its easy separation process. The authors stated that the
reusability of the catalyst was 100% up to 3 times with a simple
magnetic separation, which was decreased down to 86.6% at fifth
cycle [95]. However, high basicity of catalyst can cause saponifica-
tion in the presence of free fatty acid. Hence, for the low grade
feedstock, use of amphoteric transition metal oxides which are less
susceptible to free fatty acid are essential. However, they are effec-
tive at high temperature and requires more reaction time in com-
parison to the alkaline metal oxide. Nevertheless, they does not
cause leaching, even after repeated usage, and can perform esteri-
fication and transesterification simultaneously (due to Lewis base
character). In addition, their non-corrosive nature and ease of
separation and regeneration, affix their practical applicability in
the biofuel industry. For instance, Jamil et al. investigated the role
of Mn@MgO-ZrO2 having 45.78 m2 g 1 surface area and pore diam-
eter of 17.06 nm, as a solid-basic catalyst for biodiesel production
using low-grade feedstock of the waste kernel oil. Under the opti-
mized experimental conditions of 90 °C, 15:1 methanol: oil molar
ratio and catalyst loading of 3% (w/w), a 96.4% biodiesel yield
was obtained after 4 h [96]. From these examples, it can be con-
cluded that low reaction time, methanol: oil ratio and catalyst con-
centrations as well as mild reaction parameters are required for
transesterification reaction using solid-base catalyst. Yet the
decrease in the reusability and the reactive conditions during bulk
production are the major concerns. Hence, an optimized doping of
transition metals into basic oxides can complement each other, by
providing stability along with the high catalytic activity at mild
reaction conditions using low grade feedstock, making this process
economically feasible for scale up production.
5. Mechanism of heterogeneous catalysis
The essential step in transesterification reaction is adsorption.
Heterogeneous catalysts provide reaction site for the reactants
(adsorbents) to be adsorbed, and thus catalyzes the reaction. Diffu-
sion is one of the major problem in heterogeneous catalysis of oil
[114]. Hence, to reduce the diffusion and for a proper adsorption
reaction, a heterogeneous catalyst must possess certain character-
istics such as; hefty surface area, uniform distribution of numerous
pores of optimum pore sizes. Solid-acid catalyst provides positively
charged active site for the adsorption of fatty acid and solid-base
catalysts provide negatively charged active site for the adsorption
of methanol. In solid-base catalysis, a tetrahedral intermediate is
formed due to the reaction between alkoxide ion to the alkyl group
of triglyceride, followed by its reaction with the alcohol. The rear-
rangement of this intermediate produces the ester and diglycerides
(See Fig. 4). In solid-acid catalysis, a carbocation is formed, which
due to the attack of nucleophile (alcohol) gives rise to tetrahedral
intermediate, which excludes glycerol and forms a new ester
regenerating the catalyst (See Fig. 3). In summary, physical adsorp-
tion of oil or alcohol under optimized conditions takes place at the
active sites of the heterogeneous catalysts depending on the type
of catalysts. Intermediates are formed, which lower the activation
energy barrier and facilitates biodiesel production. There are vari-
ous other factors, which governs the adsorption of the adsorbents
at the active site of the adsorbate such as; concentration of active
sites, stability of catalyst on the basis of its leaching activity and
surface poisoning effects, overall catalyst surface hydrophobicity,
18 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21
and repulsion to polar compounds. Hence, an ideal heterogeneous
catalyst must possess all these given characteristics to facilitate the
effective and efficient biodiesel production. Alteration in any of
these properties may lead to the failure or delaying of the transes-
terification reaction.
6. Conclusion
Biodiesel is proven to be an efficient, eco-friendly and sustain-
able substitute to conventional fuels. However, the economics of
its production is a major bottleneck to be addressed by the
research communities. In this direction, non-edible feedstocks i.e.
Jatropha oils and waste cooking oils etc. are explored as a cheaper
raw materials as compare to the edible oils. Mild reaction condi-
tions and optimum molar ratio of alcohol are essential for eco-
nomic production of biodiesel. Yield of produced biodiesel is still
a major challenge for its economic viability. In this context, nano-
porous materials based heterogeneous catalysts play a crucial role
for the effective and efficient conversion of feedstocks to biodiesel
with an added feature of reusability. These nanoporous materials
enhance the specific surface area of the catalyst for the maximized
adsorption of oil and methanol and hence manifest the biodiesel
production. Various heterogeneous acid and base catalysts have
been explored using various feedstocks and different optimum bio-
diesel yields are reported based on reaction temperature, time, and
catalyst concentrations. Generally, mild reaction conditions and
lower time intervals are required using solid-base catalysts than
that of solid-acid catalyst. Even though solid-base catalysts are
more efficient for spontaneous transesterification reaction, yet
one of the major concerns while using solid-base catalyst is
reusability, which gets down to many folds after consecutive reac-
tions. In order to remove these lags, heterogeneous catalysts must
possess both base site as well as the acid site. This can possibly be
achieved by doping of transition metal ions into the solid-base
catalysts.
Fig. 5. The proposed transesterification mechanism of biodiesel production using engineered nanoporous heterogeneous acid-base bifunctional catalyst.
7. Challenges and future prospective
Although researchers have explored various feedstocks as well
as catalysts for obtaining more than 95% yield of biodiesel, yet
the commercialization of the biodiesel has not been accomplished.
The major reason behind this lag is the type of feedstocks, cata-
lysts, their availability and production cost. Conventional homoge-
neous catalysts are efficiently being used in transesterification of
edible/ nonedible feedstock yet their reusability is the major con-
cern. Heterogeneous catalysts overcome various side effects of
homogeneous and enzyme catalysts such as their hygroscopic nat-
ure, water production with alcohol, reusability, and hectic separa-
tion processes. However, the major disadvantage of heterogeneous
catalyst includes the formation immiscible phases with reactants
during transesterification reaction i.e. oil, alcohol (water), and cat-
alysts (solid) [114]. This subsequently leads to diffusion limita-
tions, thus decreases the rate of the reaction. This limitation can
be diminished by the incorporation of co-solvents as discussed in
Section 2. The catalyst support can also be introduced with more
surface area and pore volume of active sites for the reaction of
large triglyceride molecules.
Nanocomposites can play a master role in this direction, as
composites carry the properties of both filler as well as the matrix.
In addition, they form more stable structure than that of bulk solid-
acid or solid-base catalysts, which in turn can enhance the
reusability of the catalyst. Nanoporous composite of solid acid-
base catalyst may provide all the necessary requirements for the
transesterification reaction such as high surface to volume ratio,
elevated number of pores, and reactive acid and base sites for
transesterification reaction. Hence, it is recommended that
nanocomposites of transition metal ions and basic metal oxides
(e.g. Zn, Fe doped CaO) for the transesterification reaction, in order
to affix the practical applicability and commercial availability of
the biodiesel production. The major drawbacks of solid-acid
catalyst and solid-base catalyst can be removed by designing a
 S. Sharma et al. / Materials Science for Energy Technologies 1 (2018) 11–21
bifunctional nanoporous heterogeneous catalyst containing both
acid and the base active sites. This can subsequently reduce the
complex reaction conditions of the solid-acid catalysts and
reusability and side effects of solid-base catalyst. Fig. 5 shows
the proposed mechanism of transesterification through bifunc-
tional catalysts depicting the successive physio sorption of triglyc-
erides and methanol on the surface of nanoporous heterogenous
catalyst, producing biodiesel and glycerol as by products. Hence,
nanocomposites, containing both acid and base sites, with high
surface to volume ratio and larger pore distribution can provide a
solution for the bulk production of the biodiesel.
Acknowledgement
The authors are grateful to the Department of Science and Technol-
ogy, Government of India for financial supports (Sanction Nos:
DST/INSPIRE/04/2014/002020, ECR/2016/001027) and Department
of biosciences and bioengineering of IIT Guwahati for providing all
necessary facilities for conducting the research. PC acknowledges
DST Ramanujan Fellowship award (SB/S2/RJN-042/2015).
Conflict of interest
The authors declare that the research was conducted in the
absence of any commercial or financial relationships that could
be construed as a potential conflict of interest.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.mset.2018.05.002.
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