Journal Pre-proof

Biomimetic Oxygen Activation and Electron Transfer Mechanism for

Oxidative Desulfurization

Mingyue Chi, Ting Su, Lulu Sun, Zhiguo Zhu, Weiping Liao,
Wanzhong Ren, Yuchao Zhao, Hongying Lü

PII: S0926-3373(20)30549-X
DOI: https://doi.org/10.1016/j.apcatb.2020.119134
Reference: APCATB 119134

To appear in: Applied Catalysis B: Environmental

Received Date: 6 December 2019

Revised Date: 26 April 2020
Accepted Date: 13 May 2020

Please cite this article as: Chi M, Su T, Sun L, Zhu Z, Liao W, Ren W, Zhao Y, Lü H,
Biomimetic Oxygen Activation and Electron Transfer Mechanism for Oxidative Desulfurization,
Applied Catalysis B: Environmental (2020), doi: https://doi.org/10.1016/j.apcatb.2020.119134

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Biomimetic Oxygen Activation and Electron Transfer
Mechanism for Oxidative Desulfurization

Mingyue Chi,a Ting Su,*a Lulu Sun,a Zhiguo Zhu,a Weiping Liao,a Wanzhong Ren,b

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Yuchao Zhao,b and Hongying Lü*a

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a. Green Chemistry Centre, College of Chemistry and Chemical Engineering, Yantai Uni-
versity, Yantai 264005 (China)

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b. Collaborative Innovation Center of Light Hydrocarbon Transformation and Utilization,
College of Chemistry and Chemical Engineering Yantai University, Yantai, 264005
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(China)
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Corresponding Address:
E-mail address: [email protected] (H. Lü); [email protected] (T. Su)
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Graphical abstract
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Highlights
 A green aerobic oxidative desulfurization biomimetic system was designed.
 The catalytic system combined high catalytic activity and stability.


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Cyclic voltammetry measurements showed a 17-fold increase in current density.
The biomimetic oxygen activation and electron transfers mechanism was revealed.
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ABSTRACT
Construction of biomimetic catalytic systems is recognized as one of the most prospective,
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but is challenging approaches to achieve efficient aerobic oxidative transformations. Herein, a

green aerobic oxidative desulfurization (AODS) biomimetic system was designed, which combined
an Anderson polyoxometalate (POM) -based ionic liquid (IL) with deep eutectic solvent (DES).
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The 3-(pyridine-1-ium-1-yl) propane-1-sulfonate]3 Co(OH)6Mo6O18 {abbreviate as

[PyPS]3Co(OH)6Mo6O18} combined high catalytic activity and stability with perfect synthetic
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availability on the desulfurization of diesel. Also, excellent recoverability showing little decrease
in activity after 5 cycles has aroused the great interest. Cyclic voltammogram measurement shows
conclusive evidence of oxygen activation with a 17-fold current density increase, further confirm-
ing the reduction of the aerobic oxidation reaction barrier. It revealed the biomimetic oxygen acti-
vation and synergistic electron transfers mechanism for ODS, which may provide a new insight
into the construction of biomimetic system in the future.

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KEY WORDS: deep eutectic solvents, polyoxometalate, oxidation desulfurization; biomimetics

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1 INTRODUCTION
Sulfur oxides (SOx), mainly from the burning of fossil fuels, the discharge of industrial waste
gas and automobile exhaust gas, are the main pollutants contributing to environmental acidifica-
tion.[1,2] Therefore, many countries have established a number of regulations that limit the sulfur
content of fuel[3]. A valid control of SOx is a matter of great urgency reducing harmful influences
on the environment as well as healthy daily life [4,5]. So far, hydrodesulfurization (HDS) technol-
ogy has matured in the production of low-sulfur diesel fuel with highly efficient in removing mer-
captans, sulfides and disulfides. Considering harsh reaction conditions (high temperature, pressure,
cost of production etc.) and the removal difficulty of 4,6-DMDBT compounds and its deriva-

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tives[6,7], many non-hydrodesulfurization methods such as oxidative desulfurization (ODS)[8–
12], adsorption desulfurization (ADS)[13,14] and bio-desulfurization[15] have entered the visual

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field, among which ODS has the most promising development prospect[12]. The principle of oxi-
dative desulfurization is to oxidize the sulfide in the oil to sulfoxide and sulfone with an oxidizing
agent, and then the sulfone compounds could be removed by extraction[7,16].

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A variety of oxidants, such as dioxygen[17], hydrogen peroxide[18,19], ozone[20,21], NO2
[22], etc. have been used in ODS system, where dioxygen is the most environmentally compatibil-
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ity and low-cost oxidant. Considering a triplet ground state of molecular oxygen, it is commonly
accepted that direct oxidation by O2 is often kinetically unfavored due to high activation energy
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under mild conditions. Therefore, various of catalysts have been employed in the aerobic oxidation
desulfurization (AODS). Good performance can only be achieved at high temperature or with a
sacrificial agent, increasing the cost or possibilities for side reactions. Polyoxometalates (POMs)
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attract considerable attentions as high activity catalysts due to the tunable acidic as well as redox
properties and tailored cations, which have been reported excellent performances under mild con-
dition in AODS[23,24]. POMs are considered as a series of promising catalysts in ODS systems
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because of the oxidation and compatibility with various oxygen source. Among several structural
types of POMs, Anderson-type polyanions show a striking planar structure and contain a central
metal-oxygen octahedron surrounded by MO6 (M = W or Mo) octahedrons sharing six edges. And
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each skeleton metal atom (W or Mo) has two terminal oxygen atoms[24]. Therefore Anderson-type
catalysts have very special polymetallic oxygen clusters, which makes them highly reactive in cat-
alytic reactions. However, the homogenous AODS system based on POMs catalyst still exists draw-
backs like lower recovery of catalyst. Thus, it’s important to design the POM catalyst AODS system

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with better recycling performance as well as high activity. To circumvent this problem, it’s ex-
tremely important to construct heterogenous AODS system as well as gain in-depth and systematic
understanding on oxidation desulfurization system.
Deep eutectic solvents (DESs), which are consisted of a hydrogen bond acceptor (HBA) and
a hydrogen bond donor (HBD) through hydrogen bond interaction, have promising application pro-
spects on a large scale for kinds of catalytic system[25–28]. Compared with traditional ILs, DESs
possess the similar physicochemical properties as well as cheaper and more environmentally
friendly. The synthetic processes of DESs are smoothly under mild conditions with the natural and
readily starting materials. After mixing in the proper ratio under heating, without any purification,

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a homogenous liquid is formed with 100% atom utilization. Up to date, DESs can be used as alter-
native of ionic liquids and have a very broad development prospect, like polymerizations,[15] bio-

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mass processing,[29,30] enzyme-catalyzed reactions,[31–33] extraction,[34–37] nanotechnol-
ogy,[38], and oxidative desulfurization[34,39,40].
In typical ODS reactions, peroxyorganic acids are usually acted as oxidant through an oxida-

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tion reaction of organic acids with hydrogen peroxides, which is actually the rate limited step of
ODS[23]. However, those peracids are hard to be obtained under mild conditions with dioxygen as
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the oxidant. Following a nature’s biomimetic way, the application of electron-transfer mediators
(ETMs) would bring dawn and hope to lower the activation energy through breaking up the whole
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into several parts, which means the reaction process can be controlled by multiple interconnected
redox cycles rather than a single oxidation reaction[38,41,42]. Enlightened by some previous re-
searches, an innovative biomimetic system was designed with excellent AODS performance and
polyoxometalate acted as the ETM for transferring electron, in which the rate limited step can be
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promoted by two lower energy steps in the biomimetic system[23,24]. However, deep understand-
ing for the ODS biomimetic system mechanism and the specific information of system construction
remains challenging issues. One of the most important questions is that it is almost impossible to
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capture specific path of electronic transfer or conclusive evidence of oxygen activation. Therefore,
researchers need to spare no effort for improvement in the construction mechanism, dual activation
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process and synergistic effect of electron transfers in the biomimetic system.

In this work, an innovative biomimetic system combined with POM-based IL and DESs was
proposed under mild conditions. In our earlier work, kinds of difficulties have been solved, such as
searching for a high activity and selectivity in ODS using IL under quite mild conditions[43], re-
placing IL with environmentally benign DES and exploring the mechanism preliminarily[44]. In
this work, the designed Anderson-type POM [PyPS]3Co(OH)6Mo6O18 and DESs were introduced
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aerobic oxidative desulfurization (AODS), displaying an outstanding activity and stability for die-
sel DBT under mild conditions. The properties of the POM-based IL and DES as well as the dy-
namics analysis of the ODS system were detailed investigated. For the first time, cyclic voltammo-
gram (CV) was used to gain insights into biomimetic oxygen activation and synergistic electron
transfer in aerobic oxidative desulfurization. Significantly, these new ideas could afford an ap-
proach on efficient aerobic oxidative transformations because of its similarities to biological sys-
tems. Overall, those results conclude that the CV measurement could be utilized as efficient method
for the mechanism exploration and the biomimetic catalytic systems in AODS may provide a step
towards integrating biomimetic systems into the design of diverse catalytic fields.

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2 EXPERIMENTAL
2.1 Materials, Solvents, and Reagents.

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All chemicals were analytical and used as received without further purification.

2.2 [PyPS]3Co(OH)6Mo6O18 Synthesis and Characterization

based on the procedures in the

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Anderson polyoxometalates (NH4)3Co(OH)6Mo6O18 and N-propionylpyridine were prepared
literature[45–47]. The preparation method of
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[PyPS]3Co(OH)6Mo6O18 is shown as follows in Scheme S1, 0.3090 g N-propionylpyridine was
added to 0.5395 g (0.0005 mol) (NH4)3Co(OH)6Mo6O18 solution (20 mL deionized water), and
stirred at room temperature for 24 h. The water was removed by steaming and dried under vacuum
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to obtain the final POM.[47]

The X-ray diffraction (XRD) of [PyPS]3Co(OH)6Mo6O18 was characterized by a X-ray dif-
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fractometer (Rigaku Smart Lab3) with CuKα radiation at 35 kV and 25 Ma (λ = 1.5405 Å). The
pattern was recorded in steps of 0.02 ° at a scan rate of 10 ° min-1 from 20 to 80 °. Scanning electron
microscope (SEM) micrographs were analyzed by Rili SU 8000HSD Series Hitachi New Genera-
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tion Cold Field Emission SEM. The Fourier-transform infrared spectroscopy (FT-IR) spectra of the
sample was recorded using KBr as a background on a SHIMADZU IRAffinity-1S FT-IR spectrom-
eter in transmittance mode. X-ray photoelectron spectroscopic (XPS) analyses were performed on
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an AXIS-ULTRA DLD-600W spectrometer. UV-vis diffuse reflectance spectrum was recorded on

a Tu-1901 with a scanning range of 200 to 800 nm at room temperature with a step size of 5 nm,
using BaSO4 as the standard substance (Beijing General Analysis Instrument Co., Ltd.). Conduc-
tivity was measured on a DDS-302 conductivity meter, and viscosity was tested on a DV2T vis-
cometer. Cyclic voltammogram (CV) was recorded on an CHI660e electrochemical potentiostat.

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In a typical process, CV curves were detected with three‐electrode measurements with glassy car-
bon electrode (GC) as working electrode, a platinum wire as counter electrode, a standard Ag/AgCl
as a reference electrode. The measurement was conducted in 0.1 mol L-1 H2SO4 acetonitrile solution
with scan rate 50 mV s-1. The volume of the electrolyte was 2~4 mL. 0.1g POM was dissolved in
the above solution in order to ensure the solution saturation. DESs was directly dropped in the
electrolyte and dissolved after stirring. To ensure accuracy, the curves are recorded for at least 6
circles until the signal is stable, and choosing the stable cycle as the CV data.

2.3 Preparation of DESs

A series of DESs were synthesized by selecting as a hydrogen bond donor (HBD) and poly-

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ethylene glycol (PEG) of different molecular weights as a hydrogen bond acceptor (HBA).In a
typical run, in a round-bottomed flask benzenesulfonic acid (BSA) was mixed with HBA such as

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PEG1000 at an HBD/HBA molar ratio of 1:1~3, and then this mixture was stirred vigorously in an
oil bath at 80 oC. After about 1 h, the homogeneous liquid that is the as-synthesized DESs were
obtained, denoted as PEG/BSA. And the products were labeled as PEG1000/BSA, PEG2000/BSA,
PEG4000/BSA and PEG6000/BSA, respectively.

2.4 Oxidation of the model diesel and commercial diesel -p

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Model diesel was first prepared by BT, DBT or 4,6-DMDBT dissolved in decalin, and the
sulfur concentration was 500 ppm. Desulfurization reactions were carried out in a three-necked
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round-bottomed flask. In order to prevent volatilization of decalin, the middle bottle mouth was
equipped with a condensation tube at a temperature below zero. The second bottle mouth was
closed with a rubber plug connected to the O2, and the last one was closed unless sampling. At 60
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°C, 20 mL model oil was first subjected to extraction desulfurization with 4 mL DESs. Then 0.02
g POM was added under vigorous stirring. The reaction solution was stirred with molecular oxygen
(flow rate of 60 mL min–1) and the upper phase was periodically sampled, and the sulfur content
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was determined by Gas chromatography (GC-FID).

3 RESULTS AND DISCUSSION

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3.1 Characterization of the [PyPS]3Co(OH)6Mo6O18

The ultimate synthesized [PyPS]3Co(OH)6Mo6O18 is illustrated in Figure 1A and the color of
the POM is light green. XRD patterns of PyPS, (NH4)3Co(OH)6Mo6O18 and
[PyPS]3Co(OH)6Mo6O18 were shown in Figure S1 to analyze the structural properties and phase
purity. The characteristic and relative intense peak of (NH4)3Co(OH)6Mo6O18 were determined at
2θ =15.1, 16.8, 23.9, 33.7, 51.4 and 60.9 o, which were in accordance with JCPDS 04-0226 of
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(NH4)3Co(OH)6Mo6O18. However, after the introduction of ionic liquid section PyPS, the pattern
of [PyPS]3Co(OH)6Mo6O18 changed a lot and showed a weaker crystallization. The main peaks of
[PyPS]3Co(OH)6Mo6O18 were similar with the pattern of PyPS at 2θ = 14.6, 17.5, 21.0, 24.1, 29.9
and 37.5 o, but the peaks were too strong to see (NH4)3Co(OH)6Mo6O18. The morphology of the
(NH4)3Co(OH)6Mo6O18 and [PyPS]3Co(OH)6Mo6O18 were analyzed by SEM in Figure S2. It can
be seen that most of [PyPS]3Co(OH)6Mo6O18 are flat sheet materials with many fragmentary parti-
cles. Compared with the SEM of (NH4)3Co(OH)6Mo6O18, there was more irregular-shaped particles
in [PyPS]3Co(OH)6Mo6O18.
Meanwhile, the POM was detected by FT-IR spectroscopy shown in Figure 1B. The peaks of

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648 575 and 775 cm-1 belonged to the characteristic vibration peak of Mo-O-Mo bond, 1035, 937,
917 and 899 cm-1 were Mo=O terminal base stretching vibration peak, and 445 cm-1 was a Mo-O-

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Co bond[48,49], proving the existence of Anderson structure of [Co(OH)6Mo6O18]3-. In addition,
1485 and 1400 cm-1 were stretching vibration peaks of a pyridine ring C=C and the peak of 1197cm-
1
was characteristic peaks of SO2OH[44]. The above peaks demonstrated the successful synthesis

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of the t [PyPS]3Co(OH)6Mo6O18. In order to further detect the structure of the POM, UV-vis spec-
troscopy of solid state of POM was employed. As shown in Figure 1C, there exhibited strong
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absorption in the range of 200-300 nm, which was corresponding to the structural characteristics
of Mo-O-Mo caused by the octahedral coordination charge transfer process of O2- to Mo6+ in the
polyanion[44,49]. Also there showed two relatively weak absorption band centered at 415 and 604
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nm, which could be attributed to the metal centered lowest energy electronic transition from HOMO
t2g* to LUMO eg* transition of Co3+ in polyanions[48]. The optical energy gap (Eg) can be calculated
according to Tauc plot, as shown in the equation: (αhν)2 = A(hν - Eg), where Eg is the band gap, α
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stands for absorption coefficient, h represents Planck’s constant, ν is the frequency of light vibra-
tion, and A is the proportional constant[50,51]. On the basis of Tauc plot, Eg was determined to be
ca. 1.66 eV (Figure 1D) identified as Co3+ 3d-shell (3d6) state. The result of Eg was located at the
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range of typical inorganic semiconductor, which may possess electron transfer catalytic prop-
erty[52]
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To access more insight into the POM, XPS was further applied to investigate the transfor-
mation of surface chemical bonding environment in polyoxometalate. As indicated in Figure S3A,
the XPS survey spectra show six obvious signal peaks, indicating that the main elements in
[PyPS]3Co(OH)6Mo6O18 including Co, Mo, O, C, N and S. The O 1s spectra can be deconvoluted
into three components attributed to O2- on the surface of the catalyst, surface OH group and ab-
sorbed H2O (Figure S3B). Figure S3C and Figure S3D shown the signal bands of C 1s and N 1s,

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respectively. The original XPS spectra of Co 2p and Mo 3d were deconvoluted into several peaks
as shown in Figure 1E. There are two signal bands in Co element at around 796.1 and 780.9 eV,
which can be attributed to 2p1/2 and 2p3/2 photoelectrons of Co3+ species. In addition, there is a
certain amount of Co with low valence in XPS spectrum. Considering our earlier work, it was
inferred that the existence of low valence Mo and Co could be attributed to the addition of PyPS,
which acted as electron-donating group in the catalyst[43].During the conformation of catalyst, the
electron transferred from PyPS group to [Co(OH)6Mo6O18]3-, leading to the appearance of low va-
lence Mo and Co. In Figure 1F, typical peaks of Mo 3d in [PyPS]3Co(OH)6Mo6O18 on the XPS
spectrum were analyzed and mixed-valence of Mo 3d could be observed. The contribution of Lo-

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rentzian–Gaussian peaks centered at 231.8 eV was assigned to Mo5+, while the small peaks centered
at 232.3 eV were attributed to Mo6+, suggesting the exclusive mixed valence molybdenum species.
On the basis of the above analyses, the Anderson-type [PyPS]3Co(OH)6Mo6O18 polyoxometalate

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was successfully prepared.

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Figure 1. (A) The synthesis diagram, (B) IR spectrum, (C) UV–vis spectrum, (D) the optical
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energy gap of [PyPS]3Co(OH)6Mo6O18 and its XPS spectra (E) Co 2p and (F) Mo 3d.

3.2 Characterization of DESs

DESs in this work were prepared from benzenesulfonic acid and polyethylene glycol (PEG)
of different molecular weights, including PEG1000, PEG2000, PEG4000, and PEG6000, respec-
tively. The interaction between BSA and PEG2000 in DESs was investigated by infrared spectros-
copy in Figure S4. Comparing BSA and BSA/PEG2000, the peak of SO2OH at the peak intensity
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of 1188, 1130, 1037, 1019 cm-1 disappeared. The results gave supports to the strong interaction
between BSA and PEG2000. In comparison with PEG2000 and BSA/PEG2000, it was found that
the peak intensity of 1113, 963, and 842 cm-1 was weakened, which may be resulted from the for-
mation of hydrogen bonds[41].

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Figure 2. (A) conductivity of different DESs measured at 60 oC; (B) viscosity of different
DESs measured from 60 oC to 80 oC.
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In addition, the conductivities of four DESs, including BSA/PEG1000, BSA/PEG2000,
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BSA/PEG4000 and BSA/PEG6000, were measured at 60 oC. In Figure 2A, it was obvious that the
conductivity for BSA/PEG reduced with the increase of PEG molecular weight. BSA/PEG1000
had the biggest conductivity (53.50 μs cm-1) and BSA/PEG6000 displayed the smallest conductiv-
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ity (2.49 μs cm-1). It is commonly believed that the liquid conductivity is related to charge car-
rier[28]. To a certain extent, better conductivity may lead to larger ions mobility and the following
oxidation reaction. Therefore, the bigger conductivity of BSA/PEG1000 (53.50 μs cm-1) may shed
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light on the high redox performance.

Viscosity of different DESs was also measured from 60 oC to 80 oC, which was also associated
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with the ions’ mobility. Figure 2B exhibited the viscosity of different DESs declined slowly with
rising of temperature. The results revealed that the higher PEG molecular weight of DESs, the
worse the liquidity at various testing temperature: BSA/PEG6000 > BSA/PEG4000 >
BSA/PEG2000 > BSA/PEG1000. Considered both aspects, it can be speculated that the conductiv-
ity and viscosity may play a comprehensive effect on the catalytic performance. In other words, it

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was difficult to conclude that the correlation among conductivity, viscosity and desulfurization ca-
pability was positive or negative.

3.3 Performance of different desulfurization systems on removal of DBT

At the beginning of desulfurization, research on the selection of DESs was developed due to
the key role of DESs[54]. A series of DESs named BSA/PEG1000, BSA/PEG2000, BSA/PEG4000
and BSA/PEG6000 were insoluble in the model oil, whereas the [PyPS]3Co(OH)6Mo6O18 was dis-
solved in the DESs, leading to a two-phase desulfurization system including the upper layer model
diesel and the lower layer DESs alongside with the dissolved POM. All the desulfurization perfor-
mance of different DESs system could achieve 100% sulfur removal in 7 h as shown in Table 1.

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When PEG2000/BSA was employed, the removal of DBT can reach 99% in 4 hours. It indicated
that on the removal of DBT, there was an excellent promotion of PEG/BSA DESs system.

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To elucidate the indispensable synergistic effect between DESs and [PyPS]3Co(OH)6Mo6O18,
different desulfurization systems were investigated systematically. As illustrated in Table 1 (No.

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1–7), the catalytic performance was poor in absence of DESs, and only 3% DBT was removed even
with catalyst and oxygen. The extraction desulfurization (EDS) achieved almost the same perfor-
mance after the addition of PEG2000, suggesting the role as an extractant of DESs in ODS (No. 4–
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7). Also, it was obvious that DBT was hardly oxidized if any of DESs, oxygen or POM was missing
in the desulfurization system, emphasizing the irreplaceable role of all the three parts including
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[PyPS]3Co(OH)6Mo6O18, oxygen and DESs. (No. 2, 5, 6, 9) And DES acts as the reaction media,
extractant and electron donor for the oxidative desulfurization, promoting the synergistic interac-
tion between [PyPS]3Co(OH)6Mo6O18 and oxygen. When the desulfurization system consisted of
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the three inseparable parts, different molar amounts of DESs PEG2000/BSA were further compared
(No. 7–9) and the removal of DBT at ratio 1:2 was 98% at 3 h, identifying the fact that
[PyPS]3Co(OH)6Mo6O18 had the ability to activate oxygen[13,16,55,56]. Besides PEG2000,
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PEG1000, PEG4000 and PEG6000 were applied as HBA to get deeper insights into the effect of
molecular weight on the sulfur removal (No. 9–12). With the increase of PEG molecular weight,
the removal of DBT first rose and then dropped, indicating the same fact with Figure 2 that ODS
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performance couldn't be determined by a single factor, which was the result of the synergistic effect
of all parts. At this point, it can be concluded that the synergistic effect between
[PyPS]3Co(OH)6Mo6O18 and DESs PEG2000/BSA has a tremendous influence on the oxidation
desulfurization.
Given that [PyPS]3Co(OH)6Mo6O18 can be soluble in the DESs, EDS process begun first and
then EAODS happened mainly in the lower DESs layer. With the addition of dioxygen, DBT was
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oxidized into DBTO2, leading to sulfur content decrease in model diesel. The structure of the white
precipitate was confirmed by infrared spectroscopy. As shown in the Figure S5, two new absorp-
tion peaks of 1166 and 1288 cm-1 corresponded to the infrared curve oxidation product of DBT. It
could be ascribed to be the vibration absorption peak of the S=O bond according to the related
literature[19], which proved the oxidation product is dibenzothiophene sulfone (DBTO2). These
results are in good agreement with the GC-MS results (Figure S9).

Table 1. The removal of DBT in different AODS systems.

Sulfur removal (%)

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No. Name POM (mg) Time (h)
EDSd EAODSe
1 --- --- 4 0 0

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2 --- 20 4 0 3
3 BSA --- 4 3 2
4
5
PEG2000
PEG2000/BSA
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4
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26
25
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6 PEG2000/BSA 20 4 24 25
7 PEG2000/BSAa 20 3 23 86
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8 PEG2000/BSAb 20 3 24 84
9 PEG2000/BSA 20 3 28 98
10 PEG1000/BSA 20 3 28 80
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11 PEG4000/BSA 20 3 34 91
12 PEG6000/BSA 20 3 29 73
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a
The molar amounts of PEG2000 and BSA were equal.
b
The molar amounts of PEG2000 and BSA were 1:3.
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c
Without the addition of O2.
d
Indicating extraction process. Conditions: 20 mL model diesel (500 ppm); DES if added, 4
mL; 60 °C; 30 min.
e
Indicating catalytic step after extraction. Conditions: 20 mL model diesel (500 ppm); DES if
added, 4 mL; POM if added, 20 mg; 60 °C; 1 atm O2 pressure; 60 mL min–1 O2 flow rate.

3.4 Aerobic catalytic activity of desulfurization system

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Figure 3. Aerobic catalytic activity parameters including (A) different temperature and (B)

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different sulfur-containing substrates on the sulfur removal. Reaction condition: m (DES) = 4 g,
HBA : HBD (molar ratio) = 1:2, V (model oil) = 20 mL, m (POM) = 20 mg, T = 60 °C, O2 (1 atm,
60 mL min-1).
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The catalytic activity of [PyPS]3Co(OH)6Mo6O18 in PEG2000/BSA was tested in the AODS.
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Typically, the sulfur removal reactions were carried out with molecular oxygen as the oxidant under
atmospheric pressure. The desulfurization effect at different temperatures ranging from 50 °C to 80
°C was shown in Figure 3A. It can be clearly seen that the desulfurization rate increased as the
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temperature increased. With the temperature increasing, the desulfurization was able to reach 100%
at 60 °C in less than 4 h, and higher rate of sulfur removal at 70 °C and 80 °C. The results proved
that DESs and POM can maintain high catalytic activity under mild conditions. Considered the
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similar desulfurization performance at 60 °C, 70 °C, and 80 °C and energy conservation, 60 °C was
chose in the desulfurization process.
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The dependence of the POM dosage from 5 mg to 20 mg was shown in Figure S6. It is obvious
that the mass of the POM plays a very important role in this reaction. The mass range of the POM
was selected from 5 mg to 50 mg, and all systems with various dosages exhibited 100% desulfuri-
zation. It can also be seen from the figure that the effect of the POM dosage of 20 mg and 50 mg
was more effective leading to almost 99% sulfur removal at 3 h, and the difference between the

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two was so small as to be ignored. Therefore, from the viewpoint of cost saving, the final POM
dosage was 20 mg.
Different structures of sulfur-containing substrates are also important factors affecting the ef-
ficiency in the bi-phase AODS system. Under the same reaction conditions, the other two main
thiophene sulfides 4,6-DMDBT and BT were studied using molecular oxygen as an oxidant (Figure
3B). Comparisons were obtained from the results that all of the above sulfur-containing compounds
could be oxidized to the corresponding sulfones after 8 h. The catalytic activity of the sulfur-con-
taining compound was decreased as DBT > 4,6-DMDBT > BT. It was worth noting that the sulfur
removal of DBT can achieve 99% only in 4 h whereas the removal of 4, 6-DMDBT reached 100%

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after 6 h and BT after 8 h. The removal of BT was worse to that of the other two sulfur-containing
substrates, and the reason lay in the difference of S electron density. According to literatures[57],

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S electron density of S-containing compounds is 5.758 for DBT, 5.760 for 4,6-DMDBT and 5.739
for BT. It is generally believed that high S electron density contributes for desulfurization perfor-
mance under the same conditions[19]. BT has the smallest S electron density of all used sulfur-

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containing substrates. Also, the result proved the steric effect of methyl groups might play a vital
position on sulfur-containing substrates removal. Therefore, in comparison with DBT, the inferior
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performance of DBT derivative could be ascribed to the stereo-hindrance as well as large molecular
weight. Based on the results, this AODS system coupling DESs with POM-based IL has shown
great potential in other S-containing organics both large-sized like 4,6-DMDBT and small-size BT.
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3.5 Possible mechanism of the AODS process with DESs

Desulfurization mechanism is extremely important to comprehend the AODS system from the
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perspective of a biomimetic process. In light of the aforementioned results and some previous work,
a possible desulfurization mechanism for the novel PEG/BSA DESs would involve a dual activa-
tion concept and was proved from different perspectives. The systematically exposition of AODS
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mechanism in DESs was studied by infrared spectroscopy. Figure S7 showed the infrared spectrum
of PEG2000/BSA, DBT and a mixture of both (molar ratio 1:1) to understand the nature of inter-
action between the DES and DBT. The strong interaction between DES and S-compounds has been
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proved in our earlier results[58,59]. In this work, in comparison with DBT, the peak at 970 and 700
cm-1 in the mixture was disappeared, which was consistent with the earlier work. Thus, the fading
peaks may be the consequence of interactions between DESs and sulfides in the AODS system.
[44,58,60,61].
The UV-vis spectrum of POM-based IL under different conditions in acetonitrile were rec-
orded. Figure 4A display UV-vis spectrum of POM in acetonitrile in the presence of N2 or O2, it
15
was obvious they had nearly the same spectrum. The results indicated that there was little or very
weak interaction between the catalyst and oxygen. As is depicted in Figure 4B the UV-visible
spectrum of BSA-based DESs dissolved in acetonitrile showed a little change in the presence of
nitrogen or molecular oxygen. However, when the POM-based IL was added to the DES-containing
acetonitrile solution, the peaks at 232 nm disappeared markedly after oxygen bubbling for 1 h. It’s
impossible for molecular oxygen to form peroxosulfonate with BSA directly due to the high energy
barrier, but the dual function of POMs and DESs contributes for the ultimate oxygen molecules
activation. According to the analysis above, this phenomenon of UV was consistent with the results
of the following electrochemical experiments shown in Figure 5, proving the combination effect

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of POMs and DESs in AODS system[57].

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Figure 4. UV-Vis spectrum of POM in acetonitrile in different atmosphere (A) no DES and
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(B) with DES.

It has been proposed in our previous work that POM in combination of DESs could function
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as electron transfer mediator and electron donor during molecular oxygen activation[23]. In view
of this, oxygen reduction in the presence of POM and DESs was investigated by cyclic voltammetry
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(CV) in order to provide insight into the electron transfer mechanism. Many literatures have applied
CV to test the electrochemical property of POM catalyst and further to verify its semiconductor
behavior, such as gaining the electroactivity of POM through the redox processes, determining the
range of electrochemical stability of the ILs[62] or extending the application in photoelectronic
catalysis reaction[52]. However, there is no results using CV to convincing the biomimetic oxygen
activation in ODS process, especially the system with the addition of DES. As shown in Figure

16
5A, cyclic voltammogram of [PyPS]3Co(OH)6Mo6O18 under N2 atmosphere displays three quasi-
reversible reduction processes at, Epc = -0.09, -0.27 and -0.70 V, respectively, which can be at-
tributed to the reversible oxidation-reduction steps of molybdenum[52,63]. When the electrolyte
was bubbled with O2, the reduction event at -0.09 V was not interfered. By contrast, instead of the
two reduction events at -0.27 and -0.70 V, a new reversible reduction event with Epc = -0.61 V was
observed. Besides, the peak current for the new reduction event was more than two times of that
under N2 atmosphere, suggesting that new species produced from the [PyPS]3Co(OH)6Mo6O18 dur-
ing bubbling the electrolyte with O2. The CV profile provide strong support that the POM-based IL
can capture the O2 molecule and generate active intermediator, which would be expected for pro-

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motion on the reaction between the p-TsOH in DESs and O2 molecules. As shown in Figure 5B,
the oxygen reduction in the presence of DESs took place at Epc = -0.56 V. However, the peak current
was only 28 μA, indicating a little amount of oxygen consumption near the surface of the DESs.

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This is reasonable that direct electron transfer from p-TsOH to an O2 molecule for oxygen activation
is rather difficult as reported in our previous work[43]. However, the peak current for oxygen re-

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duction was increased to be 470 μA with addition of catalyst in the electrolyte, which was nearly
17 times of that of without catalyst. Presumably, the large amount of oxygen consumption near the
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surface of the electrode was ascribed to catalytic generation of the peroxysulfonic acid. In compar-
ison with the results of UV-vis, CV curves have shown strong response to different systems like
DES or POM+DES treated with N2 and O2, implying the more sensitive electrochemical detection
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method for the process or mechanism of catalytic reaction, which is very consistent with results in
Table 1. Possible redox electron transfer equations (1) – (3) in CV process were speculated as
follows.
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Mo=O + O2 → Mo(O2) (1)

-SO3H + Mo(O2) → -SO4H + Mo=O (2)

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-SO4H + DBT →-SO3H + DBTO2 (3)

Under the activation of oxygen, Mo=O transferred to Mo(O2) species in the DESs layer. BSA
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was chose as HBD in the DESs which can react with Mo(O2) and form peroxysulfonic acid species.
As is shown in the research, peroxysulfonic acid species played a vital role in the catalytic perfor-
mance in AODS system, it contributed to the oxidation of DBT to DBTO2 to fulfill the desulfuri-
zation reaction. CV results provide solid evidences of oxygen activation with a dramatic current
density increase, thus discovering a new route for deep insight of catalytic reactions.

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Figure 5. cyclic voltammograms curves of different systems, (A) POM in N2 or O2 and (B)
DES in N2 or O2 or POM + DES in N2 or O2.

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Based on some earlier works, and the results of UV-vis, FTIR, CV and GC-MS (Figure S9),

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a plausible mechanism of the AODS through a biomimetic dual activated approach of synergistic
electron transfer process was depicted in Scheme 1. Firstly, POM-based IL formed peroxopolyacid
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anions POM[O] under oxygen atmosphere, which acted as ETM then nucleophilically substituted
with BSA-based DESs system to form phenylperoxysulfonic acid. It is known that compounds like
DBT and its derivatives with electron-rich S atoms was preferential attacked by peroxysulfonate,
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and then oxidized to DBTO2 At the same time, peroxysulfonate and POM were reduced[43]. The
reduced phenylperoxysulfonic acid and POM were oxidized by dioxygen to initiate a novel dual
activated catalytic cycle. Accordingly, the coupled redox systems with ETMs facilitated the reac-
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tion process along a low-energy pathway. The electrons were transported from Co-POM to DESs
and finally DBT was prone to oxidize to DBTO2. The mechanism of AODS was involved in mul-
tistep electron transfer through a biomimetic approach, where existed multiple interconnected re-
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dox cycles. According to the experimental results, the catalyst was first enlightened by O2, and the
electrons transfer routes were consistent with the step by step reaction. DESs cannot contribute for
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the desulfurization until the previous step completion of POM oxidation. With this prerequisite,
peroxysulfonic acid had the possibility to function and the DBT is capable to be oxidized into
DBTO2. Also, the results elucidated that the coupled redox system and ETMs were used to facilitate
the reaction process by transporting electrons from the BSA-based DESs to the oxidant along a low
energy pathway, consisting with the results in our previous work. Therefore, the rate limited step

18
of ODS, the oxidation of organic acid to peroxy-acid, was cleverly transformed into two low-energy
step reactions, which was the soul of peroxidase mimetics concept.

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Scheme 1 Proposed dual activated catalytic cycle for the biomimetic oxidative desulfuriza-
tion.

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3.6 Dynamics analysis and apparent activation energy of the ODS system
Reaction kinetics method was further applied for the reaction evaluation of the catalytic ca-
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pacity of DESs in the ODS system. In general, the ODS reaction was identified with first order
kinetics according to previous researches[64,65]. The reaction kinetic constants were obtained by
calculation from the experimental data for the effect of different sulfur compounds on the desulfu-
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rization efficiency using equations (4) – (6), where k is the pseudo-first-order reaction rate constant
and X is the sulfur removal rate, which can be calculated by Equation 2.
𝑑𝑐𝑡
𝑟=− 𝑑𝑡
= 𝑘𝑐𝑡 (4)
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𝑐
ln( 𝑐𝑡 ) = −𝑘𝑡 (5)
0

ln(1 − 𝑋) = −𝑘𝑡 (6)

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As depicted in Figure 6A, the R2 as the correlation coefficient values for DBT and 4,6-
DMDBT, were 0.9972 and 0.9837, respectively, indicating that the reaction in the PEG2000/BSA
AODS system followed first order kinetics, which was consistent with literature reports[66]. Fur-
thermore, the k value of the different sulfides decreased in the order DBT > 4,6-DMDBT, which
was in agreement with the results of different sulfur-containing substrates in Figure 3B.

19
 Based on the results above, the AODS reaction in this study followed first order kinetics. Dy-
namics analysis of DBT was performed at different reaction temperatures, as shown in Figure 6B
(dynamics analyses of 4,6-DMDBT were depicted in Figure S8). The k values were 1.890, 1.277,
0.6554 and 0.2077 h1 at temperatures of 50C, 60 C, 70 C and 80 C, respectively, proving that
the reaction rate was faster with increasing temperature. According to the Arrhenius equation,
where Ea is the apparent activation energy and A is the Arrhenius constant, the Ea for this DES/O2/oil
reaction system could be calculated. Ea values of 4,6-DMDBT and DBT were 71.74 and 69.54 kJ
mol-1, respectively, as shown in Figure 6C. The Dynamics results provided more coincident results
with previous result and offered accurate evidence of reaction details, also, the lowest Ea values

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explained the reason of high efficiency of the DBT reaction.

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Figure 6. (A) Dynamics analysis with different sulfur compounds, (B) Dynamics analysis of
DBT at different reaction temperatures and (C) Apparent activation energy. Recycle of the reaction
system, (D) Reaction condition: m (DES) = 4 g, HBA : HBD (molar ratio) = 1:2, V (model oil) =
20 mL, T = 60 °C, m (POM) = 20 mg, O2 (1 atm, 60 mL min-1).

20
3.7 Recycling and commercial diesel test
In most homogeneous ODS systems employing polyoxometalates, recycling of the catalysts
from the reaction system is too complex to resolve. In this work, the recycling performance of ODS
system was studied as shown in Figure 6D. Using a direct recovery method, the reaction system
showed excellent recoverability. The summary recycling flow was as follows, the ODS system was
allowed to stand overnight after completion of the desulfurization reaction. The upper oil layer was
separated by decantation method. The lower DESs layer, including DESs, [PyPS]3Co(OH)6Mo6O18
and the reaction product, was directly reused through rotary evaporation in order to proceed the
next cycle. The ODS system was allowed to stand overnight after completion of the desulfurization

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reaction. The upper oil layer was separated by decantation method. The lower DESs layer included
DESs, [PyPS]3Co(OH)6Mo6O18, trace water and the reaction product DBTO2. The trace water was

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removed by rotary evaporation and then DES was directly reused for the next cycle. Subsequently,
the fresh model oil was introduced into above-mentioned DESs with continued O2 flow for the next
run, taking the sample at the end of the experiment for testing. As is shown in the figure, the removal

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of sulfur showed little decrease as the number of cycles increases. After 5 cycles, the desulfurization
efficiency shown only a little decrease, probably due to the saturation of sulfone in DES system.
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The remarkable recovery performance made this innovate desulfurization method widely applica-
ble.
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Considering the outstanding ODS performance, commercially available diesel was selected to
sulfur removal of this system further, including Commercial Diesel I and II. The commercial diesels
before and after the desulfurization were analyzed by the sulfur-specific GC-FPD. The difference
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between Diesel I and Diesel II was that Diesel I was composed of alkyl substituted BTs besides
DBTs and its derivatives, while Diesel II mainly consisted of DBTs and its derivatives. The results
of Commercial Diesel I and II were shown in Table 2, and the initial S content of Diesel I and II
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was 242 ppm and 24 ppm, respectively. After the first ODS, the peaks ascribed to DBTs and BTs
of the commercial Diesel I sharply decreased. As shown in Figure 7A, the S content was decreased
from 242 to 79 ppm. The peaks ascribed to DBTs was much lower indicating that in comparison
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with BTs, the DBTs was much easier to remove. Due to the insufficient oxidation of BTs, some
BTs were remained thus the DESs were introduced again to oxidize and remove the left BTs. After
the second ODS cycle, the S content were lowered to 21 ppm and the sulfur removal was about
91%. The initial S content of Diesel II is 24 ppm (Figure 7B). After only one cycle, the S content
dropped sharply to 4 ppm. In consequence, the ODS of commercial diesel strongly confirmed that

21
a green catalytic oxidative desulfurization system could be accomplished with this biomimetic
AODS system.

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Figure 7. Specific sulfur-containing GC-FPD spectra of (a) initial sulfur contents, (b) the first

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and (c) the second EAODS process for (A) commercial Diesel I and (B) commercial Diesel II.
Reaction condition: m (DES) = 4 g, HBA : HBD (molar ratio) = 1:2, V (diesel) = 10 mL, T = 80
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°C, m (POM) = 20 mg, 1 atm, O2 (60 mL min-1).

Table 2 Sulfur-specific GC-FPD chromatograms of the commercial diesel, the commercial

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diesel after EAODS and the desulfurized diesel under 80 ‐ after 8 h. (a) Diesel (I) and (b) Diesel
(II).
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Sulfur content (ppm)

Diesel Sulfur removal (%)
Original diesel EAODS diesel

‐ 24 4 82
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‐ 242 21 91
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4 CONCLUSIONS
In summary, a multistep biomimetic AODS system, using a novel POM-based IL
[PyPS]3Co(OH)6Mo6O18 in DESs, displayed excellent performance in desulfurization of diesel. The
characteristics of biomimetic catalytic systems including synergistic electron transfer properties
and the dual activated EAODS systems were elucidated through various methods especially with

22
cyclic voltammogram measurement for the dramatic increased current density. Multiple intercon-
nected redox cycles were elucidated about the transportation of the electrons from Co-POM to the
DESs along a low-energy pathway, taking a detour from two low energy routes. Overall, our results
highlight the potential of using CV responses to biomimetic aerobic oxidative desulfurization and
will provide a blueprint for designing efficient aerobic oxidative transformations in the future.

Supporting Information
Supplementary data associated with this article can be found, in the online version, at doi:

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https://doi.org/

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Author contributions

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Mingyue Chi and Lulu Sun performed the experiments, characterization. and catalytic tests. Zhiguo Zhu,
Weiping Liao, Wanzhong Ren and Yuchao Zhao performed the data analysis and offered helpful suggestions.
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Hongying Lü and Ting Su designed this study, analysed the data and wrote the paper.
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CONFLICTS OF INTEREST
There are no competing financial conflicts to declare.
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ACKNOWLEDGEMENTS
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We are grateful for the funding supported by National Natural Science Foundation of China (NSFC
Grant No. 21676230 and 21373177). This work also partly supported by Natural Science Founda-
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tion of Shandong Province (ZR2018BB004)

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