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Current Organic Chemistry, 2019, 23, 2190-2203

REVIEW ARTICLE
ISSN: 1385-2728
eISSN: 1875-5348

Chemo-catalytic Esterification and Transesterification over Organic Polymer-Based Impact

Factor:
2.029

Catalysts for Biodiesel Synthesis

BENTHAM
SCIENCE

Heng Zhang1,2, Chunbao (Charles) Xu2, Kaichen Zhou1 and Song Yang1,*

1
State Key Laboratory Breeding Base of Green Pesticide & Agricultural Bioengineering, Key Laboratory of Green Pesticide & Agri-
cultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for
Research & Development of Fine Chemicals, Gizhou University, Guiyang, Guizhou 550025, P.R. China; 2Institute for Chemicals and
Fuels from Alternative Resources (ICFAR), Department of Chemical and Biochemical Engineering, Western University, London,
Ontrario N6A 5B9, Canada
Abstract: The major sources of fuels in today's world predominantly come from tradi-
tional fossil resources such as coal, petroleum and natural gas, which are limited and non-
renewable. Meanwhile, their consumption releases large undesirable greenhouse gas and
ARTICLE HISTORY noxious gases. Therefore, the development of renewable and sustainable feedstocks to re-
place traditional fossil resources has attracted great interest. Biodiesel, mainly produced
Received: May 11, 2019
Revised: May 30, 2019 through esterification and transesterification reaction from renewable oil resources using
Accepted: May 30, 2019
acids and bases as catalysts, is deemed as a green and renewable biofuel that shows enor-
DOI: mous potential to replace fossil diesel. Compared to homogeneous catalytic systems, the
Current Organic Chemistry

10.2174/1385272823666190715124659
development of efficient and stable heterogeneous catalysts is vital to synthesizing biodie-
sel in an efficient and green manner. Among the developed solid catalysts, organic poly-
mer-based catalytic materials are an extremely important topic, wherein distinct advantages of higher concen-
tration of active sites and better stability of active groups are associated with each other. In this review, effec-
tive catalytic valorization of sustainable feedstocks into biodiesel via transesterification and esterification reac-
tions mediated by functionalized organic polymer-based catalysts is discussed. Special emphasis has been
given to the synthetic routes to the versatile organic polymers-based catalytic materials, and some other inter-
esting catalytic roles derived from physicochemical property, like adjustable hydrophilicity and hydrophobicity
along with swelling property in transesterification and esterification, are also illustrated.

Keywords: Biodiesel, organic polymers, transesterification, esterification, acid-base catalysis, hydrophilicity/hydrophobicity.

1. INTRODUCTION improved reusability in a wide range of acid-catalyzed reactions

To make the industrial chemical processes effective and
prompt, active catalysts which can simultaneously reduce the reac-
tion time and steps are often crucially needed [1-4]. In addition,
from the viewpoint of green chemistry, the use of the relevant cata-
lysts having high efficiency and selectivity will reduce the envi-
ronmental influence in terms of lowering energy consumption and
waste generation, especially for promoting the important organic
reactions [5-10]. Homogeneous catalysts generally show relatively
high activity and selectivity for given target reactions, while exist
kenspeckle shortcomings including corrosion, difficulty in separa-
tion, and complex wastes disposal. Taking “green synthesis”, the
hotspot of organic synthesis with respect to academia and industry
into account, heterogeneously catalytic systems, which can be sim-
ply recycled having environmental compatibility, have aroused
great attention [11]. Among the various types of solid acids,
heteropolyacids, metal oxides, sulfonated metal oxides, phosphates,
and strongly acidic resins have shown good catalytic activity and
*Address correspondence to this author at the State Key Laboratory Breeding Base of
Green Pesticide & Agricultural Bioengineering, Key Laboratory of Green Pesticide &
Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for
Comprehensive Utilization of Biomass, Center for Research & Development of Fine
Chemicals, Gizhou University, Guiyang, Guizhou 550025, P.R. China; Tel:
+86(851)8829 2171; Fax: +86(851)8829 2170; E-mail: jhzx.msm@gmail.com
[12, 13]. However, because of their low surface areas, the number
of active sites that can be accessed by substrates is very limited, and
the diffusion barrier is very high [14]. Nanoporous inorganic-oxides
usually exhibit low catalytic activity owing to their low acid con-
tents. Although nanoporous sulfated inorganic-oxides show im-
proved acidity, the leakage of acidic sites with the subsequent
deactivation of the catalyst is still a major issue in industrial appli-
cations [15, 16]. Zeolitic solid acids, which have abundant micro-
pores embedded in their frameworks, have been shown to have
increased surface areas and improved catalytic performance. They
offer excellent stability for long-term use, selectivity for target
products, and tunability for acidic strength. [17]. However, the rela-
tively small sizes of the micropores (< 2 nm) in zeolites limit their
applications in catalyzing the conversion of bulky molecules such
as biomass and heavy oils [18-21]. It is noteworthy that the devel-
opment of polymer-based catalytic materials is an extremely impor-
tant topic. Polymeric acids/bases have the advantages of higher
active site concentration and active group stability [22, 23], and
they exhibit wide applications in gas storage and adsorption [24-
26], sensing [27, 28], organic catalysis transformations [29-34], and
so on. In particular, thanks to their high surface area, excellent sta-
bility, and adjustable physicochemical characters, functionalized
porous organic polymers give rise to tremendous opportunities with
the aim of supporting homogeneous catalysts [35].

1875-5348/19 $58.00+.00 © 2019 Bentham Science Publishers

Chemo-catalytic Esterification and Transesterification Current Organic Chemistry, 2019, Vol. 23, No. 20 2191

(a) OH
H2C
H2C OOC R1 O
Catalyst HC OOC R2
HC OOC R2 + CH3OH H3C O C R1 +
Step 1 H2C OOC R3
H2C OOC R3

TG FAME DG

H2C OH H2C OH
O
HC OOC R2 Catalyst HC OH
+ CH3OH H3C O C R2 +
H2C OOC R3 Step 2 H2C OOC R3

DG FAME MG

H2C OH
H2C OH
HC OH O
Catalyst HC OH
H2C OOC R3 + CH3OH H3C O C R3 +
Step 2 H2C OH
MG FAME Glycerol

(b)
O O
Catalyst
+ CH3OH H3C O C R3 + H2O
R OH Step 2

FAME

Scheme 1. (a) Schematic illustration for transesterification of triglycerides with methanol, and (b) esterification of fatty acid with methanol.

Due to the declining oil reserves, concerns over climate changes
related to CO2 emissions, and increasing demands on energy have
intensified the interest and efforts in the utilization of bio-renewable
resources for biofuels and value-added chemicals [36-39]. Biodie-
sel, having remarkable merits such as biodegradability, free of
sulfur, renewability, and high lubricity, is being deemed as a re-
newable and biodegradable fuel [40-42]. Direct utilization of bio-
diesel can reduce exhaust emissions of hydrocarbons, particulate
matters and CO2 by 70%, 50% and close to 80%, respectively. Fur-
thermore, owing to the high O2 concentration of biodiesel, the
emissions of unburned hydrocarbons (in the form of VOC) and SO2
are also negligible in biodiesel combustion [43-45]. Biodiesel is
widely accepted consisting of long-chain fatty acid monoalkyl
esters, which are commercially manufactured from renewable oil
resources (i.e., non-edible oils) by transesterification with short-
chain alcohols (Scheme 1a) [46]. It is worth mentioning that esteri-
fication of long-chain free fatty acids (FFAs) derived from food
processing byproducts with short carbon-chain alcohols, has also
acquired great attention regarding biodiesel production especially
from low-cost feedstocks (Scheme 1b). Compared to the bio-
catalytic process using expensive enzyme, chemo catalytic proto-
cols should be preferable [47]. As for biodiesel synthesis, trans-
esterification can be accelerated by both acids and alkalis, while
esterification can only be catalyzed by acids. From the perspective
of green and sustainable technology, heterogeneous catalytic sys-
tems exhibit enormous potential without a doubt for the sake of
obtaining high-yield production of biodiesel.
As far as we know, recent progress in biodiesel via catalytic es-
terification and transesterification by using functionalized organic
polymer-based catalysts has not been systematically described.
Herein, in this review, we aimed to summarize advancements and
applications of organic polymers-based catalytic materials for bio-
diesel synthesis by chemo-catalyzing esterification and transesteri-
fication reactions.
2. ORGANIC POLYMER
2.1. Acidic Porous Polymer
In fact, in comparison to homogeneous catalysts, with the aim
of improving the isolation and recycling of catalysts, many hetero-
geneous catalytic materials are extensively employed [48]. Among
them, directly sulfonating polymer frameworks to introduce active
sulfonic acid group (-SO3H), which shows a satisfactory activity
and reasonable recyclability in esterification and transesterification
for biodiesel synthesis, is regarded as a simple and convenient
manner.
FDU-15-SO3H, manufactured by sulfonation of FDU-15
mesoporous polymer, was reported to be used as an active solid
acid for biodiesel production, including palmitic acid esterification
with methanol and oils transesterification [49]. Thanks to its ther-
mally stable organic structures, large surface area (447 m2/g),
unique mesoporous channels (2.7 nm) and abundant acid amount
(1.0 mmol/g), 99.0% yield of fatty acid methyl esters (FAMEs)
could be achieved from the transesterification of soybean oil at
140°C with methanol/oil weight ratio of 1:1. With respect to this
kind of acid polymers for biodiesel production, Liang et al. devel-
oped several -SO3H functionalized organic polymer acids for bio-
diesel synthesis via transesterification of crude oils [50-52]. As
depicted in Scheme 2, sulfonic acid functionalized resorcinol–
furaldehyde was prepared by using resorcinol–furaldehyde and
hydroxy-ethylsulfonic acid, and its high acid density was deter-
mined to be 4.5 mmol/g. Along with a BET surface of 143 m2/g,
nearly 100% FAMEs yield could be obtained at 70°C in 8 h [50].
Due to the fixation of water by surface hydroxyl group that would
prevent the hydrolysis of esters, even 96.4% yield of FAMEs could
be maintained when adding 20% water content. More importantly,
after washing with petrol ether and drying at 80°C for 4 h, the re-
covered activities remained unchanged during six recycles, indicat-
ing its good stability. By copolymerization of 3-[(2-sulfoethoxy)
carbonyl] acrylic acid with divinylbenzene (DVB), a novel polymer
2192 Current Organic Chemistry, 2019, Vol. 23, No. 20
HO OH
HO SO3H
+ C
CHO 80 °C, 72 h
OH
O
Scheme 2. Resorcinol–furfural based polymer acid synthetic path [50].
CH2Cl
AIBN
+
* * CH2Cl
H3PW12O40 or H4SiW12O40
* * H2C
Scheme 3. Preparation of the two polymeric acid catalysts [58].
acid bearing both sulfonic and carbonyl acid groups was developed
[51]. Similarly, through the chemical oxidation, -SO3H functional-
ized polypyrrole polymer solid acid was also prepared via polym-
erization of N-butanesulfonic acid pyrrole [52]. Thees two catalysts
were then developed successfully for biodiesel preparation by
transesterification of rapeseed oil, showing a high yield of FAMEs.
However, Liu’s research group investigated the properties of
poly-divinylbenzenes based polymer acid catalyst for biodiesel
synthesis in-depth, especially focusing on dilatability, hydrophobic-
ity, and oleophilicity [53-56]. By polymerization under hydrother-
mal reaction condition using DVB as a monomer, azobisisobuty-
ronitrile (AIBN) as an initiator, and THF/H2O as a solvent, swelling
mesoporous PDVB was synthesized successfully. After using
chlorosulfonic acid for sulfonation in CH2Cl2, effective solid poly-
mer acid catalysts bearing neat organic framework were developed,
exhibiting large surface area (280-380 m2/g), high mesoporosity,
and high concentration of -SO3H (3.9-4.1 mmol/g). Non only the
esterification reaction activity was found to be higher than that of
Amberlyst-15 with greater stability [53]. Furthermore, in order to
study the vital superhydrophobic-oleophilic properties of biodiesel
production by transesterification, a mesoporous, acidic polymer
catalytic material (p-PDVB-SO3H) synthesized through copolym-
erization of DVB and sodium 4-vinyl benzenesulfonate was used
[55]. According to the contact angle test, p-PDVB-SO3H exhibited
superhydrophobic–oleophilic property for triolein and methanol,
which resulted in fine miscibility and high exposition degree of
catalytic sites for various organic reactants. Compared to common
ZSM-5 zeolite, carbon acid, and Amberlyst-15 catalysts, p-PDVB-
SO3H performed better in terms of both activity and recyclability
towards transesterification. From the industrial view of point, to
Zhang et al.
SO3H
OH HO3S
H HO SO3H
SO3H
180 °C, 4 h
O
n HO3S
SO3H
NH2
* *
N
H2N NH2
NH2
* * H2C
N N
H
*
NH2
PDVB-VBC-TAEA/PW12
NH2R R= H3PW12O40
or
PDVB-VBC-TAEA/SiW12
N N R= H4SiW12O40
HR
NH2R
establish a highly efficient means for biodiesel production, the use
of waste acidulated bone oil has been reported as a novel synergis-
tic catalysis process coupled with organic polymer acid (H-PDVB-
SO3H) and K2O doped porous γ-Al2O3 solid base (γ-Al2O3-K2O).
Due to its commendable reaction activity and satisfying recyclabil-
ity, an effective and economic catalytic system to convert waste oils
into high-quality biodiesel needs to be developed [56]. Although
the afore-mentioned catalysts performed well in both esterification
and transesterification, some extremely dangerous chemicals such
as ClSO3H are used. Zhang et al. presented a simple process by
using sulfonic monomer directly to form a stable polymer acid that
was cross-linked with poly(ether sulfone) containing high -SO3 H
content [57]. Because of its stronger acid strength and better swel-
ling property as compared to Amberlyst-15, the esterification activ-
ity was determined to be five times greater than that of Amberlyst-
15. The well-dispersed H3PW12O40/H4SiW12O40 nanoparticles im-
mobilized in a mesoporous polymer, PDVB-VBC-TAEA-
PW12/PDVB-VBC-TAEA-SiW12 Scheme 3, were fabricated and
served as heterogeneous acid catalysts for highly efficient and se-
lective esterification of lauric acid to methyl laurate [58]. Methyl
laurate yield of 98% was obtained at 65°C for 3h, and the high yield
could still remain when the reaction volume increased to 100 mL,
accordingly. More importantly, the environmental-benign and sus-
tainable catalysts showed good stability during five cycles, indicat-
ing their great potential in prospective utilization.
Sustainably, appropriate disposal of polymeric wastes (i.e.,
modification of polymeric wastes into useful products) is treated as
a major concern currently, so as to make some vital contributions to
the survival of our modern society [59]. With respect to this con-
text, innovative ways for utilization of waste expanded polystyrene
Chemo-catalytic Esterification and Transesterification
N (I) AIBN, solvothermal, 120 °C, 24 h
+ (II) ClSO3H, RT, 4 h
Triallylamin 1,4-Divinylbenzene
3H
SO
N
SO3H
HO3S SO3H HO3S SO3H
Scheme 4. Schematic synthesis of the sulfonated porous organic polymer PDVTA-SO 3H.
to synthesize interesting solid polymer acid catalyst are needed. To
our delight, some valuable researches were reported regarding this
vital project [60-63], including polystyrene cross-linked with di-
vinylbenzene containing -SO3H, hypercross-linked polystyrene
sulfonic acid catalysts, partially sulfonated polystyrene, and poly-
styrene-supported fluoroalkyl superacid. It is noteworthy that su-
peracid polymer-supported catalyst has rarely been reported to date,
other than commercial Nafion with low acidity of 0.9 mmol/g and
low surface area that will limit practical application regarding or-
ganic synthesis [64]. According to a combination of iridium-
catalyzed C–H borylation and Suzuki–Miyaura coupling reactions,
polystyrene-supported superacid fluoroalkyl sulfonic acid (sPS-S)
was successfully developed and used in the esterification of dode-
canoic acid and transesterification of triglycerides with methanol.
The sPS-S catalyst exhibited remarkably better activity than that of
Amberlyst-15, along with wonderful reusability in quantitative
recovery yields during ten consecutive runs.
Apart from polystyrene, polyaniline was synthesized through
the oxidative polymerization of aniline [65]. On the account of their
nitrogen-containing groups, alkaline nature of polyaniline will al-
low this polymer to be easily doped with protonic acids, aiming to
obtain the “polyaniline salt”. It was reported that the polyaniline
salts possessed a high level of acidic sites, exhibiting good envi-
ronmental and thermal stability [66]. Accordingly, these favorable
properties make polyaniline salt as a potential catalytic material to
be used for biodiesel production. Drelinkiewicz et al. prepared
some organo-sulfonic acids modified polyaniline acid catalysts,
including methanosulfonic (MSA-Pani), camphorosulfonic (CSA-
Pani) and lignosulfonic (LG-Pani) acids, and applied in transesteri-
fication and esterification reactions for biodiesel synthesis [67]. It
was found that the acid site strength and surface chemical proper-
ties of the catalysts demonstrated the important effect in their cata-
lytic performance. Among all investigated catalysts, LG-Pani and
MSA-Pani samples were determined as the two most potentials,
which should be ascribed to their high-activity and well-stability in
the reaction mixture, especially for transesterification of triglyc-
erides with methanol. Similarly, p-toluenesulfonic acid functional-
ized polyaniline polymer acid catalyst was also synthesized and
Current Organic Chemistry, 2019, Vol. 23, No. 20 2193
SO3H
SO3H
3
H
SO
SO3H
HO3S
HO3S SO3H
utilized for producing biodiesel from waste cooking oils [68]. The
physicochemical property of the as-synthesized catalytic material
was characterized detailly, and upon being employed in transesteri-
fication the biodiesel yield was obtained by 97.1%. Furthermore,
the catalyst performed good stability during consecutive 10 cycles,
showing its industrial potential for biodiesel production.
A new hypercrosslinked supermicroporous polymer, being in-
expensive and scalable, was developed as an efficient metal-free
solid acid catalyst for biodiesel production via esterification of
FFAs [69]. It was prepared by Friedel–Crafts alkylation between
carbazole and α,α’-dibromo-p-xylene using Lewis acid catalyst
FeCl3, followed by direct sulfonation with ClSO3H. The obtained
HMP-1-SO3H polymer solid acid catalyst showed a BET surface
area of 346 m2/g, the pore size distribution of 1.54 nm, and a high
acid density of 3.7 mmol/g. Due to to its good physicochemical
property, the new hypercrosslinked microporous organic polymer
HMP-1-SO3H exhibited excellent activity and stability regarding
biodiesel production at room temperature, showing huge potential
in future applications. In a similar manner, as developed by the
same group, another sulfonic acid functionalized porous organic
polymer (PDVTA-SO3H) that was synthesized by solvothermal co-
polymerization of DVB with triallyl amine followed by sulfonation
using ClSO3H (Scheme 4) was also evaluated for biodiesel synthe-
sis via esterification of FFAs at room temperature [70]. Owing to its
high surface area of 406 m2/g, hierarchical porosity distribution of
1.5 nm, 2.6 nm and 4.8 nm, and relatively high Brønsted acidity of
2.3 mmol/g, high yields (92-98%) of various biodiesel compounds
at room temperature could be achieved by using this active and
reusable polymer acid.
Considering the perspective of green and sustainable catalysis,
the finely heterogeneous organic porous catalysts employed for
producing biodiesel with high yield require certain crucial features,
including (a) adjustable hydrophilicity and hydrophobicity, (b)
good swelling property, (c) ordered interconnected system of pores,
and (d) strong active acid sites [71, 72]. With regard to these, Pan et
al. developed an innovative and effective mesoporous polymer
acidic catalyst (PD-En-SO3H) with multi-SO3H groups, and the
2194 Current Organic Chemistry, 2019, Vol. 23, No. 20
N O THF, RT N N
N + S
O O 72 h
Azobisisobutyronitrile
PDVB
AIBN
Scheme 5. The pathway for the preparation of the acidic core-shell IL polymer catalyst.
sulfonation of ethylenediamine (En)-functionalization of meso-
porous poly-divinylbenzene (PD) was regarded as the key synthetic
step [73]. The resulting PD-En-SO3H catalyst was illustrated to
possess abundant mesoporosity, high BET surface area (369.0
m2/g), and high acid density (2.1 mmol/g). For both the esterifica-
tion of FFAs to produce biodiesel and the synthesis of levulinate
esters (biodiesel additive) from fructose, PD-En-SO3H showed
satisfactory yields, which were better than those of commercial
Amberlyst-15 and Nafion NR50. In addition, during the consecu-
tive four cycles, no obvious loss of its reactivity was determined.
Interestingly, sulfonic acid-functionalized organic knitted porous
polyaromatic (OPPs) microspheres, which were synthesized from
pyrene, anthracene, and naphthalene by Friedel–Crafts alkylation,
crosslinking and self-polymerization reactions [74], were also suc-
cessfully fabricated and employed in biodiesel synthesis from es-
terification of FFAs and transesterification of triglycerides. Because
of having a large number of acid sites, high swelling ability, and
excellent hydrophobicity, pyrene-based OPPSO3H-1 exhibited the
best performance among all the synthesized materials. Furthermore,
OPPSO3H-1, OPPSO3H-2, and OPPSO3H-3 were all determined to
be stable without any activity decreases upon being employed dur-
ing the five consecutive recycles, indicating their large promising
applications for green and sustainable chemistry. Solvent-free tech-
niques for ordered mesoporous polymers production were devel-
oped by Liu et al., such as amino functionalized ordered
mesoporous polymers (OMP-NH2) [75], and sulfonic acid-
functionalized mesoporous organo-silica [76]. By simply grinding
the mixtures of solid raw precursors (aminophenol, terephthalde-
hyde), using block copolymer templates, and curing at 140-180°C,
OMP-NH2 can be achieved accordingly [75]. After being function-
alized with active acid sites, multifunctional polymeric catalysts
bearing the vital large surface area, abundant and ordered
mesopores, good thermal stability, controllable concentrations, and
homogeneous dispersion of active sites were obtained and used in
conversion of low-grade resources into valuable chemicals and
clean biofuels with excellent catalytic activities, especially for the
transesterification of sunflower oil with methanol. The solvent-free
methodology could be regarded as a facile, green and sustainable
manner to synthesize OMPs that can be modified with versatile
groups. More importantly, this will offer great potential for the
production of value-added chemicals and biofuels via heterogene-
ously catalytic approaches industrially.
Although most of the above-mentioned functionalized organic
polymers exhibited good activity and selectivity for biodiesel syn-
thesis by esterification and transesterification, the utilization of
relative expensive precursor, singleness structure and need of some
Zhang et al.
SO3 H2SO4 N N SO3H
HSO4
IL
SO3H
Shell N
EtOH, IL N
n HSO4
AIBN Core
extremely dangerous chemicals such as ClSO3H for modification
will restrict their flourish development, to some extent. With re-
spect to these, direct using the sulfonic monomer as a precursor,
modifying polymeric wastes into useful products, and introducing
green synthesis techniques such as solvent-free approach could be
deemed as the possible future improvements.
2.2. Acidic Ionic Liquid Polymer
Ionic liquids (ILs), a new eco-benign approach towards modern
chemistry, containing advantages of negligible vapor pressure, fine
physicochemical stability along with widely electrochemical poten-
tial window, are applicated in wide fields such as catalysis, organic
synthesis, and gas absorption [77-82]. However, large-scale appli-
cation of ILs is restricted due to their disadvantages including high
viscosity, expensive cost, and tanglesome recovery protocol. With
respect to this, a combination of ILs with the supported materials
(i.e., molecular sieves, polystyrene, and magnetic nanoparticles)
that show advantages including high surface areas, simple recy-
clability, and fine stability, were found to demonstrate outstanding
performance regarding the catalysis area [83-87]. However, it is
suggested that the incorporation of ILs into the polymer chains
could combine the specific characteristics of ILs with common
natures of polymers, presenting innovative functionalities [88, 89].
In addition, ideally, polymer ILs (PILs) which can integrate the
synergistic advantages of ILs and polymers into a whole will also
provide the interesting multifunctional polymeric ILs materials as
to improve their catalytic performance [90].
In addition to several acidic porous polymers contributions,
Liang et al. also presented some other interesting studies on the
development of acidic ILs polymers for biodiesel production [91-
95]. Similarly, three acidic ILs polymers prepared by the copolym-
erization of acid ILs oligomers with DVB were evaluated for bio-
diesel production using the waste oils as sources [91-93]. It was
found that through both the transesterification of triglycerides and
the esterification of FFAs, total biodiesel yield could reach 99.0%
at a relatively low temperature of 70°C. However, because of the
poor solvent medium and lower DVB content adopted during the
precipitation polymerizations for poly divinylbenzene (PDVB)
synthesis, rich residual double bonds were found accordingly [96].
As illustrated in Scheme 5, core-shell structure acidic ILs polymer
catalyst was developed by radical capture of the acidic IL monomer
[SO3H(CH2)3Vim][HSO4] connected through the residual double
bonds located at the surface of PDVB. On the account of active acid
ILs that were attached on the surface of PDVB sphere, the active
sites could be accessed by the reactants easily, leading to high bio-
diesel yield through the one-pot manner using waste oils feedstocks
under mild reaction conditions (70°C). In a similar manner, co-
Chemo-catalytic Esterification and Transesterification
* *
N N
100 °C, 24 h
N +
N N
* *
Vim DVB PDVB-Vim
Scheme 6. Synthetic route of PDVB-[C1Vim][SO3CF3 ].
polymerization of acidic ILs protonated by phosphoric acid with
DVB to fabricate PILs was also developed [97]. Starting from the
vegetable oil, high conversion of 94.2% was achieved at 70°C
within 4 h, and the reusability of this PILs could be maintained for
four times.
Although the afore-mentioned PILs catalysts have been deter-
mined to exhibit good performance for biodiesel production, the
detailed structure-function relationship in terms of the important
physicochemical properties such as hydrophobicity and swelling
ability were ignored. Accordingly, Liu et al. made a very significant
contribution to this context [98]. As depicted in Scheme 6, a super-
hydrophobic mesoporous polymer PDVB-[C1Vim][SO3CF3] was
prepared by cascade processes involving solvothermal copolymeri-
zation method, quaternary ammonization, and anion-exchange with
CF3SO3H. It was determined that the high BET surface of 181 m2/g,
contact angle (CA) of 80° for water droplet and close to zero for
methanol, and tripalmitin of PDVB-[C1Vim][SO3CF3] were the key
points for the excellent catalytic activity in the transesterification
reaction. Interestingly, the hydrophobic mesoporous polymer ILs
catalyst was found to perform better even than that of the corre-
sponding homogeneous ILs, along with very good recyclability. In
the same synthetic way, Liu et al. presented another two interesting
polymeric materials [99, 100]. In particular, a micro–meso–
macroporous polymer (MOPs) functionalized with strong acidic ILs
(MOP-aniline-[C4][SO3CF3])was successfully developed and util-
ized for biodiesel production via transesterification of sunflower oil
with methanol [100]. In the assitance of the strong acidic sites of
ILs in MOP-aniline-[C4][SO3CF3], >90% yield of biodiesel was
obtained at 80°C for 16 h, which were higher than H3PW12O40,
Amberlyst-15, and SBA-15-SO3H respectively.
Wu et al. proposed a novel approach for the synthesis of acidic
PILs catalytic materials with macro-porous structure, wherein
Fe3O4 particles were used as the hard template [101]. By free radi-
cal polymerization of Brønsted acid IL [VSIM][HSO4] and removal
of Fe3O4, the acidic PILs with macroporous polymeric networks
were obtained and employed in esterification reaction of oleic acid
with ethanol for biodiesel production, accordingly. The combina-
tion of macropore with PILs matrix that could markedly lower the
mass transfer resistance and strong acid IL sites afforded a high
biodiesel yield of 92.6% at 80°C. Moreover, this interesting PILs
could be simply separated and demonstrated good recyclability
during 6 times, indicating its significance in a green chemical proc-
ess. A neoteric PIL catalyst, P(VB-VS)HSO4, which was prepared
by facile immobilization of ILs onto the 1-vinylimidazole-based
crosslinked copolymer microsphere, was developed for biodiesel
production from a novel non-edible resource soapberry oil by
(trans)esterification reaction [102]. Benefiting from their distinct
physicochemical properties, including the high surface area (100.1
m2/g), abundant surface-inter mesopores (18.9 nm of average pore
diameter), good mechanical strength (81 N), superior thermal sta-
Current Organic Chemistry, 2019, Vol. 23, No. 20 2195
* * * *
N N
CH3I CF3SO3H
N
I CF3SO3
* * * *
PDVB-[C1vim][I] PDVB-[C1vim][CF3SO3]
bility, and oleophilic-hydrophobic feature, a high biodiesel yield of
95.2% was acquired under the optimized reaction conditions:
150°C, 8.0 h, 29:1 methanol to oil molar ratio, and 8.7 wt% catalyst
dosage. In addition, admirable recyclability was also determined,
and the main soapberry biodiesel fuel properties were determined
to meet the biodiesel standard ASTM D6751. Pan et al. developed
mesoporous polymeric solid acid (MPD-SO3H-IL) bearing both
acidic ILs moieties and sulfonic acid group (Scheme 7), which was
used for biodiesel production from crude Jatropha curcas oils
[103]. Impressively, MPD-SO3H-IL was found to possess abundant
mesopores (27.0 nm), high surface area (281.0 m2/g), and high acid
density (2.6 mmol/g). Upon assessing its catalytic activity, 98%
oleic acid conversion was determined in the esterification of oleic
acid with methanol, and 94% biodiesel yield was also achieved by
simultaneous transesterification and esterification of crude Jatropha
curcas oil at 160°C in 8 h. However, most of the aforesaid PILs that
were prepared using expensive precursor-like DVB, it is desirable
and challenging to synthesize acidic polymers catalyst from cheap
sources. With respect to this context, to continue their works, acid
ILs-functionalized mesoporous melamine-formaldehyde polymers
catalysts were also developed by Pan et al. [104]. As demonstrated
in Scheme 8, the novel acid ILs-functionalized mesoporous cova-
lent organic polymer (MMFP-IL) was prepared by quaternary
ammonization of both abundant aminal groups and triazine rings in
the low-cost mesoporous melamine-formaldehyde polymer
(MMFP) with 1,3-propanesultone, followed by treatment with
H3PW12O40 (HPW). Biodiesel yield of 95% via esterification of
oleic acid was obtained at 90 °C within 3 h, which was found to
outperform than those of some other commercial acids (i.e., Amber-
lyst-15, Nafion NR50). Additionally, relatively low activation en-
ergy of Ea=35.3 kJ/mol was assessed by kinetic analysis of the
first-order reaction. In addition, to verify the catalytic performance
of MMFP-IL, the comparative study of various acid catalysts for
the esterification reaction was carried out under the reaction condi-
tions of MeOH to an oleic acid molar ratio of 12:1 and the catalyst
dosage based on 0.18 mmol H+ content at 90 °C for 3 h. Physico-
chemical properties and catalytic performance of different acid
catalysts were demonstrated in Table 1. When there was no catalyst
in the reaction mixture, the yield was very low (entry 1). Although
commercial acid resins (i.e., Amberlyst-15 and Nafion NR50) are
effective for numerous reactions, their catalytic rates and biodiesel
yields were inferior to those of MMFP-IL (entries 3–4). The similar
results were also found for MFP-IL, which might be due to its
low acid density and BET surface area (entry 5). But, MMFP-IL
exhibited outstanding catalytic performance with a high yield
(95%) under the mild reaction conditions, which was even compa-
rable to that of homogeneous H3PW12O40 (entry 2). The outstanding
catalytic performances of MMFP-IL could be ascribed to its re-
markable properties, such as abundant mesoporous structure with
large BET surface area, strong acidity, high acid density, and fine
distribution of acid sites.
2196 Current Organic Chemistry, 2019, Vol. 23, No. 20 Zhang et al.

O O
* * S
O
AIBN,ethyl acetate N 1.
N
N *
100 °C, 24 h N 2. H2SO4

* * * *
SO3H
N N
N 3. ClSO3H
N
HSO4 * HSO4 *

SO3H SO3H

Scheme 7. Preparation of the mesoporous polymeric solid acid (MPD-SO3H-IL).

NH

NH2 N N

N N Solvothermal method HN N NH
Paraformaldehyde
H2N N NH3
HN NH

Low cost N N N N

N N N N N N
H H H H

O O
S
O

NH
H2PW12O40
NH
N N SO3H
N N SO3
H2N N NH H3PW12O40
H2PW12O40 H2PW12O40 HN N NH

HN NH SO3H
HN NH SO3
N N N N
N N N N
N N N N N N
H H H H
N N N N N N
H2PW12O40 H H H H
H2PW12O40

SO3H HO3S
SO3 SO3

Scheme 8. Synthetic routes of MMFP-IL polymer catalyst.

Chemo-catalytic Esterification and Transesterification
Table 1. Physicochemical characteristics and activities of different acid catalysts [104].
Entry Catalyst Aciditya [mmol/g] SBETb [m2/g]
1 Blank n.a.e
2 H3PW12O40 1.7
3 Nafion NR50 0.8
4 Amberlyst-15 4.7
5 MFP-IL 1.1
6 MMFP-IL 2.2
a
Acidity identified by the titration.
b
BET surface area.
c
Temp.=Temperature.
d
Molar ratio of MeOH to oleic acid.
e
n.a.=not available.
f
The dosage of the catalyst is based on 0.18 mmol H+ content.
Combination of active ILs with organic polymers provide
versatile PILs catalytic materials that can not only perform well in
biodiesel synthesis but also show multi-functionalization. However,
the relatively expensive ILs, the low loading capacity of ILs, and
ambiguous structure of PILs are the presentative disadvantages.
Therefore, how to immobilize more active ILs onto the polymers
and introduction of advanced characterization techniques to identify
the detailed structure-function relationship, may open a significant
door for PILs.
2.3. Basic Organic Polymer
In addition to acidic polymers catalysts, some more active and
basic polymeric materials for catalytic transesterification reaction to
prepare biodiesel were also presented [105-109]. Verkade et al.
described an interesting basic organic polymer catalyst (Merrifield
resin-supported azidoproazaphosphatrane catalyst resin-
N3=P(MeNCH2-CH2)3N) for biodiesel production from soybean oil
and methanol [105]. At room temperature, nearly quantitative con-
version of oils could be achieved and the activity of the polymer-
supported catalyst was twice as that of the homogeneous analog
PhCH2N3dP(MeNCH2CH2)3N for transesterification. It was sug-
gested that the Lewis basic azido moiety, which was stabilized by
electron richness and steric protection supplied by the methyl-
substituted proazaphosphatrane moiety, was determined as the ac-
tive center. Active NaOH supported onto poly (sodium acrylate)
polymers (NaOH/NaPAA) was synthesized by in situ polymeriza-
tion of acrylic acid with an over-neutralization by adding an excess
of NaOH and employed for biodiesel production via transesterifica-
tion of rubber seed oil with methanol [106]. To be served as a base
superabsorbent catalytic material along with good water absorbency
and water retention and a strong base strength of 15.0 < H_ < 18.4,
NaOH/NaPAA afforded a high biodiesel yield, which was compa-
rable to homogeneous NaOH catalyst. More importantly, it demon-
strated a good water resistance (water concentration less than 2
wt.%) for transesterification, opening the promising ability to em-
ploy low-grade oils as to lower the cost for biodiesel production,
accordingly.
Among factors affecting catalytic properties, textural parame-
ters, wettability, and adsorption features were reported as the most
important kinds [110, 111]. With respect to these, superhydropho-
bic porous solid base and superhydrophobic porous PIL solid base
[107, 109], were designed and synthesized for biodiesel synthesis
by transesterification of oils with methanol. Similarly, the two stud-
Current Organic Chemistry, 2019, Vol. 23, No. 20 2197
Temp.c (oC) Time (h) Molar Ratiod Catalyst (wt%) Yield (%)
n.a.e 90 3 12 n.a.e 10
4.2 90 3 12 5f 93
f
0.1 90 3 12 11 70
f
50 90 3 12 2 74
f
20 90 3 12 8 69
f
283 90 3 12 4 95
ies both revealed that the significant super-hydrophobicity played a
critical role in enhancing its catalytic activity in terms of trans-
esterification from oils and methanol. According to contact angles
tests, the contact angles of methanol and oils were negligible, indi-
cating its good miscibility for both methanol and oils [112]. None-
theless, the high angle of 147° for hydrophilic glycerol by-product
was also found, indicating its anti-wetting properties for glycerol
and thus the molecules would quickly leave the hydrophobic cata-
lysts that could promote transesterification, accordingly. Therefore,
the two basic polymeric catalysts demonstrated super-hydro-
phobicity, good miscibility for reactants, and incompatibility with
the byproduct glycerol, which endowed high reactivity and good
reusability for transesterification.
Basic organic polymeric catalysts demonstrated excellent cata-
lytic activity for transesterification of oils, only at the methanol
reflux reaction condition. Nonetheless, high-quality oils bearing
low acid values must be employed otherwise saponification will
occur that leads to lower biodiesel yield with poor biodiesel quality.
In this regard, fabrication of basic polymers catalysts resistant to
acids/water or acid-base bifunctional polymeric catalysts is highly
preferable.
2.4. Organic-inorganic Hybrid Polymer
As mentioned above, PILs not only endow unique features of
ILs to polymers but also show exceptional characters including
mechanical and thermal stability, corrosion resistance, processabil-
ity, and durability [113-115]. Based on the versatile adjustability
and functionality of PILs, in addition to organic polymers frame-
works, of another particular interest is the heterogenization of ac-
tive PILs onto advisable inorganic solid materials to design an in-
teresting organic-inorganic hybrid polymeric catalyst for biodiesel
production, such as poly (butane sulfonic acid pyrrole) coated mag-
netic iron oxide [116], acidic IL-functionalized ordered mesoporous
polymers [117], poly(phosphotungstate-based acid ILs) immobi-
lized on magnetic nanoparticle [118], magnetically mesoporous
material (Fe3O4@SiO2@SBA-15) grafted basic PILs [119], and
magnetically recyclable acid PILs decorated with hydrophobic
regulators [120].
Wu et al. developed poly(phosphotungstate-based acid ILs)
immobilized on magnetic nanoparticle for biodiesel production via
esterification of oleic acid with ethanol [118], as depicted in
Scheme 9. It was prepared by grafting the copolymer derived from
the free radical initiation copolymerization of IL monomer [SO3H-
2198 Current Organic Chemistry, 2019, Vol. 23, No. 20 Zhang et al.

O O
S
O
N N SO3H
N
N
H2SO4 HSO4 Fe3O4 Fe3O4
1
* *

AIBN
N
H3PW12O40
3-
2 N 1/3 PW O
12 40
O
O
Fe3O4 MPS Si O *
Fe3O4 *
O SO3H
O
3

Scheme 9. The synthetic route to the poly (phosphotungstate-based IL) hybrid magnetic composite catalyst.

N N
+ Br N N
Br

1
Br
N N N
N
+ Br(CH2)4Br N N
Br
2

TEOS P123 TEOS MPTMS 1 2 AIBN

Fe3O4 Fe3O4 Fe3O4 Fe3O4 SH
NH3·H2O H+ TMAOH
nSiO2 nSiO2 nSiO2
mSiO2 mSiO2
Poly (ionic liquid) FnmS FnmS-SH

OH
Fe3O4

nSiO2 N N
mSiO2

FnmS-PIL

Scheme 10. Schematic illustration for the fabrication of magnetic mesoporous material (Fe3O 4@SiO 2@SBA-15) grafted basic PILs.

PVIM]-[HSO4] with cross-linker DVB, onto 3-(trimethoxysilyl)
propyl methacrylate (MPS)-modified Fe3O4 nanoparticle, followed
by anion exchange with HPW. By means of a response surface
methodology (RSM) which can improve the conversion and effi-
ciency of the esterification reaction, 93.4% biodiesel yield was
obtained at the optimized reaction condition of 90 °C, alcohol/oil
molar ratio of 12:1, 13 wt% catalyst dosage within 5 h. More im-
portantly, thanks to the high superparamagnetic saturation, it could
be simply separated under an external magnetic field shortly, and
good reusability could also be observed after six recycles.
However, compared with [118], immobilization of actively
acidic or basic PILs onto opportune porous supports with high sur-
face area seems to be more preferable. Moreover, in consideration
of the green process, with respect to organic transformations, to
combine active moieties with ease of separation and product recov-
ery is highly necessary. To address these, Zhang et al. developed
two interesting magnetically recyclable PILs catalysts for biodiesel
synthesis, including magnetic mesoporous material (Fe3O4@SiO2@
SBA-15) grafted basic PILs for transesterification reaction [119],
and magnetically recyclable acid PILs decorated with hydrophobic
regulators for esterification and transesterification reactions [120].
As illustrated in Scheme 10, a magnetical mesoporous support
Fe3O4@SiO2@SBA-15 (FnmS) was prepared by the facile sol-gel
and hydrothermal methods, after immobilizing PILs onto FnmS via
radical polymerization and anion exchange, the final basic FnmS-
PIL catalyst was achieved. By direct transesterification of non-
edible oil source Firmiana platanifolia L.f. with methanol, 92.8
wt% biodiesel yield was obtained under mild reaction conditions
(9/1 methanol/oil molar ratio, 4 wt% catalyst dosage at 85 °C in 5
h). This should be attributed to its uniform core-shell structure, high
surface area (153.2 m2/g), mesoporous pore size (4.1 nm), and the
high base concentration (2.3 mmol/g). In addition, by a pseudo-
first-order model, a kinetic study revealed the activation energy as
51.6 kJ/mol. More importantly, the catalysts were capable of being
recovered simply with a magnetic force and showed good reusabil-
ity during five consecutive recycles.
As reported [121], biodiesel yield will be compromised by es-
terification/hydrolysis equilibrium when a certain amount of water
exists in the reaction medium, and acidic catalytic materials used
are damaged by water to an extent. In order to circumambulate this
Chemo-catalytic Esterification and Transesterification
O O
S r.t.
N N + O
N N
+ Br(CH2)4Br
TEOS P123 TEOS
Fe3O4 Fe3O4
NH3·H2O H+
nSiO2
Poly (ionic liquid)
1 2 AIBN
CF3SO3H, H2SO4, HCl, Fe3O4
H3O40PW12
nSiO2
mSiO2
FnmS-PIL
Scheme 11. Synthesis of magnetically hydrophobic acid catalysts.
issue, magnetically acidic PILs with varying hydrophobicity and
controllable acidity were designed and utilized to produce biodiesel
through the esterification of oleic acid and (trans)esterification of
crude Euphorbia lathyris L. oils, as demonstrated in Scheme 11
[120]. Accordingly, FnmS-PIL (1a, C8) core-shell structure catalyst
was determined to have a large BET surface area (128.1 m2/g),
uniform mesoporous structure (4.2 nm), strong magnetism (12.4
emu/g), high acidity (2.14 mmol/g), strong acid strength (strong
electron-withdrawing anion CF3SO3− effect, −8.2 < H0 < −5.6), and
strong hydrophobicity (water contact angle: 115.4°). Importantly,
when using crude Euphorbia lathyris L. oils with an acid value of
24.59 mg KOH/g as the feedstock, a high biodiesel yield of 91.7%
was obtained by simultaneous esterification and transesterification
reactions. It is worth noting that biodiesel yield could be maintained
above 90% even with a water content of 6 wt% of Euphorbia lathy-
ris L. oils. More importantly, the FnmS-PIL (1a, C8) catalyst could
be recycled facilely by a magnet and showed robust catalytic activ-
ity toward biodiesel synthesis with 87.5% yield in five recycles.
Heterogenization of active PILs on advisable inorganic solid
materials to design an interesting organic-inorganic hybrid polymer
catalyst is of high interest for biodiesel synthesis. The
physicochemical property of inorganic material such as porosity,
surface area, and magnetism is recommended to be considered
firstly. Moreover, immobilization of more content of active PILs
will also be of help to achieve a high yield of biodiesel.
2.5. Functionalized Biopolymer
In addition to the aforesaid as-synthesized organic polymers ac-
cording to some corresponding organic reactions such as oxidation,
free radical polymerization, Friedel–Crafts alkylation and so on,
direct utilization of natural abundant biopolymers followed by sim-
ple modification as to prepare the functionalized organic bio-
polymers is also being deemed as a valuable manner. In this con-
text, some interesting studies were presented with relevant com-
mendable results, accordingly. A biopolymer, chitosan, was used as
a novel substrate for the immobilization of calcium oxide (CaO). In
Current Organic Chemistry, 2019, Vol. 23, No. 20 2199
N N SO3
1
Br
N N
N N
Br
2
MPTS
Fe3O4 Fe3O4 SH
C2H5Si(OC2H5)3
nSiO2 or CH3(CH2)7Si(OC2H5)3 nSiO2
mSiO2 mSiO2
FnmS =C2, C8
FnmS-SH (C2, C8)
3-
CF3SO3, HSO4, Cl, 1/3 PW12O40
N N
SO3H
3-
1a CF3SO3, C8 2a HSO4, C8 3a Cl, C8 4a 1/3PW12O40 , C8
3-
1b CF3SO3, C2 2b HSO4, C2 3b Cl, C2 4b 1/3PW12O40 , C2
detail, to obtain a stable immobilized catalyst, the chitosan beads
with immobilized CaO were cross-linked with glutaraldehyde. Two
crosslinking parameters including crosslinking time and glutaralde-
hyde concentration were studied to reveal the optimal immobiliza-
tion conditions, which were 30 min and 0.22 mol L−1, respectively.
Under those conditions, an immobilized catalyst with a very low
degree of CaO leaching could be obtained. By catalyzing the trans-
esterification of soybean oil with methanol, under the optimal reac-
tion conditions of 3 h of reaction time at 60°C, methanol to oil mo-
lar ratio of 13.4 and catalyst loading of 13.78 wt%, the equilibrium
conversion of soybean oil was 97%. In addition, the chitosan-based
immobilized CaO catalyst synthesized by an easy and energy-
efficient process could be reused at least five times. [122]. In a
similar manner, chitosan with sulfonic acid groups was also devel-
oped as an efficient, environmentally friendly heterogeneous cata-
lyst for the esterification of palmitic acid with methanol into biodie-
sel. The sulfonic acid groups were introduced onto chitosan (CT)
through cross-linking with sulfosuccinic acid (SSA). It was found
that the catalytic activity increased as the number of sulfonic acid
groups present in chitosan was increased, while the catalytic activ-
ity decreased with large amounts of sulfonic acid groups which
should be attributed to the limitation of diffusion. The catalytic
stability of the CT4 (2.08 mmol sulfonic acid groups/g) sample was
evaluated through consecutive batch runs performed with the same
catalyst sample, and its catalytic activity could be stabilized after
the second batch. The CT4 catalyst was also used as a catalyst in
the esterification of oleic and stearic acids and methanol. A good
catalytic activity of CT4 for the different substrates used in the
esterification was also determined, accordingly [123]. Another im-
portant biopolymer, cellulose, is widely distributed in nature and
it exhibits biocompatibility to biological molecules, easy modifica-
tion with usual ligands, and suitable porosity for high adsorption
capacity [124-126]. Porous cellulose beads (CBs) were prepared
using the ionic liquid as a solvent and then further modified using
different reagents including ethylenediamine (EDA), diethylene-
triamine (DETA), triethylene tetramine (TETA), and 4-
2200 Current Organic Chemistry, 2019, Vol. 23, No. 20
aminostyrene (AST). These CBs were used as the carriers for im-
mobilization of H3PW12O40 (HPW). The results indicated that CB-
(AST-HPW)n possessed higher amounts of HPW and stronger cata-
lytic activity for biodiesel production, showing a high biodiesel
conversion yield of 96.2% under optimal conditions for yellow horn
oil esterification [127].
CONCLUSION AND OUTLOOK
Efficiently selective transformation of liquid biomass resources
into biodiesel catalyzed by heterogeneous acid or base catalytic
materials is arousing considerable attention because of the promis-
ing advantages such as recyclability, easy separation and environ-
mental friendliness of solid catalysts. In this review, several versa-
tile functionalized polymers-based catalysts synthesized by various
strategies for biodiesel synthesis via transesterification and esterifi-
cation have been summarized. The practical methods for the fabri-
cation of polymeric catalysts usually involve the solvothermal
method, free radical polymerization and acid/base modifications.
However, the obtained catalytic materials are generally mono-
functionalized and disorderly structured. More stimulating studies
must be undertaken for the development of more active, selective,
durable, and multifunctional (i.e., controllable active sites and
strength, and tunable hydrophilicity or hydrophobicity) heterogene-
ous polymer-based catalytic materials for biomass transformations.
The exploration of an easy manner for the large-scale and low-cost
manufacture of porous polymeric catalysts and extension of their
applications from model reactions to real biodiesel production are
also highly required.
Moreover, difficulties in separation and recovery of traditional
organic polymers catalysts from reaction mixtures will restrict their
utilization during biodiesel synthetic process. A feasible solution to
tackle this issue is the development of polymeric composite with
the magnetic property such as the introduction of magnetic Fe3O4,
aiming to provide the new organic polymeric catalysts with the
magnetic property which will allow the efficient recovery by exter-
nal magnetic field without impacting their activity and selectivity.
Last but not least, it is necessary to get more insight into the reac-
tion mechanism and the structure-function relationships of the cata-
lysts, which is of important implication from both a scientific and
practical viewpoint.
CONSENT FOR PUBLICATION
Not applicable.
FUNDING
This work was financially supported by the National Natural
Science Foundation of China (21576059, 21666008), Fok Ying-
Tong Education Foundation (161030), Key Technologies R&D
Program of China (2014BAD23B01), Chinese State Scholarship
Fund (No. 201706670012), and Guizhou Science & Technology
Foundation ([2018]1037, [2017]5788).
CONFLICT OF INTEREST
The authors declare no conflict of interest, financial or oth-
erwise.
ACKNOWLEDGEMENTS
Declared none.
Zhang et al.
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