Effective hydrodeoxygenation of dibenzofuran by a bimetallic catalyst in water

Article abstract of DOI:10.1039/c5nj02164b

Effective hydrodeoxygenation (HDO) of dibenzofuran (DBF) catalyzed by a bimetallic nickel/platinum (Ni/Pt) catalyst in water was demonstrated at 200 °C and 1.2 MPa hydrogen (H₂) pressure. The bimetallic catalysts prepared by a wet chemical method exhibit prominent activity that overcomes the limitations of use of a single Ni or Pt metal catalyst. The yield of HDO products can be up to 90%. Reaction results indicate that the conversion of DBF was affected by the reaction temperature and H₂ pressure. The deoxygenation selectivity was strongly dependent on reaction temperature. The reaction pathway is also proposed.

Full text of DOI:10.1039/c5nj02164b

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Effective Hydrodeoxygenation of Dibenzofuran by Bimetallic Catalyst in Water
Peng Donga, Guo-ping Lua, and Chun Caia*
Received 00th January 20xx,
Accepted 00th January 20xx
Effective hydrodeoxygenation (HDO) of dibenzofuran (DBF) catalyzed by bimetallic Ni/Pt catalyst in water was
demonstrated at 200 °C and 1.2 MPa H2 pressure. The bimetallic catalysts prepared by a wet chemical method exhibit
prominent activity that overcomes the limitations of single metal catalyst Ni or Pt. The yield of hydrodeoxygenation
products can be achieved up to 90%. Reaction results indicate that the conversion of dibenzofuran was affected by the
reaction temperature and H2 pressure. The deoxygenation selectivity was strongly depended on reaction temperature. The
reaction pathway was also proposed.
DOI: 10.1039/x0xx00000x
www.rsc.org/
noble metal (Ru, Rh, Pd, Pt, etc.) catalysts are known to be efficient
for HDO of oxygen-containing aromatics under mild conditions 14-17
.
1. Introduction
Coal tar, as an important by-product of coal processing industry,
Recently, Pt supported on mesoporous ZSM-5 zeolites was used as
catalyst for HDO of DBF at 200oC, 4MPa H2 pressure 18. And HDO of
DBF over supported Pt, Pd, and Ru catalysts at 280-300 °C and
3MPa H2 were reported by C. Liang et al. 19-21. These catalytic
performances of HDO reactions were attributed to hydrogenation
ability of the active metal sites and cleavage of the C–O bond
promoted by acidic sites, which requires a nearly completely
saturated benzene ring before the removal of heteroatom oxygen.
Besides precious metal catalysts, supported Ni catalysts in the
absence of adjacent acid sites can also hydrogenolyze aromatic
contains a wide-range of compounds with different molecular
1,
weights and functionalities 2. They can cause ubiquitous and
persistent environmental pollutants to be released to the
environment 3, 6. Dibenzofuran (DBF) is one of the typical oxygen-
containing compound in coal tar. Hydrodeoxygenation (HDO) of
DBF can convert O-containing wastes to usable products 7. In
addition, DBF is an important intermediate in the biomass
gasification 8. High oxygen content of bio-oils leads to their high
viscosity, low heating value and poor thermal stability 9, 10. As we
known, catalytic HDO is a promising process to upgrade the bio-oils
to hydrocarbon fuels. Therein, DBF was chosen as the HDO model
compound for our research.
22-
ether bonds on Ni sites, which was disclosed by A. Lercher group
25-
24. Noble metal (Pt, Ru, Pd) have superior hydrogenation activity
26
and Ni catalysts have high selectivity and moderate activity for
27-30
Conventional CoMo sulfide and NiMo sulfide supported catalysts
used for HDO of DBF have been conducted, and several HDO
reaction pathways of DBF have been proposed 11, 12. However, there
are several disadvantages of metal sulfide catalysts, such as extra
sulfide is needed to maintain the activity of the catalyst 13, and
sulfur may be introduced into the products at the process and
result in products contamination. Besides sulphide /oxide catalysts,
HDO of oxygen-containing aromatics
. Therefore, the
combination of these two kinds of metals to be bimetallic catalysts
for HDO of DBF was taken into consideration in this study.
Many kinds of bimetallic catalysts have been reported for
34
different reaction purpose, such as 31-33, Ni/Cu and Fe/Pd, Ni/Pd,
Ni/Au bimetallic catalysts 35-40. The method with the addition of
noble metal to Ni-based catalyst to improve the catalytic activity of
aromatic C-O cleavage in aqueous phase was developed by J. Zhang
et al 40. Ni/M (M = Ru, Rh, and Pd) catalysts inherited the
39,
a.Chemical Engineering College, Nanjing University of Science & Technology,
Nanjing, Jiangsu 210094, People’s Republic of China.
advantages of both components, in which noble metal increased
the hydrogenation activity of catalyst, and Ni modified the
selectivity of noble metal to favor the C−O bond cleavage. The
synergistic effects of the bimetallic catalyst lead to the improved
Fax : (+86)-25-8431-5030; phone: (+86)-25-8431-5514; e-mail: c.cai@njust.edu.cn
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catalytic performance. In addition, as catalytic HDO of oxygen- added in one portion under vigorous stirring. A black colloid was
containing aromatics will produce water as byproduct, water- obtained immediately.
tolerant catalysts would be more beneficial choices for this type of
2.2.2. Preparations of NixPd100-x Catalysts
reaction. This approach also makes the separation of HDO products
NixPd100−x (x/molar percentage of Ni = 0, 75, 80, 85, 86, 90, 100)
catalysts were prepared using a wet chemical method by aqueous
phase reduction of metal salts with NaBH4, employing PVP as a
stabilizing agent. Because PdCl2 is not dissolved in water, so PdCl2
was dissolved in an aqueous solution containing NaCl to form
Na2PdCl4. A typical preparation procedure for Ni85Pt15 is described
here. PdCl2 (1.8mg, 0.0103 mmol) was dissolved in an aqueous
solution (4 mL) containing NaCl (3.5mg, 0.0618 mmol) to form
Na2PdCl4. To this solution, NiCl2·6H2O (13.8mg, 0.0582 mmol), and
PVP (100 mg, 0.9 mmol based on monomer) were added, and the
suspension was stirred for 30 s for dissolution. To this mixture, a
freshly prepared aqueous solution of NaBH4 (13.5 mg, 0.35 mmol, in
2 mL H2O) was added in one portion under vigorous stirring. A black
colloid was obtained immediately.
easier from the reaction mixture.
2. Experimental
2.1. General
All reagents were purchased from commercial sources and used
without treatment. Transmission electron microscopy (TEM) images
were taken using a PHILIPS Tecnai12 microscope operating at 120
kv. X-ray photoelectron spectroscopy (XPS) were performed on a
ESCALAB 250Xi spectrometer, using a Al Kα X-ray source (1350 eV of
photons) and calibrated by setting the C 1s peak to 284.80 eV.
Catalytic hydrodeoxygenation reactions were conducted in an
EYELA ChemiStation PPV-CTRL1 high pressure parallel reactor.
Hydrodeoxygenation
products
were
analyzed
by
gas
chromatography (GC) on an Agilent 7890A gas chromatograph with
a flame ionization detector (FID), equipped with HP-5 capillary
columns, and gas chromatography/mass spectroscopy (GC/MS)
with an thermo scientific trace1300 GC/MS instrument equipped
with TR-5MS columns. Most products were known compounds and
identified by comparison of their physical and spectra data with
those of authentic samples.
2.3. Characterizations of NixM100-x Catalysts
2.3.1. Transmission electron microscopy (TEM)
Transmission electron microscopy (TEM) images were taken
using a PHILIPS Tecnai12 microscope operating at 120 kv. The
freshly prepared catalyst solution was passivized by bubbling with
N2 for 20 minutes, to prevent the oxidation of the catalysts,
immediately after synthesis. TEM samples were prepared by
diluting the solution (0.05 mL) with methanol (3 mL), following
which one drop of the solution was placed on a carbon film covered
copper grid and dried under air.
2.2. Preparations of NixM100-x Catalysts
2.2.1. Preparations of NixPt100-x Catalysts
A series of NixM100−x (x/molar percentage of Ni = 0, 75, 80, 85, 86,
90, 100) catalysts were prepared using a wet chemical method by
aqueous phase reduction of metal salts with NaBH4, employing PVP
as a stabilizing agent 39-41. A water solution (4 mL) of metal salt or
metal salts mixture and PVP were added to a 20 mL specially
2.3.2. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) measurements were
performed on a ESCALAB 250Xi spectrometer, using a Al Kα X-ray
source (1350 eV of photons) and calibrated by setting the C 1s peak
to 284.80 eV. The fresh catalyst solution (10mL) was mixed with
acetone (80 ml). The mixture was centrifuged and semi-solid
material at the bottom of the centrifugation was collected, dried
under vacuum, and analyzed by XPS. Note that Ni atoms in the
oxide form due to post-oxidation during sample preparation.
reinforced tube. To this mixture,
a freshly prepared aqueous
solution of NaBH4 was added in one portion under vigorous stirring.
A black colloid was obtained immediately. A typical preparation
procedure for Ni86Pt14 is described here. A water solution (4 mL) of
NiCl2·6H2O (14 mg, 0.0589 mmol), PtCl6·6H2O (5 mg, 0.0096 mmol),
and PVP (100 mg, 0.90 mmol based on monomer) were added to a
20 mL specially reinforced tube. To this mixture, a freshly prepared
aqueous solution of NaBH4 (13.5 mg, 0.35 mmol, in 2 mL H2O) was
2.4. Hydrodeoxygenation Reaction with Dibenzofuran
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In a typical HDO experiment, a freshly prepared catalyst (0.0685 a Reaction conditions: 0.228 mmol Dibenzofuran, 6 mL freshly
prepared aqueous solution containing 0.44 mmol PVP, 0.0685mmol
mmol) colloid was transferred into the reactor (20 mL) with a
catalyst, H2, 1.2MPa, 200 o C, 10h.
magnetic stirrer for the hydrodeoxygenation. The substrate DBF (38
b Hydrodeoxygenation products (compounds 1- 4).
mg, 0.228 mmol) was added. After flushing with H2 four times, the
c Hydrogenolysis products (compounds 5- 9).
reactor was charged with 1.2 MPa of H2 and the temperature was
raised to 200 o C with a stirring speed of 500 rpm. After the reaction
complete, the mixture was cooled to ambient temperature,
extracted with ethyl acetate (20 mL) and the organic phase was
analyzed by GC/MS.
d Hydrogenation products (compounds 10- 12).
e Standard errors obtained from3 groups of parallel experiments.
100
95
90
85
80
75
70
65
60
55
50
3. Results and discussion
Fig.1. Twelve products identified after of Dibenzofuran
hydrodeoxygenation
0
1
2
3
4
5
6
7
8
9
10
11
12
Entry(catalysts)
Table 1. Hydrodeoxygenation of dibenzofuran over Ni, Pt and
Figure2. The plot of the reaction conversions
NixPt100-x catalysts.
3.1. Products Distribution of Dibenzofuran Hydrodeoxygenation
Selectivity a (%)
Standard
Error e
Conv.
(%)
At first, monometallic catalysts (Ni, Pd and Pt) were used for the
HDO of dibenzofuran (Table 1). Twelve main products were
identified by GC-MS analysis (1-12; see Fig. 1) and there were no
single-ring products observed from the HDO of DBF. Compounds 1-
4 which lost the oxygen were derived from the hydrogenation
deoxygenation of the substrate. Compounds 5-9 were products
retaining one of C-O bond through another C-O bond
hydrogenolysis. Compounds 10-12 were products generated by
hydrogenation of the substrate without the cleavage of the C-O
bond. So, the products were categorized as hydrodeoxygenation
products A: 1–4, hydrogenolysis products B: 5–9 and hydrogenation
products C: 10-12. Ni monometallic catalyst achieved 59%
conversion and 73% selectivity toward hydrodeoxygenation product
(entry 1). Pt monometallic catalyst showed higher activity (entry 3)
with 99% conversion of DBF, but the hydrodeoxygenation product
selectivity was only 32%. Pd monometallic catalyst has poorer
hydrodeoxygenation selectivity with 99% conversion and 2%
Entry Catalyst
A b
73
2
B c
15
0
C d
12
98
41
96
95
26
17
13
3
1
2
Ni
59
99
99
64
78
63
75
82
99
92
81
3.8
0.5
0.5
3.7
3.5
2.8
2.6
2.4
0.8
2.0
2.4
Pd
3
Pt
32
2
27
2
4
Ni75Pd25
Ni85Pd15
Ni75Pt25
Ni80Pt20
Ni82Pt18
Ni86Pt14
Ni88Pt12
Ni90Pt10
5
3
2
6
63
70
77
92
82
75
11
13
10
5
7
8
9
hydrodeoxygenation product selectivity. Ni catalyst showed
a
10
11
12
13
6
highest selectivity towards hydrodeoxygenation products although
the reaction did not have the highest conversion. Then, we
evaluated the performance of several bimetallic catalysts to
12
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improve the activity of the Ni catalysts and the product selectivity conversion can reach above 99% and the selectivity of product 3
over different catalysts were summarized in table 1. The plot of the
reaction conversions as a function of the catalysts used were
showed in Figure 2. The Error bars on data points of figure2 were
the results of 3 measurements. By incorporating Pd into Ni, the
Ni/Pd catalysts did not improve the reaction selectivity as desired.
The main products were also the hydrogenation products, which
further indicated that Pd catalyst has higher hydrogenation activity
than deoxygenation activity. By incorporating Pt into Ni, as Ni has a
low content the products selectivity were similar with pt
monometallic catalyst. With the increasing of Ni content, the Ni/Pt
catalysts inherited the advantages of both components and Ni86Pt14
catalyst has the best performence with 99% conversion and 92%
hydrodeoxygenation product selectivity. The selectivity of higher-
Ni-content catalysts was maintained while the activity dropped
gradually. Thus, Ni86Pt14 was chosen for further investigation. The
reaction conditions were optimized and the results were
summarized in Table 2, Table3 and Table4
reached 88% (Table 4).
3.3. Transmission electron microscopy (TEM)
Figure3. (a) TEM image of Ni. (b) TEM image of Ni86Pt14. (c)
TEM image of Pt. (d) TEM image of Pd. (b) TEM image of Ni85Pd15
.
Transmission electron microscopy (TEM) was applied to probe
the structure of the bimetallic catalyst, which indicates that the
Ni86Pt14 catalyst is spherical with a diameter of 5.0 ± 0.5 nm (see
Figure 3 b), similar to pure Pt particle (3.0 ± 0.5 nm ) (see Figure 3
c) but smaller than the Ni catalyst (11.5 ± 3.5 nm) (see Figure3 a).
Ni85Pd15 catalyst is spherical with a diameter of 10 nm ± 1.5 nm (see
Figure 3 e), similar to pure Ni particle but bigger than the Pd
catalyst (5.0 ± 0.5 nm) (see Figure3 d). The structural features of the
Ni86Pt14 catalyst corresponded to synergistic effect, which was well
documented that the combination of two metals could result in
drastically enhanced catalytic performance. Compared with Ni86Pt14
catalyst, Ni85Pd15 has a bigger diameter. The different structural
features of Ni86Pt14 and Ni85Pd15 catalysts corresponded to the
different reactivity and selectivity of these two bimetallic catalysts
(see Table 1).
3.2. Effect of Reaction Conditions
At 200o C, the hydrodeoxygenation products selectivity was up to
92% with the excellent high selectivity of compound 3 with 88%
selectivity. At 150 o C, the hydrodeoxygenation products selectivity
was 10%, and the yield of 3 decreased to 9 %. In contrast, 6 and 7
increased to 63 % which were not detected at the reaction
condition of 200 o C. At lower temperature (100 o C), the reaction
became slow, thus, the hydrodeoxygenation selectivity only turned
to 22 % and the total conversion was 9 % (Table 2). Above all, it
could be concluded that temperature has great influence on total
conversion and catalyst hydrodeoxygenation selectivity, which may
due to the strong aromatic ether linkage of dibenzofuran.
Reaction pressure was another important influencing factor for
the hydrodeoxygenation reaction. The conversion of DBF increases
sharply from 59% to 100% when hydrogen pressure changes from
0.8 to 1.4 MPa. High hydrogen pressure may largely promotes the
hydrogenation of aromatic rings of DBF to yield more product 11
and 12, and then C–O bond cleavage is enhanced with up to 92%
selectivity toward hydrodeoxygenation products and product 3 was
the main product with 88% yield (Table 3, entry 4). The reaction
time also affected the conversion rate of the substrate and the
selectivity of the products. When reacting for 10 h the total
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Table 2. HDO of dibenzofuran over Ni86Pt14 catalyst under different reaction temperature.
Temp.
(o C)
100
Selectivity a (%)
Entry
Conv. (%)
12
1
0
0
2
2
0
0
0
3
14
9
4
8
1
2
5
0
2
0
6
0
2
0
7
0
8
0
2
5
9
0
0
0
10
0
11
42
3
1
2
3
36
9
150
61
0
0
20
79
200
88
0
3
0
99
a Reaction conditions: 0.228 mmol Dibenzofuran, 6 mL freshly prepared aqueous solution containing 0.0685 mmol Ni86Pt14 and 0.44 mmol
PVP, 1200 KPa H2, 10 h.
Table 3. HDO of dibenzofuran over Ni86Pt14 catalyst with different hydrogen pressure.
PH2
(KPa)
800
Selectivity a (%)
Entry
Conv. (%)
1
2
4
2
2
12
12
0
3
4
8
2
2
5
0
0
0
6
0
0
0
7
0
0
0
8
3
4
5
9
1
1
0
10
0
11
8
12
5
1
2
3
4
61
61
88
59
63
1000
1200
1400
0
7
9
0
3
0
99
13
31
56
0
0
0
0
0
0
0
0
0
100
a Reaction conditions: 0.228 mmol Dibenzofuran, 6 mL freshly prepared aqueous solution containing 0.0685 mmol Ni86Pt14 and 0.44 mmol
PVP, H2, 200 o C, 10 h.
Table 4. HDO of dibenzofuran over Ni86Pt14 catalyst with different reaction time.
Selectivity a (%)
Entry
Time (h)
Conv. (%)
1
0
2
2
2
2
0
4
0
1
3
4
6
5
0
1
0
0
6
0
0
0
0
7
0
0
0
0
8
6
9
5
6
9
3
1
0
0
10
0
11
10
6
12
29
6
1
2
3
4
1
5
46
42
88
82
26
85
29
2
0
10
15
0
3
0
99
1
0
4
4
100
a Reaction conditions: 0.228 mmol Dibenzofuran, 6 mL freshly prepared aqueous solution containing 0.0685 mmol Ni86Pt14 and 0.44 mmol
PVP, 200 o C, 1200 KPa H2.
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phenol was rapidly hydrogenated to cyclohexanol. Subsequently,
the intermolecular dehydration reaction of 5 and 7 will happen to
form O-free 4-1. Due to the rapid hydrogenation dehydration rate,
7200
7000
6800
6600
6400
6200
6000
5800
5600
5400
5200
Ni Pt
86 14
a
856.5 eV
6, 7 were not easily detected during dibenzofuran conversion. It has
Ni 2P
3/2,
+2Ni
874.5eV
Ni 2P
8, 9, 11
+2 Ni
1/2,
been reported another pathway of HDO of DBF like III
,
however in this research there were little biphenyl or 2-hydroxyl
biphenyl detected. So we proposed pathways I and II were the main
reaction pathways in this research.
885
880
875
870
865
860
855
850
Binding Energy (eV）
1200
1100
1000
900
Ni Pt
86 14
b
70.8 eV
Pt4f7/2, Pt metal
800
71.8 eV
700
Pt4f7/2, +2Pt
600
500
400
82
80
78
76
74
72
70
68
66
Binding Energy (eV)
Scheme 1. Proposed Reaction Pathways of Dibenzofuran Conversion
over Ni/Pt Catalysts.
Figure 4. XPS spectra for Ni86Pt14 catalysts.
3.4 X-ray photoelectron spectroscopy (XPS)
4. Conclusions
In summary, bimetallic Ni86Pt14 catalyst exhibits good activity in
the hydrodeoxygenation of dibenzofuran, at 200 °C and 1200 kPa H2
pressure. Based on the TEM and XPS characterization, Ni/Pt
bimetallic catalysts have smaller particle size than corresponding
single metal catalysts and Ni were enriched in the catalysts surface.
The combination of the two single component exhibits prominent
effects overcoming the limitations of a single component catalyst. It
is interesting to see that Ni/Pt catalysts were effective in the
hydrogenolysis deoxygenation of sp2 C-O bond here. The structural
characteristics of the Ni/Pt bimetallic catalysts may be the reason of
their high catalytic activity and selectivity. We proposed
hydrogenation of the aromatic rings is the first step, following by
the C−O ether bonds cleavage and the deoxygenaꢀon of
cyclohexanol to produce O-free cyclohexylbenzene. In addition, the
aqueous phase reaction has the advantages of low cost, non-toxic
and harmless to the environment and easy to separate organic
products from the reaction system, which makes catalysts
recyclable.
XPS was employed to characterize valence state and surface
composition of Ni86Pt14 catalysts. As shown in Figure 4, the spectra
for Ni86Pt14 in Ni 2p region are revealing oxidation of Ni has
occurred during the sample preparation. The appearance of the Pt
4f peak indicates the existence of near-surface Pt in the Ni84Pt16
catalyst. Using the Ni 2p3/2 and Pt 4f7/2 peak areas, the surface
ratio of Ni/Pt can be determined as 8.4:1, which is higher than the
precursors’ ratio, 6.1:1, indicating that Ni is probably surface
enriched.
3.5. Reaction Pathway of HDO of DBF over Ni/Pt Catalyst
According to the obtained experimental results, a proposed
reaction pathway for dibenzofuran conversion over Ni/Pt catalyst
under the current conditions is illustrated in Scheme 1. Typically, it
is easy to achieve the hydrogenation products 10, 11 and 12
through hydrogenation of aromatic rings of dibenzofuran at high H2
pressure over Ni/Pt catalysts, followed by the cleavage of C-O
bonds to produce 8, 9 (pathways I and II). Moreover, 12 can also be
converted to 6 and 7 through direct hydrogenolysis, and then,
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34 H. P. Reddy Kannapu, C. A. Mullen, Y. Elkasabi, and A. A.
Boateng, Fuel Processing Technology, 2015, 137, 220–228.
35 J. K. Kima, J. K. Leea, K. H. Kanga, J. C. Song, and K. Song,
Appl. Catal. A, 2015, 498, 142–149.
36 J. Sun, A.M. Karim, H. Zhang, L. Kovarik, X.S. Li, A.J. Hensley,
J-S. McEwen, Y. Wang, J. Catal., 2013, 306, 47–57.
37 H. Konnerth, J. Zhang, D. Mac, M. H. G. Prechtl, and Ning
Yana, Chemi. Engin.Sci., 2015, 123, 155–163.
38 S. Fu, G. Yang, Y. Zhou, H.-B. Pan, C. M. Wai, D. Dua, and Y.
Lin, RSC Adv., 2015, 5, 32685–32689.
39 J. Zhang, H. Asakura, and N. Yan, Green Chem., 2014, 16,
2432-2337.
Acknowledgements
This work is supported by the Fundamental Research
Funds for the Central Universities, 30915011315.
Notes and references
1
J. G. Mueller, P. J. Chapman, P. H. Pritehard, Environ. Sci.
Technol., 1989, 23(10), 1197-1201.
2
3
T.V. Choudhary, C.B. Phillips, Appl. Catal. A 2011, 397, 1–12.
D. Zamfirescu, P. Grathwohl, J. Contam. Hydrol., 2001, 53
407-427.
40 J. Zhang, J. Teo, X. Chen, H. Asakura, T. Tanaka, K. Teramura,
and N. Yan, ACS Catal., 2014, 4 , 1574-1583.
41 S. K. Ghosh, M. Mandal, S. Kundu, S. Nath, T. Pal, Appl. Catal.
A, 2004, 268, 61-66.
4
5
6
S. S. Johansen , E. Arvin , H. Mosbæk and A. B. Hansen,
Toxicological & Environmental Chem., 1998, 66, 195-228.
M. Cobas, L. Ferreira, T. Tavares, M.A Sanromán, and M.
Pazos, Chemosphere, 2013, 91, 711-716.
P. Blum, A. Sagner, A. Tiehm, P. Martus, T. Wendel, and P.
Grathwohl, J. Contam. Hydrol., 2011, 126, 181-194.
E. Furimsky, Appl. Catal. A, 2000, 199, 147-190.
C. M. Huelsman and P. E. Savage, Phys. Chem. Chem. Phys.,
2012, 14, 2900-2910.
7
8
9
J. Lu, A. Heyden, J. Catal., 2015, 321, 39-50.
10 D. Leckel, Energy & Fuels, 2006, 20, 1761-1766.
11 S. Krishnamurthy, S. Panvelker, and Y.T. Shah, AIChE J., 1981,
27, 994-1001.
12 V. L.Vopa, C. N. Satterfield, Energy & Fuels, 1987, 1, 323-331.
13 S. Boullosa-Eirasa, E. A. Blekkana, Catal. Today, 2014, 223,
44-53.
14 P.M. Mortensen, J.-D. Grunwaldt, and A.D. Jensen, Appl.
Catal., 2011, 407, 1-19.
15 P. M. Souza, R.C. Rabelo-Neto, and F. B. Noronha, ACS Catal.,
2015, 5, 1318-1329.
16 K. T. shige, Y. Nakagawa, and M. Tamura, Top. Curr. Chem.,
2014, 353, 127-162.
17 N. Yan and P. J. Dyson, Curr. Opin. Chem. Engin., 2013, 2,
178-183.
18 Y. Wang, Y. Fang, and J. Wu, Catal. Commun., 2011, 12,
1201-1205.
19 L.Wang, H. Wan, S. Jin, X. Chen, C. Li and C. Liang, Catal. Sci.
Technol., 2014, 5, 465-474.
20 L. Wang, M. Zhang, M. Zhang, G. Sha, and C.Liang, Energy
Fuels, 2013, 27, 2209−2217.
21 L.Wang, C. Li, W. Li, S. Jin, and C. Liang, Catal. Lett., 2014,
144, 809–816.
22 C. Zhao and J. A. Lercher, Angew. Chem., 2012, 124, 1 – 7.
23 J. He, C. Zhao, and J. A. Lercher, J. Am. Chem. Soc., 2012, 134,
20768−20775.
24 J. Hea, C. Zhao, D. Meib, and J.A. Lercher, J. Catal., 2014, 309,
280–290.
25 C.H. Lee, J.S. Yoon, and Y.-K. Park, Catal. Commun., 2012, 17,
54–58.
26 B. Güvenatama, O. Kursuna, E. H. J. Heeresb, E.A. Pidkoa, and
E. J. M. Hensena, Catal. Today, 2014, 233, 83–91.
27 A. G. Sergeev, J. D. Webb, and J. F. Hartwig, J. Am. Chem. Soc.,
2012, 134, 20226−20229.
28 S. Jin, Z. Xiao, X .Chen, L. Wang, J. Guo, and M. Zhang,
Industrial & Engineering Chemistry Research, 2015, 54 (8),
2302-2310.
29 V.M. Roberts, V. Stein, T. Reiner, A. Lemonidou, X. Li, and J.
A. Lercher, Chem. Eur. J., 2011, 17, 5939- 5948.
30 A. I. Molina, E. Gralberg, J. A. Cecilia, E. Finocchio, and E. R.-
Castellón, Catal. Sci. Technol., 2015, 1-36.
31 A.K. Singh, Q. Xu, ChemCatChem, 2013, 5, 652–676.
32 R. M. Navarro, B. Pawelec, J. M. Trejo, R. Mariscal, and J. L.
G. Fierro, J. Catal., 2000, 189, 184–194.
33 A.R. Ardiyantia, A. Gutierrezb, M.L. Honkelab, A.O.I. Krauseb,
H.J. Heeresa, Appl. Catal. A, 2011, 407, 56– 66.
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DOI: 10.1039/C5NJ02164B