Molecular Catalysis 441 (2017) 168–178

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Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat

Research Paper

Catalytic transfer hydrogenation of ethyl levulinate to ␥-valerolactone

over zirconium (IV) Schiff base complexes on mesoporous silica with
isopropanol as hydrogen source
Ruiying Wang a , Jianjia Wang a , Huimin Zi a , Yongmei Xia b , Haijun Wang a,∗ , Xiang Liu a
a
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi
214122, Jiangsu, China
b
State Key Laboratory of Food Science & Technology, Wuxi 214122, Jiangsu, China

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

Article history: Zr(IV)-salphen-MCM-41 was prepared by immobilizing a zirconium(IV) Schiff base complex onto the
Received 24 May 2017 surface of MCM-41. The structural properties of the heterogeneous catalysts were characterized by FT-
Received in revised form 8 July 2017 IR, UV, TG, XRD, SEM, TEM, BET, EDX, CO2 -TPD, NH3 -TPD and ICP-OES. Studies on the catalytic properties
Accepted 31 July 2017
of the immobilized Zr(IV)-Schiff base complexes were performed using the reduction and cyclization of
ethyl levulinate (EL) to ␥-valerolactone (GVL) with isopropanol as the hydrogen source. Various reaction
Keywords:
parameters, such as temperature, reaction time, solvent and catalyst loading were carefully investigated.
Ethyl levulinate
The optimal conditions (GVL yield up to 90%) involved the utilization of Zr(Salphen)-MCM-41 as the
Zr(IV)-schiff base complexes
MCM-41
catalyst in isopropanol. The key to heightened reaction performance was the incorporation of the phe-
Isopropanol nolate and aniline groups in the ligands of bound to Zr. This increased the basicity of the catalyst, which
␥-valerolactone subsequently enhances the efficiency of the transfer hydrogenation reported herein. Meanwhile, the
immobilized catalyst can be easily separated and efficiently recycled at least five times without signif-
icant loss of activity. Finally, we proposed a plausible reaction mechanism based on experimental and
characterization data.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
The gradual depletion of fossil fuels and rapid growth of world
population have led researchers on a quest to develop efficient
technology for the generation of sustainable liquid fuels and versa-
tile chemicals from other natural resources [1]. Biomass represents
the fourth most abundant source which can be readily converted
to useful compounds [2,3], such as gluconic acid [4], succinic acid
[5], sorbitol [6], various alcohols [7], 5-hydroxymethylfurfural [8],
levulinic acid (LA) [9], EL [10], GVL [11], etc. The discovery of
biomass-derived molecules has strengthened the energy potential
of this fuel source by bridging biomass raw materials and new target
products [17]. Among those products listed above, GVL has received
considerable attention due to its utility in various research formats
[16]. Notably, it has been used as a monomer for polymers [12], fuel
additives in gasoline and diesel [13], a green solvent for lacquers
∗ Corresponding author at: School of Chemical and Material Engineering, Jiangnan
University, Wuxi, Jiangsu, 214122, China.
E-mail address: wanghj329@outlook.com (H. Wang).
[14], and a coupling agent in dye baths [15]. Currently, GVL is pro-
duced from hemicellulose [18], furfural [19], LA or its ester [20]. A
major strategy that has been explored for GVL synthesis is catalytic
transfer hydrogenation (CTH) of LA and EL [21]. We were particu-
larly interested in EL as it can be derived from cellulose through a
simple hydrolysis process. Additional, EL as the feedstock over LA
considering as a model compound which possibly would not block
the basic sites of the catalyst as LA dose [22], the production of ester
EL from lignocellulose has higher yield, and the products separation
is easier relative to LA [23].
The transformation of EL to GVL can be performed through three
different reduction strategies. One route is the hydrogenation of EL
to GVL in the presence of various metal catalysts (Pd, Ru, Rh, Pt, Re,
Ni, Co, Mo and Cu) under high H2 pressure. This is a less desireable
approach as H2 is obtained through reforming non-renewable natu-
ral gas or fossil [24,25]. Additionally, the catalysts involved in these
strategies often suffer from either low stability or reactivity. The
second approach involves using formic acid (FA), which is a byprod-
uct formed in equimolar proportion during the decomposition of
biomass [26], as an alternative to H2 . Although hydrogen gener-
ation from FA has been reported, these strategies require noble

http://dx.doi.org/10.1016/j.mcat.2017.07.026
2468-8231/© 2017 Elsevier B.V. All rights reserved.
 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178
metals as catalysts (e.g. Pd, Rh, Au, Ru), harsh reaction conditions,
toxic solvents, acids and an external H-donor to initiate catalyst
activity [27]. The third approach enlists the use of alcohols as H-
donors for CTH of EL leading to GVL production. Notably, isopropyl
alcohol (IPA), which is produced from cellulose via degradation
of beta-glucosidase and subsequent reduction of bio-derived ace-
tone, serves as an optimal solvent and H-donor with high hydrogen
generation capacity [28].
The third approach was designed according to Meerwein-
Ponndorf-Verley (MPV) reduction. The reduction reaction of EL
catalyzed by some catalysts (such as ZrO2 [29], ZrO(OH)2 [30], Al-
Zr mixed oxides [31], Zr-HBA [32], Zr-Beta [33], Zr-PhyA [34], etc.)
has been reported. Song and coworkers found that the presence
of a phenolate group could increase the basicity of the catalyst
(Zr-HBA) [32]. Xue and coworkers designed an efficient catalyst (Zr-
CA) with higher basicity by using CA as the building block, which
has phenolate and pyridinic groups around the catalyst, permit-
ting efficient access to GVL from EL [35]. It has also been reported
that increasing the basicity of the catalyst could be favorable for
the CTH reaction [36]. In contrast to the work involving an MPV
reaction, Cu, Fe and Ni also show promise in the selective con-
version of LA and LA-esters to GVL. Xu and coworkers prepared
and screened a series of copper catalysts for the efficient hydro-
genation of LA to GVL in ethanol. Cai and coworkers designed a
Robust Cu−Ni bimetallic catalyst that enhanced the efficiency of
CTH of EL to GVL [37]. However, the activity of catalysts containing
copper, iron and nickel is far less active than the zirconium-based
systems described earlier. The MPV reduction has the high chemical
selectivity toward the groups of aldehydes and ketones. There-
fore, a variety of catalysts mainly based on zirconium as metal
center would be designed within a period of time. Although the
effectiveness of these catalysts has been well demonstrated, sev-
eral obstacles still exist and need to be overcome. This includes
high reaction temperature, long reaction time and low stability or
reactivity of the catalyst.
Transition metal complexes containing Schiff-bases have been
extensively studied due to their potential as catalysts in Suzuki-
Miyaura coupling reactions [38], oxidations of alcohols [39],
epoxidations of olefins [40], and asymmetric methodology [41].
Zirconium-based catalysts also show greater potential due to their
high coordination numbers (as high as 8) and efficiency to form
metal-organic complexes with Schiff base ligands [42]. Interest-
ingly, several heterogeneous materials have also been shown
to support Schiff base ligated metals [43]. Recently, the use of
mesoporous silica has been explored as a metal support. More
specifically, MCM-41has been greatly investigated, due to its high
thermal stability, high surface area, high dispersion, efficient sur-
face functionalization protocols and tunable pore size [44,45].
Moreover, MCM-41 serves as an organic-inorganic mesoporous
hybrid material due to the abundance of surface hydroxyl groups,
which can serve as Brönsted acids to facilitate reactions [46].
With this insight and the results from our previous work, we
sought to fix the zirconium complexes we developed on the sur-
face of a mesoporous silica support to catalyze the CTH of EL
[32].
Herein, we have synthesized the catalyst by anchoring a zirco-
nium(IV) Schiff base complex on the surface of mesoporous silica,
MCM-41. As described earlier, the higher basicity brought on by
the phenate and aniline group enhance the efficiency of the CTH
reaction. Notably, this is the first application of these catalysts in
the conversion of EL to GVL. The results indicated that the immo-
bilized complexes exhibited much higher catalytic performance
than the corresponding homogeneous complexes. Furthermore,
the catalysts exhibit high activity for the hydrogenation of EL to
GVL (Scheme 1). The overall stability of these catalysts was also
investigated and will be discussed herein.
169
2. Experimental
2.1. Materials
5-Chlorosalicylaldehyde, o-Vanillin, salicylaldehyde,
o-phenylenediamine, Ethylenediamine, 2-aminophenol,
DETA(diethylenetriamine), 4,4 -diaminobiphenyl, zirconium
chloride (Zr(Cl)4 , 98%), ethyl levulinate, ␥-valerolactone (GVL)
and 3-Aminopropyltrimetyoxysilane were purchased from Shang-
hai Aladdin Industrial Inc.; Cetyltrimethy-lammonium bromide
(CTAB), Tetraethyl orthosilicate (TEOS), Ethylenediamine were
obtained from Sinopharm Chemical Reagent Co. Ltd.; Solvents
and reagents were purchased from commercial sources and used
without further purification. Deionized water was produced by
using a laboratory water-purification system (RO DI Digital plus).
2.2. Catalyst preparation
We report a new and simple procedure for the generation of the
immobilized zirconium(IV) Schiff base complex on the mesoporous
silica. These systems would serve as effective and reusable catalysts
for a CTH reaction.
2.2.1. Preparation of MCM-41
The synthetic procedures for mesoporous MCM-41 was
described in previous literature [47], though a slight change was
performed here. In this report, CTAB (2.72 g, 7.4 mmol) was added
to deionized water (100 mL) at room temperature with rapid stir-
ring until a clear solution resulted. TEOS (10.4 mL) was then added
dropwise under stirring. The reaction mixtures were made alka-
line with aqueous ammonia (25 wt%) until the pH of the solution
was adjusted to 10.5. The resulting mixture was then stirred for 3 h.
The mixture was then transferred into a Teflon-lined autoclave and
crystallized at 105 ◦ C for 24 h. The gel was washed three times with
distilled water and ethanol respectively, followed by filtration and
drying at 80 ◦ C. The dry material was then calcined at 650 ◦ C for 6 h.
2.2.2. Synthesis of ligands
The synthetic procedure for making Salphen-type ligands was
based on a previous literature report. [48] The appropriate sub-
stituted o-phenylenediamine (1.08 g 10 mmol) was stirred in
methanol (50 mL) at 60 ◦ C until a clear solution was obtained. Sali-
cylaldehyde (2.44 g 20 mmol) was then added to the solution. The
mixture was refluxed for 3 h at 60 ◦ C and cooled to room tem-
perature. A luminous yellow needle-like solid formed and was
collected by filtration. The solid was recrystallized from methanol,
filtered and dried at 70 ◦ C in a vacuum oven. The preparation of
various ligands was performed by selecting different backbones,
such as 5-Chlorosalicylaldehyde, o-Vanillin, salicylaldehyde, o-
phenylenediamine, DETA(diethylenetriamine), Ethylenediamine,
4,4 -diaminobiphenyl or 2-aminophenol. In total, seven Schiff base
ligands were prepared and assessed. The Salphen-type ligand was
characterized by 1 H NMR, and UV–vis spectroscopy (see ESI Fig. S2,
S3†).
2.2.3. Synthesis of the zirconium(IV) complexes
The zirconium(IV) complexes were prepared using a new coor-
dination mode. A similar synthetic procedure for the complex
has been described in the literature [49]. In this procedure:
Zr(Cl)4 (0.233 g, 1 mmol) was dissolved in 20 mL of methanol and
added dropwise into a methanol solution (10 mL) containing 0.31 g
(1 mmol) of the Salphen-type ligand. The suspension was refluxed
for 10 h under a nitrogen atmosphere, and then cooled to room
temperature. After filtering, the solid was washed with methanol,
collected and dried under vacuum at 60 ◦ C. The resulting zirco-
nium(IV) Schiff base complexes (1)–(7) were synthesized by the
170 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178

Scheme 1. Catalytic transfer hydrogenation of EL to GVL using Zr(Salphen)-MCM-41.

Scheme 2. Synthesis of the zirconium(IV) complexes derivatives (1)–(7).

reaction of ZrCl4 with the corresponding ligands as shown in
Scheme 2. Complexes (1)–(7) were characterized by FT-IR (see ESI
Fig. S1†). The Salphen-type zirconium(IV) complex was also char-
acterized by 1 H NMR and UV–vis (see ESI Fig. S2 (b), S3†).
2.2.4. Synthesis of the amino-functionalization zirconium(IV)
complex
A mixture of Zr(Salphen) (10 mmol) and (3-Aminopropyl)-
triethoxysilane (10 mmol) in 30 mL alcohol was heated to reflux
under N2 atmosphere for 24 h. After the reaction, the solvent was
evaporated completely under reduced pressure to give compound
1: NH2 -Zr(salphen).
2.2.5. Synthesis of the heterogeneous zirconium(IV) complexes
catalysts
0.5 g of freshly dried mesoporous silica MCM-41 and 0.5 g com-
pound 1 were added to 50 mL of dry toluene. The mixture was then
heated to 110 ◦ C under N2 atmosphere for 24 h. The mixture was
then cooled to room temperature and filtered. The resulting pow-
der was washed for 24 h in a Soxhlet extractor using an equal ratio
of acetonitrile and ethanol (1:1) as solvent, then the solid prod-
 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178
Scheme 3. (a) Synthetic route of zirconium(IV) complexes, (b) Synthetic route of Zr-supported catalyst of the mesoporous silica.
uct was dried at 60 ◦ C overnight. The synthetic route for catalyst
Zr(Salphen)-MCM-41 is described in Scheme 3.
2.3. Characterization techniques
The SEM used to study the morphological properties of the
catalysts was a HITACHI S-4800 field-emission scanning electron
microscope. TEM was recorded by using a JEOL JEM model 2100
microscope operated at 200 kV. FT-IR spectra were recorded on a
Nicolet 360 FTIR spectrometer (using KBr pellets) in the range of
4000–500 cm−1 . TG analysis was carried out on a STA409 instru-
ment in dry air, using a ramp rate of 20 ◦ C/min from ambient
temperature to 600 ◦ C. UV–vis analyses were performed using TU-
1901 dual-beam UV–vis spectrophotometer in the 200–800 nm
region. XRD patterns were obtained by using a Bruker D8 Advance
powder diffractometer with a Ni-filtered Cu/K␣ radiation source
(40 kV, 20 mA, 1◦ /min). 1 H NMR measurements were recorded
on a Bruker DPX 300 spectrometer at ambient temperature
using TMS as the internal reference in DMSO or CDCl3 . BET-N2
adsorption/desorption measurements were done at 77 K using a
Micromeritics ASAP 2020. The specific surface areas were evalu-
ated using the Brunauer-Emmett-Teller (BET) method and the pore
volume was determined by the single point method over the range
P/P0 = 0.05–0.30, where a linear relationship was maintained. Pore
size distributions were evaluated using the Barrett-Joyner-Halenda
(BJH) model. NH3 -TPD and CO2 -TPD measured the acidic and basic
properties of the catalysts, respectively. The TPD profiles of cata-
lysts were obtained on a Micromeritics AutoChem II 2920 V3.05
apparatus equipped with a thermal conductivity detector. Samples
were pretreated by dehydration and heated from room tempera-
ture to 300 ◦ C at a rate of 10 ◦ C/min and activated for 5 h at constant
temperature under a flow of He (50 cm3 /min) to remove mois-
ture and other adsorbates from the sample. Subsequently, activated
samples were exposed to NH3 or CO2 gases at 100 ◦ C with a flow
of He (50 cm3 /min) until the sample adsorbs NH3 or CO2 to sat-
uration. Initially, the sample was purged with helium gas for 1 h
until the baseline was stable. TPD data were recorded from 100 ◦ C
to 700 ◦ C with a heating rate of 10 ◦ C/min. Energy dispersive X-ray
Spectroscopy (EDX, FESEMTESCAN MIRA3) studies of Zr(salphen)-
MCM-41 confirm the presence of zirconium in the catalyst. ICP-OES
were recorded using PerkinElmer, Optima 8300 ICP-OES Spectrom-
eter. The solid was obtained from the evaporated the mother liquor
of Zr(salphen)- MCM-41, which was treated with 6 mL aqua regia
171
(HNO3 :HCl; 3:1), 5 mL HF, 5 drops HClO4, heated at 120 ◦ C on a heat-
ing plate until the acids were removed completely, then made up to
25 mL by 0.5 M HNO3 . The solid in the mother liquor of ZrO2 was iso-
lated from the evaporation of the supernatant. The solid obtained
was treated with 5 mL HNO3 and 5 drops HF, heated at 120 ◦ C on
a heating plate until the acids were evaporated completely, then
made up to 25 mL by 0.5 M HNO3 .
2.4. Catalytic reactions
All the catalytic reactions were conducted in a 20 mL stainless-
steel reactor equipped with a magnetic stir bar. In a typical
experiment, EL (100 mg), catalyst (60 mg), naphthalene (0.17 g) as
an internal standard and IPA (5 mL) as hydrogen source were added
into the stainless-steel reactor. The reaction mixture was heated to
a specific temperature with an oil bath for the desired time. After
the reaction was complete, the catalyst was recovered by filtration.
The liquid sample was analyzed by gas chromatography (GC). GVL
was characterized by 1 H NMR and 13 C NMR (see ESI S4, S5 †).
2.5. Analysis
The liquid samples were analyzed by gas chromatography (GC,
FID detector and HP-5 column). GC–MS (Bruker SCTONSQ-456-GC)
was used for identification of products. The conversion of EL and
the yield of GVL were evaluated through Eqs. (1) and (2):
 moles of EL

EL conversion (mol%) = 1− × 100 (1)
starting moles of EL
 
moles of GVL
Product yield (mol%) = × 100 (2)
starting moles of EL
3. Results and discussion
3.1. Catalyst characterization
3.1.1. SEM and TEM analysis
The SEM micrographs allowed us to examine the surface mor-
phology of MCM-41 and Zr(Salphen)-MCM-41 as illustrated in
Fig. 1(a) and (b) respectively. These mesoporous silica materials
were likely spherical, but the surface of the functionalized meso-
porous molecular sieves has been changed. This is due to the
incorporation of amino-functionalized zirconium(IV) complexes.
172 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178
Fig. 1. (a) SEM image of the pure MCM-41, (b) SEM image of the catalyst Zr(Salphen)MCM-41, (c) TEM image of the catalyst Zr(Salphen)-MCM-41.
Fig. 2. FT-IR spectras of Salphen (a), Zr(Salphen) (b), Zr(Salphen)-MCM-41(c).
The TEM micrograph revealed a material with long-range order
and uniform pore structure, which confirmed that the distribution
of the complexes was uniform inside the channels of MCM-41 as
seen from Fig. 1(c) and (d) [48,50].
3.1.2. FT-IR spectroscopy
A band at 1614 cm−1 for the azomethine group (C N) in the
ligands could be observed. After complex preparation, the imine
band shifted to a lower frequency (1607 cm−1 ), confirming coor-
dination of the Schiff-base with zirconium (Fig. 2(a) and (b)).[51]
In addition, the FT-IR spectra of Zr CA displayed the characteris-
tic asymmetric (1556 cm−1 ) and symmetric vibrational excitation
(1448 cm−1 ) of phenate groups in deprotonated CA, which were
narrower compared to the spectrum of CA. Furthermore, signals at
1090 cm−1 and 800 cm−1 were consistent with excitation arising in
the Si O Si grafted onto the functionalized silica. The presence of
Fig. 3. TG-DTG analysis for the Zr(Salphen)-MCM-41 catalyst.
a broad peak was seen close to 3450 cm−1 , due to the stretching of
Si OH groups and absorbed water (Fig. 2(c)).
3.1.3. Thermal analysis
The TG and DTG image of a Zr(shalphen)-MCM-41 sample is
shown in Fig. 3, which allows us to gather some insight regarding
the stability of the catalyst. The TG curve indicates a minor weight
loss of 1.8% from 25 to 160 ◦ C, which is associated with absorbed
water in the surface of the silica. Subsequently, the weight elim-
inated by only 0.6% at higher temperature (160–250 ◦ C), which
is probably is due to the removal of weakly coordinated water
molecules. Furthermore, the zirconium complex covalently grafted
on to MCM-41 was rapidly eliminated between 290 to 450 ◦ C, while
the weight percent loss of organic material was about 11% in this
step. Meanwhile, the most rapid weight loss seen by DTG occurred
between 240 to 450 ◦ C. Therefore, we can conclude that the catalyst
exhibits good thermal stability below 290 ◦ C (Fig. 3). The MCM-41
was also investigated by thermal analysis (ESI, Fig. S7).
 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178 173

Fig. 4. Low angle powder XRD patterns of MCM-41(a) and Zr(Salphen)-MCM-41(b).

Table 1
Physico-chemical properties of MCM-41 and Zr(Salphen) -MCM-41.
Fig. 5. Nitrogen physisorption isotherms for (a) MCM-41, (b) Zr(Salphen-MCM-41).
Entry Sample type Surface area Pore volume Average pore size Pore size distribution (inset) for (b) Zr(Salphen-MCM-41).
[m2 g−1 ] [cm3 g−1 ] [nm]

1 MCM-41 878.9 1.276 5.8

2 Zr(Salphen)-MCM-41 664.1 0.587 3.5

3.1.4. Low angle X-ray diffraction studies

The small angle XRD patterns of MCM-41 and Zr(Salphen)-
MCM-41 are presented in Fig. 4, which confirmed the meso-
structure inherent to these systems. The powder X-ray diffraction
patterns of the parent MCM-41 and the complex-immobilized
MCM-41 all showed a sharp reflection around 2␪ angel of
2–3◦ , corresponding to the (100) plane of the hexagonal unit
cell, which confirmed the retention of the hexagonal symmetry
long-range order even after the incorporation of Zr(IV) Salphen
complex [40,48]. A decrease in the intensity of (100) reflection
and the absence of the two higher angel weaker reflections (110,
200) with lower intensities at 3.79◦ and 4.5◦ respectively was
observed (Fig. 4(a)). These results provide further evidence that the
organometallic groups are highly dispersed inside the channels of
MCM-41 [52,53].
Fig. 6. EDX spectrum of the Zr(Salphen)-MCM-41 catalyst.
3.1.5. N2 sorption studies
The N2 adsorption-desorption isotherm data revealed that
the type-IV-shaped isotherm (the patterns with the hysteresis
loops present at high relative pressures) and mesoporous struc- bilized on MCM-41 due to the existence of N, Zr, Cl and Si on the
ture of samples exists, as dictated by the classification guidelines surface of the catalyst.
described by the International Union of Pure and Applied Chem-
istry (IUPAC) classification, as shown in Fig. 5. Furthermore, the
pores of Zr(Salphen-MCM-41) were sharply distributed around
2.4 nm (see inset of Fig. 5), suggesting that the mesostructure of 3.1.7. Explanation of the catalytic activity of
the support was retained [54]. Meanwhile, the data of the sur- Zr(Salphen)-MCM-41
face area and pore size distribution are shown in Table 1, which We examined the basicity by the CO2 -TPD method (Fig. 7). As
also demonstrated that the immobilized complexes have main- shown in Fig. 7, the prepared catalyst has much stronger basic-
tained appreciable mesoporous structure. In contrast to MCM-41, ity. In Zr(Salphen)-MCM-41, there were many phenate and aniline
Zr(Salphen-MCM-41) showed a decrease in surface area, average groups, which could increase the basicity of the catalyst [35]. It had
pore volume and pore size, which confirmed the presence of pen- been reported that higher basicity leads to higher catalyst activity
dant functional groups in channels of the mesoporous material [36]. The basic sites were beneficial in facilitating the dissocia-
[55]. tion of isopropyl alcohol to the corresponding proton and alkoxide
[56]. The NH3 -TPD curve of Zr(Salphen)- MCM-41 was shown in
3.1.6. The EDX analysis of Zr(Salphen)-MCM-41 Fig. 6 (b). We found that many acid sites existed. Additionally, a
The energy dispersive X-ray spectroscopy (EDX) image of the peak around 600 ◦ C could be observed, which mainly results from
surface element composition of Zr(Salphen)-MCM-41 is shown in the Zr4+ (as Lewis acid) [57]. As described earlier, there are many
Fig. 6. The peaks of C, O, N, Si, Zr, and Cl were found. These EDX hydroxyl groups on the surface of MCM-41,which act as Brönsted
results indicated that the complexes have been successfully immo- acid sites at about 550 ◦ C.
174 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178

Fig. 7. CO2 -TPD (a) and NH3 -TPD (b) spectrum of the Zr(Salphen)-MCM-41 catalyst.

Table 2
CTH reaction of EL in IPA catalyzed by various catalysts.a

Entry catalyst Tem.b (◦ C) Time (h) Con.c (%) Yieldd (%) Ref.

1 none 160 12 0 0 –
2 MCM-41+ Salphen 160 12 3 0 This work
3 ZrO2 160 12 8.2 3.1 This work
4 Zr(Salphen) 160 14 75.1 53.8 This work
5 Zr(Salphen)-MCM-41 160 12 95.5 90.0 This work
6 Zr(Salphen)-MCM-41 160 24 99.2 92.1 This work
7e Zr-HA 150 11 99.5 84.2 [58]
8f 10Cu-5Ni/Al2 O3 150 12 100 97 [59]
9e UiO-66-S60 140 9 98 85 [60]
10d Hf-ATMP 150 4 95 86 [61]
a
Conditions: EL 0.1 g, catalyst 70 mg, IPA 5 mL.
b
Tem. = temperature.
c
Conversion (Con.).
d
GVL yield were determined by GC.
e
The hydrogen donor was IPA.
f
The hydrogen donor was 2-butanol.

Table 3 ZrO2 and Zr(Salphen) was that the acidity and basicity of ZrO2 and
The catalytic activity of different schiff base complexes on the conversion of EL to
Zr(Salphen) were much lower than Zr(Salphen)-MCM-41. It could
GVL.
also be observed that longer reaction time did not greatly enhance
Catalyst (complexes) Temperature (◦ C) Time (h) Conversion (%) EL Yield (%) the yield of GVL (Table 2, entry 6). The Zr(Salphen)-MCM-41 cat-
(1) 160 14 75.1 53.8 alyst was also compared with other recently reported catalysts.
(2) 160 14 73.4 23.5 (Table 2, entries 7–10). It could be concluded that the final GVL
(3) 160 14 74.8 25.4 yield and conversion of EL were nearly the same or slightly lower
(4) 160 14 54.5 3.6
than other reported catalysts.
(5) 160 14 51.2 6.7
(6) 160 14 50.3 4.1
(7) 160 14 60.5 11.6
3.3. Conversion of EL to GVL by the homogeneous schiff base
Reaction conditions: 100 mg of EL, 5 mL of IPA, 60 mg of catalyst. complexes

The effects of different metal Schiff base complexes on the trans-

3.2. Catalytic activity of various catalysts for the conversion of EL
to GVL
The catalytic performance of Zr(Salphen)-MCM-41 was com-
pared with other catalysts (Table 2). Under optimal reaction
conditions, there was nearly no substrate conversion in the absence
of any catalyst (Table 2, entry 1). We screened the catalytic activ-
ity of MCM-41 (40 mg) and salphen (20 mg) as ctalysts. There was
only a little conversion of EL to by-product Isopropyl Levulinate
(IPL). ZrO2 showed poor conversion and yield for GVL (only 3.1%)
(Table 2, entry 3). However, when Zr(Salphen) was used as cata-
lyst, 53.8% yield of GVL and 75.1% conversion of EL was observed.
Compared to homogenous Zr-catalysts, both the activity and selec-
tivity were enhanced for the Zr(Salphen)-MCM-41 catalyst (Table 2
entries 4 and 5). The main reason for the poor catalytic activity of
formation of EL to GVL were investigated in methanol and the
results are listed in Table 3. Seven derivatives of Zirconium(IV)
complexes (1–7) were assessed and their structures are shown
in Scheme 2. The complexes (5) and (6) had little catalytic activ-
ity for the conversion of EL at 150 ◦ C for 7 h, with the yields of
GVL being 3.6% and 6.7%, respectively. Complexes (1), (2), (3), (4)
and (7) had better catalytic activity under the same conditions,
which may due to the aniline group within these catalyst deriva-
tives. The catalytic activity of –OCH3 and –Cl substituent groups
on the zirconium(IV) Schiff base complexes were also studied for
the reduction of EL (Table 3, (3) and (4)), which indicated that the
different substituent groups do not improve the activity of the cata-
lyst. A possible reason is that the electron-donating character of the
–OCH3 substituent leads to an increase in delocalization while the
electron-withdrawing character of the –Cl substituent bring about
 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178 175

Table 4
Effect of different solvents for the conversion of EL to GVL.a

Entry Solvent Temperature(◦ C) Conversion (%) Yield (%)

1 IPA 150 86.2 65.5

2 FA 150 85.3 11.3
3 IBA 150 70.3 45.2
4 ET 150 32.6 9.6
5 GL 150 0 0
6 H2 O-IPAb 150 75.5 41.4
7 H2 O-FAb 150 81.1 8.5
8 H2 O-IBAb 150 62.1 32.1
a
Reaction conditions: 100 mg of EL, 60 mg of Zr(Salphen)-MCM-41, 5 mL of sol-
vent, t = 11 h.
b
Volume ratio of H2 O/IPA, H2 O/FA, H2 O/IBA = 1:4.

Fig. 9. The GVL yield and conversion of EL with different amounts of catalyst. Reac-
tion conditions: 100 mg of EL, 5 mL of IPA, 0.17 g naphthalene. T = 160 ◦ C, t = 12 h.

temperatures ranging between 140 and 170 ◦ C. When increasing

reaction time, the conversion of EL and the yield of GVL increased.
The yield of GVL was nearly independent of temperature above
160 ◦ C and reaction times exceeding 12 h. IPL is the major side prod-
uct at lower reaction temperatures. The improvement of the GVL
yield when raising the reaction temperature is significant because
IPL undergoes CTH at higher temperature. Therefore, 160 ◦ C and
12 h were selected as the optimum condition for the reaction.

3.4.3. Effect of the amount of catalyst

Fig. 8. EL transformation into GVL in the presence of Zr(Salphen) -MCM-41. Reaction
conditions: 100 mg of EL, 5 mL of IPA, 0.17 g naphthalene. T = 160 ◦ C, t = 12 h.
a decrease in delocalization, which subdues the efficiency of the
catalysts in this reaction.
3.4. Conversion of EL to GVL by the heterogeneous catalyst
Based on the above investigations, the Schiff base complex
Zr(Salphen) showed the best catalytic activity for the conversion of
EL to GVL. Therefore, Zr(Salphen) was grated on the support as the
heterogeneous catalyst. Furthermore, the effects of solvent, tem-
perature, time and catalyst loading were also investigated for the
conversion of EL to GVL.
3.4.1. Effect of solvent
We screened several different solvents to investigate their
effects when using the catalyst Zr(Salphen)-MCM-41 at 150 ◦ C for
11 h as shown in Table 4. A conversion of 86.2.% with 60.5% GVL
yield was obtained in IPA, which is consistent with previous results
supporting that IPA has greater hydrogen generation capacity than
IBA, ET and GL (Table 4, entries 1, 3, 4 and 5). When FA was used
as solvent, a GVL yield of 11.3% was obtained. Clearly, FA is not an
effective hydrogen donor under this catalytic regime. Additionally,
the activity of the catalyst was investigated by monitoring the con-
version of EL to GVL in co-solvent systems. It was demonstrated
that systems with water as the co-solvent gave lower yields than
in the corresponding pure organic solvents (entries 6–8).
3.4.2. Effect of reaction temperature and time
Different temperatures and reaction time were investigated to
achieve the maximum yield of GVL from EL in IPA (Fig. 8). Reac-
tion times ranged from 9 to 13 h and were carried out at different
The effect of the loading of Zr(Salphen)-MCM-41 on the CTH
reaction of EL was investigated in IPA at 160 ◦ C for 12 h. The results
are shown in Fig. 9. It can be seen from the figure that increasing
the catalyst loading led to an increase in yields of GVL at the begin-
ning. A possible reason is that the more active sites of the catalyst
can be available when the more amount of catalyst was added. The
best catalyst activity (95.5% conversion of EL and 90% of GVL) was
obtained when the amount of the catalyst was 70 mg. Increasing
the amount of catalyst led to a downward trend in the yield of GVL,
mainly because the more active sites accelerated the formation of
by-products (primarily isopropyl levulinate) in the reaction pro-
cess. In summary, 70 mg was an appropriate amount of the catalyst
under the reaction condition.
3.4.4. Reusability and heterogeneity of the catalyst
A recycling test of Zr(Salphen)-MCM-41 was investigated under
the optimized reaction conditions. After every cycle, the catalyst
was separated from the product mixture by centrifugation, washed
with a solution of ethanol:water (95:5) and dried in an oven at
65 ◦ C. Only a minor decrease in the catalytic activity was observed
when the catalyst was recycled for five runs (Fig. 10). Accordingly,
the resulting Zr(Salphen)-MCM-41 (after five cycles) was charac-
terized by the following techniques:FT-IR (Fig. 11 (A)), XRD (Fig. 11
(B)), SEM (Fig. 11 (C)) and TEM (Fig. 11 (D)). The results from those
studies suggested that the structure and properties of the recov-
ered catalyst underwent only little change after being reused for
five runs. The results can be attributed to two factors:(1)The cen-
ters of the catalyst leached from the surface of the silica support
over the course of these experiments. (2) The byproduct of the
reaction was absorbed on the surface of the catalyst, blocking the
active sites of the catalyst for subsequent substrate binding. To ver-
ify the first hypothesis, a filtration test was performed (Fig. 12) by
comparing two reactions. The first was the CTH reaction of EL cat-
alyzed by Zr(Salphen)-MCM-41 as usual. The second reaction was
176 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178
Fig. 10. Reusability of the Zr(Salphen)-MCM-41 catalyst in the conversion of EL.
Reaction conditions: 70 mg of catalyst, 5 mL of IPA, 0.17 g naphthalene. T = 160 ◦ C,
t = 12 h.
stopped after 10 h and filtered to remove the catalyst. Then, the
reaction solution was stirred for extended time. The result shows
that there was no further increase of the GVL yield when the solid
was removed. Additionally, metal leaching was supported by ICP-
OES analysis of the mother liquor. The amount of Zr that leached
from Zr(Salphen)-MCM-41 (70 mg) was 0.327 ppm under the reac-
tion condition where 0.1 g EL in 5 mL IPA was mixed at 160 ◦ C for
12 h. However, 2.883 ppm Zr leached from ZrO2 (70 mg) when the
ZrO2 was used as catalyst under the same reaction condition. This
evidence supports that the active centers were leached from the
surface of the catalyst slightly and the reaction was catalyzed by a
heterogeneous species.
Fig. 11. SEM(A) and TEM(B) image, FTIR graphs(C), XRD patterns (D) of the used catalyst.
Fig. 12. (a) Time-yield plots for the CTH reaction of EL catalyzed by Zr(Salphen)-
MCM-41. Reaction conditions: 70 mg of catalyst, 5 mL of IPA, 0.17 g naphthalene.
T = 160 ◦ C. (b) The line shows the GVL yields upon removing the solid catalyst after
11 h and continued up to 14 h.
3.5. Reaction mechanism
Based on the characterization of NH3 -TPD, CO2 -TPD techniques
and the reported literature (Fig. 7), we proposed the reaction mech-
anism for EL conversion to GVL as described in Scheme 4. According
to the experimental results, we concluded that the Zr(Salphen)-
MCM-41 catalysts possess acidic sites (Zr4+ , –OH) and basic sites
(O2− , N3− ). These active sites(Zr4+ , O2− , N3− ) interacted with both
EL and IPA to activate the carbonyl group, leading to the dis-
sociation of IPA to its corresponding alkoxide and proton, then
EL accepted the proton from the dissociation of IPA to form 4-
HPE (4-hydroxypetanoate) [32,35,36]. At this stage, through a six
 R. Wang et al. / Molecular Catalysis 441 (2017) 168–178
Scheme 4. Plausible reaction mechanism for the conversion of EL into GVL on Zr(Salphen)-MCM-41 catalyst.
membered ring transition state, Brönsted acid (–OH) induces an
intramolecular esterification to give GVL, as also supported in sim-
ilar GVL forming processess [58]. Thus, the –OH present in the
channels of MCM-41 play a key role in the selective formation of
GVL. By GC–MS, we detected two major by-products: IPL and ethyl
4-isopropoxypentanoate (E4iPOPA). IPL underwent further CTH to
form GVL much like EL, which initially formed by transesterifica-
tion of EL. The formation of the other by-product, E4iPOPA, formed
by etherification of 4-HPE and IPA, serves as indirect evidence for
the formation of 4-HPE (The GC–MS could not detect 4-HPE).
4. Conclusion
In summary, the new porous Zr-catalyst containing phenate
and aniline groups, Zr(Salphen)-MCM-41, has been designed and
used for the selective conversion of EL into GVL with IPA as the
hydrogen resource. This could be achieved due to the presence of
acidic and basic sites in the heterogeneous catalyst, providing GVL
in high yield (90%) under optimal reaction conditions. The immobi-
lized catalyst could be recycled at least five times without apparent
loss of catalytic activity. In addition, the possible mechanism of this
reaction under these newly developed catalytic conditions was pro-
posed. We believe that these catalysts have a promising potential as
heterogeneous catalysts in the MPV reduction of various substrates
due to their green preparation, high activity, and high reusability.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.mcat.2017.07.
026.
177
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