Enhancement of Oxidative Desulfurization Performance over UiO-66(Zr) by Titanium Ion Exchange

Article abstract of DOI:10.1002/cphc.201700182

Oxidative desulfurization is considered to be one of the most promising methods for producing ultra-low-sulfur fuels because it can effectively remove refractory sulfur-containing aromatic compounds under mild conditions. In this work, the oxidative desulfurization performance over UiO-66(Zr) is greatly enhanced by Ti ion exchange. This strategy is not only efficient for UiO-66(Zr) with crystal defects but also for UiO-66(Zr) with high crystallinity. In particular, the performance of UiO-66(Zr) with high crystallinity in the oxidative desulfurization of dibenzothiophene can be improved more than 11-fold, which can be mainly attributed to the introduction of active Ti sites.

Full text of DOI:10.1002/cphc.201700182

Accepted Article
Title: Enhancement of oxidative desulfurization performance over
UiO-66(Zr) by Ti ion exchange
Authors: Yinyong Sun, Gan Ye, Hui Qi, Xiaolin Li, Kunyue Leng, and
Wei Xu
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To be cited as: ChemPhysChem 10.1002/cphc.201700182
Link to VoR: http://dx.doi.org/10.1002/cphc.201700182
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10.1002/cphc.201700182
ChemPhysChem
ARTICLE
Enhancement of oxidative desulfurization performance over UiO-
66(Zr) by Ti ion exchange
Gan Ye,[a] Hui Qi,[b] Xiaolin Li,[a] Kunyue Leng,[a] Yinyong Sun,*[a] and Wei Xu[c]
Abstract: Oxidative desulfurization is considered to be one of the polyoxometalates[21-27] were encapsulated into the cavities of
most promising methods for producing ultra-low sulfur fuels because some MOFs to oxidize dibenzothiophene (DBT) or 4,6-
it can effectively remove the refractory sulfur-containing aromatic dimethyldibenzothiophene (4,6-DMDBT). However, as for the
compounds under mild conditions. In this work, we reported that the supported catalysts, active phases easily blocked the pore
oxidative desulfurization (ODS) performance over UiO-66(Zr) can be channels and were likely lost during the reactions. Therefore,
greatly enhanced by Ti ion exchange. This strategy is not only development of the intrinsic catalytic performance of MOFs is of
efficient for UiO-66(Zr) with crystal defect but also for UiO-66(Zr)
with high crystallinity. Especially, the ODS performance of UiO-66(Zr)
great significance.
Indeed, there are some attempts about MOFs themselves as
with high crystallinity can be improved above 11-fold in the ODS ODS catalysts. For examples, Morsali et al. synthesized two
reaction of dibenzothiophene, which should be mainly attributed to cobalt-based metal-organic frameworks and studied their ODS
the introduction of active Ti sites.
performance in the reaction of DBT.[28] Hicks et al. evaluated
ODS activities of MIL-125 and MIL-47 in ODS reactions of
30]
heterocyclic aromatic sulfur compounds.[29,
Garcia et al.
investigated the aerobic ODS of DBT by using MIL-101(Cr) as
catalyst.[31] More recently, Balula et al. reported that deficient
UiO-66(Zr) exhibited superior desulfurization performance and
even UiO-66(Zr) with high crystallinity was not active in ODS
reactions.[32] Although some research works on MOFs have
been done, their catalytic activity need still be further improved
due to the lack of active sites.
In this work, we report that the ODS performance of UiO-66(Zr)
can be enhanced by partial Ti ion exchange. This strategy is not
only efficient for UiO-66(Zr) with crystal defect but also for UiO-
66(Zr) with high crystallinity.
1. Introduction
Various
desulfurization
adsorptive
techniques
involving
and
hydrodesulfurization,[1]
desulfurization[2-4]
oxidative desulfurization (ODS) have been widely studied for
acquiring clean fuel oil. Thereinto, oxidative desulfurization is
considered to be one of the most promising methods for
producing ultra-low sulfur fuels because it can effectively remove
the refractory sulfur-containing aromatic compounds under mild
conditions. Therefore, various kinds of heterogeneous catalysts
have been widely studied in recent years.[5-8] Of them, some
porous materials with Ti active sites exhibited highly efficient
catalytic performance in some ODS reactions.[9-12] The studies
indicated that rich porosity and large surface area are beneficial
for enhancing the ODS activity of catalysts because their mass
transfer ability can be improved.[13, 14]
2. Results and Discussion
Recently, metal-organic frameworks (MOFs) have attracted
considerable attention due to their advantages such as rich
porosity, large surface area, high thermal and chemical
stability.[15, 16] For this reason, some MOFs have been attempted
to use as ODS catalysts. Thereinto, most of studies focused on
the MOFs supported active phase catalysts. For instances, ionic
liquid as active phase was supported on UiO-66(Zr) for ODS of
benzothiophene.[17] Various phosphotungstic acids[18-20] or
Ti-UiO-66-H
UiO-66-H
Ti-UiO-66-D
UiO-66-D
Simulated UiO-66
[a]
Dr. Gan Ye, Dr. Xiaolin Li,Dr. Kunyue Leng, Prof. Yinyong Sun
MIIT Key Laboratory of Critical Materials Technology for New
Energy Conversion and Storage, School of Chemistry and Chemical
Engineering, Harbin Institute of Technology, Harbin, 150001, China
E-mail: yysn@hit.edu.cn
10
20
30
40
50
2 Theta (degree)
Figure 1. XRD patterns of various samples.
[b]
[c]
Prof. Hui Qi
The Second Hospital of Jilin University, Changchun, 130041, China
Prof. Wei Xu
State Key Lab of Inorganic Synthesis and Preparative Chemistry,
College of Chemistry, Jilin University, Changchun, 130012, China
2.1. Characterization of catalyst
The powder XRD patterns of the various samples are shown in
Fig. 1. As seen, the experimental XRD patterns of UiO-66-D and
UiO-66-H are in good agreement with the simulated patterns as
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cphc.201700182
ChemPhysChem
ARTICLE
reported in the previous literatures[33-35]. Meanwhile, the Ti-
exchanged samples also exhibited well-resolved diffraction
peaks, which are characteristic of the UiO-66 framework
structure. These results implied that the structure of UiO-66 was
not changed and the crystallinity was well maintained after Ti
ion-exchange. Moreover, no diffraction peaks assigned to the
impurities or any titanium species could be observed. This
suggested that Ti ions were possibly incorporated into the
framework of UiO-66 after ion exchange.
Fig. 2 exhibited N2 sorption isotherms of various samples. All
the samples displayed typical type I isotherms in the region of
low relative pressure, indicating that they are microporous
materials. The detailed sorption data are listed in the Table 1. As
seen, after Ti ion exchange the BET surface areas of Ti-UiO-66-
D and Ti-UiO-66-H are increased to 1109 m2 g-1 and 1346 m2 g-1
from 803 m2 g-1 and 1091 m2 g-1, respectively. The enhancement
degree on the surface area reached 50% and 20%, respectively.
These results suggested that partial Zr ions in UiO-66(Zr) were
possibly substituted by Ti ions. Additionally, Ti-UiO-66-D
exhibited pore distribution curve centered at around 1.36 nm
similar to UiO-66-D (Fig. 2 inset) and even Ti-UiO-66-H gave
larger average pore size than UiO-66-H. Meantime, pore volume
for UiO-66-D and UiO-66-H was accordingly increased to 1.06
mL/g and 0.96 mL/g from 0.66 mL/g and 0.76 mL/g after Ti ion
exchange, respectively. These data demonstrated the point
again that partial Zr ions in UiO-66(Zr) have been replaced by Ti
ions.
800
(a)
700
600
500
1.30
1.35
1.40
1.45
400
300
200
100
0
Pore width (nm)
UiO-66-D
Ti-UiO-66-D
0.0
0.2
0.4
0.6
0.8
1.0
Relative pressure (p/p0)
1000
900
800
700
600
500
400
300
200
100
0
(b)
1.20
1.25
Pore width (nm)
1.30
1.35
1.40
UiO-66-H
Ti-UiO-66-H
0.0
0.2
0.4
0.6
0.8 1.0
Relative pressure (p/p0)
Figure 2. N2 sorption isotherms and pore distribution curve (inset) of different
samples.
Table 1. Textural properties of various samples.
Figure 3. SEM images of UiO-66-D (a), Ti-UiO-66-D (b), UiO-66-H (c), Ti-UiO-
66-H (d) and EDS elemental mapping images of Ti-UiO-66-D (e) and Ti-UiO-
66-H (f).
Zr content
(wt%)[a]
Ti content
(wt%)[a]
BET surface Pore volume
Samples
(mL g-1)
area (m2 g-1)
UiO-66-D
Ti-UiO-66-D
UiO-66-H
32.9
27.7
31.8
27.0
--
5.1
--
803
0.66
1.06
0.76
0.96
1109
1091
1346
SEM images of various samples are shown in Fig. 3a-d.
Obviously, the distribution of crystal size in UiO-66-D and Ti-
UiO-66-D is wide between 50 and 200 nm (Fig. 3a -b).
Comparatively, UiO-66-H and Ti-UiO-66-H showed relatively
uniform crystal size around 150 nm (Fig. 3c-d). Moreover, to
demonstrate the presence of Ti species and observe their
Ti-UiO-66-H
4.7
[a] ICP
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10.1002/cphc.201700182
ChemPhysChem
ARTICLE
distribution state in Ti-UiO-66-D and Ti-UiO-66-H, their EDS
elemental mapping images were taken (Fig. 3e-f). Apparently,
the presence of Ti element can be observed and their
distribution was uniform in the two samples. ICP results
indicated that Ti content in Ti-UiO-66-D and Ti-UiO-66-H was
5.1 and 4.7 wt%, respectively. Based on the ICP data, the
average value of Zr in one Zr6 cluster replaced by Ti was about
1.5 for Ti-UiO-66-H and 1.56 for Ti-UiO-66-D.
activity than UiO-66-H. The removal content of DBT reached
91.3% after a reaction time of 120 min, indicating that partial Ti
ion exchange is helpful for enhancing ODS performance of UiO-
66-H.
To further verify the efficiency of this strategy, ODS activities of
UiO-66-D and Ti-UiO-66-D were also evaluated. Similarly, Ti-
UiO-66-D showed higher ODS performance than UiO-66-D.
After a reaction time of 120 min, UiO-66-D gave a DBT removal
content of 80.1%. Comparatively, the removal content of DBT
over Ti-UiO-66-D reached 98.2% (Fig. 4a). These results
demonstrated that this strategy by Ti ion exchange is efficient for
enhancing ODS performance of UiO-66(Zr).
2.2. Catalytic activity
Considering that around 50% of DBT may be extracted by
acetonitrile in the studied catalytic system, the removal content
of DBT cannot really reflect the ODS ability of the catalysts.
Therefore, the content of the product dibenzothiophene sulfone
(DBTO2) in model fuel and extraction phases was analyzed
before and after reaction by GC-MS. It was found that 94.4%,
49.3%, 33.7% and 8.3% DBT didn’t be oxidized over UiO-66-H,
100
(a)
80
60
40
UiO-66-D, Ti-UiO-66-H and Ti-UiO-66-D catalysts after
a
reaction time of 120 min, respectively (Fig. S1 and Fig. S2). By
calculation, the yield of DBTO2 over Ti-UiO-66-D is 91.7%, which
is nearly twice as that for UiO-66-D (50.7%). And the yield of
DBTO2 over Ti-UiO-66-H is 66.3%, which is about twelve times
as that for UiO-66-H (5.6%) (Fig. 4b).
Additionally, the catalytic performance of Ti-UiO-66-D was
studied in the ODS reactions of benzothiophene (BT) and 4,6-
dimethyl-dibenzothiophene (4,6-DMDBT). After a reaction time
of 120 min, the removal content of BT and 4,6-DMDBT reached
80.1% and 66.2%, respectively (Figure S3). Further, a model
diesel oil was prepared to evaluate its potential in practical
application. As shown in Figure S4, the content of sulfur in
model diesel oil can be removed above 80%, suggesting that Ti-
UiO-66-D could be a potential candidate in ODS of diesel.
UiO-66-H
UiO-66-D
Ti-UiO-66-H
20
Ti-UiO-66-D
0
0
20
40
60
80
100
120
Reaction time (min)
100
91.7%
(b)
80
60
40
20
0
66.3%
2.3. Reusability and structural stability of catalyst
50.7%
100
80
60
40
20
0
5.6%
UiO-66-D
Catalysts
Ti-UiO-66-D
UiO-66-H
Ti-UiO-66-H
Figure 4. Removal content of DBT with reaction time over various catalysts at
60 oC (a); Yield of DBTO2 over various catalysts in the ODS reaction of DBT
(b).
To evaluate the catalytic performance of catalysts, ODS of DBT
was firstly carried out at 60 oC. Fig. 4a showed the removal
content of dibenzothiophene (DBT) with reaction time over
different catalysts. As known, approximately 54% DBT could be
extracted by acetonitrile in the studied reaction system.[32,
When UiO-66-H was used as catalyst, only 58.6% DBT can be
removed. Interestingly, Ti-UiO-66-H exhibited much higher ODS
1
2
3
4
Recycle times
36]
Figure 5. Reusability of Ti-UiO-66-D in the ODS reaction of DBT.
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10.1002/cphc.201700182
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ARTICLE
Based on this fact that Ti-UiO-66-D gave superior ODS activity,
its reusability was evaluated. After each cycle, the catalyst was
recovered by centrifugation, washing with acetonitrile, and
reused in the next cycle under the same reaction conditions. As
shown in Fig. 5, the catalytic activity would decrease after each
cycle. However, the removal content of DBT can be still
maintained above 85% after the third reuse. Such decrease in
activity can be possibly attributed to the loss of partial active
sites covered by oxidation products because the activity may
almost be recovered by calcining the reused catalyst after the
third cycle. These results indicated that Ti-UiO-66-D is really a
heterogeneous catalyst and can be reused. Additionally, the
structural stability of Ti-UiO-66-D after reuse was also
investigated by FT-IR spectroscopy and XRD techniques. As
shown in Fig. S5, the reused Ti-UiO-66-D displayed similar
infrared absorption peaks to the fresh one. Further, XRD
patterns of the reused sample are in agreement with those of the
fresh one, indicating that the structure of Ti-UiO-66-D is stable
after reuse (Fig. S6).
. However, after Ti ion exchange, Zr sites can be partially
substituted by Ti sites. Meantime, some coordination
unsaturated sites around Ti sites were possibly formed during
ion exchange and thus resulted in the presence of more active
sites. Moreover, Ti sites might be more active than Zr sites
because Ti ion possessed stronger oxiditive ability than Zr ion.[39]
These factors could be the main reasons why Ti-UiO-66-H
displayed much higher ODS activity (66.3% yield of DBTO2) than
UiO-66-H. In comparison, as reported, there are many
coordination unsaturated sites in the structure of UiO-66-D with
crystal defects.[40-44] Therefore, UiO-66-D showed better ODS
activity (50.7% yield of DBTO2) than UiO-66-H. After Ti ion
exchange,
Ti-UiO-66-D
exhibited
enhanced
catalytic
performance (91.7% yield of DBTO2) compared with UiO-66-D,
indicating again that Ti sites should be more active than Zr sites.
In addition, Ti-UiO-66-D (5.1% Ti) had similar Ti content to Ti-
UiO-66-H (4.7%) but it exhibited higher ODS activity than Ti-
UiO-66-H. This result might be related to the presence of more
coordination unsaturated sites in the structure of Ti-UiO-66-D.
Certainly, considering that the molecular size of DBT (8.0 Å 
12.2 Å) and DBTO2 (8.9 Å  12.2 Å) is relatively big,[7] the
increase in surface area and pore volume of UiO-66(Zr) after Ti
ion exchange should be also beneficial factors for improving the
catalytic activity of UiO-66(Zr) due to the enhancement of mass
transfer ability.
3.4. Relationship between structure and catalytic performance
To better understand why Ti-UiO-66-H and Ti-UiO-66-D
exhibited enhanced catalytic activity in the ODS reaction of DBT,
a model was proposed about the structure of UiO-66(Zr) before
and after Ti ion exchange (Scheme 1). As known, most of Zr
sites in the structure of UiO-66-H with high crystallinity were well
coordinated by O and Cl ions.[37, 38] As a result, UiO-66-H gave
low ODS activity (5.6% yield of DBTO2), which could be
attributed to the lack of active sites.
Scheme 2. Proposed reaction mechanism over Ti-UiO-66(Zr) in ODS of DBT.
In addition, a reaction mechanism was proposed over Ti-UiO-
66(Zr) in ODS of DBT (Scheme 2). In this catalytic system, DBT
molecule was easily extracted into acetonitrile phase. Meanwhile,
both Ti and Zr sites might firstly interact with H2O2 to produce
intermediate species. Then, such species can oxidize DBT in
acetonitrile phase into DBTO2. Considering that the ODS
activity of UiO-66(Zr) was greatly enhanced after Ti ion
exchange, it is suggested that Ti sites should possess stronger
Scheme 1. Proposed structural model of UiO-66(Zr) before and after Ti ion
exchange.
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10.1002/cphc.201700182
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ARTICLE
Powder X-ray diffraction (XRD) patterns were recorded on a Rigaku
ODS ability than Zr sites. Therefore, more DBTO2 could be
formed by active Ti sites.
D/Max-2550 diffractometer equipped with
a SolX detector-Cu Ka
radiation with wavelength of λ = 1.5418 Å. Nitrogen sorption isotherms
were obtained at 77 K on a 3H-2000PS1 Gas Sorption and Porosimetry
system. Samples were normally prepared for measurement after
degassing at 423 K under vacuum until a final pressure of 1  10-3 Torr
was reached. Scanning electron microscopy (SEM) images and Energy
dispersive X-ray spectroscopy (EDX) elemental mapping were recorded
on SUPRA 55 operated with an acceleration voltage of 200 kV. Ti
content was determined by inductively coupled plasma emission
spectrometry (ICP) on a PerkinElmer Optima 5300DV atomic emission
spectrometer. Fourier Transform infrared (FT-IR) spectra were recorded
on a NicoLET iS10 spectrometer.
3. Conclusions
In summary, Ti-modified UiO-66(Zr) catalysts were prepared by
Ti ion exchange method. After ion exchange, the structure of
UiO-66(Zr) was well maintained and their BET surface areas
and pore volumes were accordingly increased, indicating that Ti
species be Incorporated into the framework of UiO-66(Zr). As a
result, Ti ion exchanged UiO-66(Zr) catalysts exhibited
enhanced ODS activity. This strategy is not only efficient for
UiO-66(Zr) with crystal defect but also for UiO-66(Zr) with high
crystallinity. Especially, the ODS performance of UiO-66(Zr) with
high crystallinity can be improved above 11-fold in the ODS
reaction of dibenzothiophene. Such catalytic performance could
be mainly attributed to the introduction of active Ti sites.
Additionally, it is demonstrated that Ti-containing UiO-66(Zr) is
really a heterogeneous catalyst and can be reused.
Catalytic tests
The oxidative desulfurization (ODS) reaction was performed using a
liquid-liquid extraction and the oxidative catalytic desulfurization stage. A
certain amount of BT, DBT or 4,6-DMDBT was dissolved in n-octane
(with a concentration of 500, 1000 and 500 ppmw of sulfur from BT, DBT
and 4,6-DMDBT, respectively) to act as model fuel. The model diesel oil
was prepared by mixing BT, DBT and 4,6-DMDBT (100, 300 and 100
ppmw, respectively) in 10 g n-octane with a total sulfur content of 500
ppmw. The reactions were performed under air in a closed 100 mL three-
neck glass flask with a vigorous magnetic stirrer (1000 r/min) and
immersed in an oil-bath at 60°C. In a standard run, the catalyst (50 mg)
was added to model fuel (10 g) and acetonitrile (10 g), and the resulting
mixture was stirred for other 15 min at 60 °C. The catalytic reaction
process is initiated by addition of H2O2 (30 wt%, 195 µL) as oxidant with
a H2O2/S molar ratio of 6:1. The agitation of reaction solution was
stopped under different times until the liquids layered. Then, the right
amount of liquid in octane phase was taken and analyzed by gas
chromatography on an Agilent 7890A GC with an FID detector using a 30
m packed HP5 column. The products were also identified by GC-MS
(5975C-7890A) analysis. DBT removal rate (R) was calculated according
to the equation R = (1-Ct/C0)  100%. Where C0 and Ct stand for the
initial concentration and the reaction concentration of DBT in n-octane
phase after t minutes, respectively.
Experimental Section
Materials
Tetrachlorobis(tetrahydrofuran)titanium(IV) [TiCl4(THF)2] was purchased
from Alfa Aesar. Benzothiophene (BT), Dibenzothiophene (DBT) and 4,6-
dimethyl-dibenzothiophene (4,6-DMDBT) were purchased by Aldrich.
Zirconium tetrachloride (ZrCl4), 1,4-benzenedicarboxylic acid (H2BDC),
N,N-dimenthylformamide (DMF), ethanol, methanol, hydrochloric acid
(HCl 37%), hydrogen peroxide (30 wt%), acetonitrile, and n-octane were
purchased from Sinopharm Chemical Reagent Co. All chemicals and
solvents are analytical purity and used without further purification.
Synthesis of catalysts
UiO-66 with crystal defect was prepared according to the reported
procedures with slight modification.[45] In a typical synthesis, ZrCl4 (0.159
g, 0.68 mmol) and H2BDC (0.113 g, 0.68 mmol) were dissolved into 70
mL DMF with the assistance of ultrasonication at room temperature.
Acknowledgements
Then, the obtained mixture was sealed in
a 100 mL Teflon-lined
autoclave and placed in a pre-heated oven at 120 °C for 24 h. After
cooling to room temperature, the resulting white solid was centrifuged
and washed with DMF and ethanol. Finally, the sample was dried under
vacuum for 12 h at 150 °C. The final sample was named as UiO-66-D.
The similar synthetic procedures to UiO-66-D were adopted to synthesize
UiO-66 with high crystallinity except that 70 uL HCl (37 %) was added.
The final sample was named as UiO-66-H. Ti ion-exchanged UiO-66 was
synthesized by the reported procedures with sight change.[46] Briefly, 100
mg TiCl4(THF)2 was dissolved into 6 mL DMF in a 20 mL dram vial. Then,
83 mg UiO-66-D or UiO-66-H was added and the mixture was incubated
at 85 °C in a pre-heated oven for 5 d. After cooling to room temperature,
the mixture was centrifuged, washed with DMF and MeOH. The resulting
solid was immersed in 10 mL fresh MeOH for 1 d. After three cycles of
soaking, the solid was centrifuged and dried under vacuum for 12 h at
150 °C. The obtained sample was named as Ti-UiO-66-D or Ti-UiO-66-H,
respectively.
We thank the financial support from the Fundamental Research
Funds for the Central Universities (Grant No. HIT. NSRIF.
2015046), Open Funding from the State Key Lab of Inorganic
Synthesis and Preparative Chemistry, Jilin University, and the
Scientific Research Foundation for the Returned Overseas
Chinese Scholars, State Education Ministry.
Keywords: UiO-66
•
Titanium
•
MOFs
•
Oxidative
desulfurization • Dibenzothiophene
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10.1002/cphc.201700182
ChemPhysChem
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Title
The oxidative desulfurization performance over UiO-66(Zr) can be greatly enhanced
by Ti ion exchange. This strategy is not only efficient for UiO-66(Zr) with crystal
defect but also for UiO-66(Zr) with high crystallinity.
This article is protected by copyright. All rights reserved.