In Situ Implanting of Single Tungsten Sites into Defective UiO-66(Zr) by Solvent-Free Route for Efficient Oxidative Desulfurization at Room Temperature

Article abstract of DOI:10.1002/anie.202107018

Design of single-site catalysts with catalytic sites at atomic-scale and high atom utilization, provides new opportunities to gain superior catalytic performance for targeted reactions. In this contribution, we report a one-pot green approach for in situ implanting of single tungsten sites (up to 12.7 wt.%) onto the nodes of defective UiO-66(Zr) structure via forming Zr-O-W bonds under solvent-free condition. The catalysts displayed extraordinary activity for the oxidative removal of sulfur compounds (1000 ppm S) at room temperature within 30 min. The turnover frequency (TOF) value can reach 44.0 h^?1 at 30 °C, which is 109.0, 12.3 and 1.2 times higher than that of pristine UiO-66(Zr), WO₃, and WCl₆ (homogeneous catalyst). Theoretical and experimental studies show that the anchored W sites can react with oxidant readily and generate W^VI-peroxo intermediates that determine the reaction activity. Our work not only manifests the application of SSCs in the field of desulfurization of fuel oil but also opens a new solvent-free avenue for fabricating MOFs based SSCs.

Full text of DOI:10.1002/anie.202107018

A Journal of the Gesellschaft Deutscher Chemiker
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International Edition Chemie
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Accepted Article
Title: In situ implanting single tungsten site into defective UiO-66(Zr) by
solvent-free route for efficient oxidative desulfurization at room
temperature
Authors: Jin Wang, Gan Ye, Hanlu Wang, Wenxin Chen, Hongqi Chu,
Jinshan Wei, Dagang Wang, and Yadong Li
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202107018
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RESEARCH ARTICLE
In situ implanting single tungsten site into defective UiO-66(Zr) by
solvent-free route for efficient oxidative desulfurization at room
temperature
Gan Ye,[a,b] Hanlu Wang, Wenxin Chen, Hongqi Chu, Jinshan Wei,
[c]
[d]
[e]
[a,b]
Dagang Wang, Jin
[a]
[a]
[f]
Wang,* and Yadong Li
[
a]
Dr. G. Ye, Dr. J. S. Wei, D. G. Wang, Prof. J. Wang
College of Materials Science and Engineering
Shenzhen University
Shenzhen 518060, China
E-mail: wangjin19@szu.edu.cn
Dr. G. Ye, Dr. J. S. Wei
[
b]
Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province
College of Optoelectronic Engineering
Shenzhen University
Shenzhen 518060, China
[
c]
d]
Prof. H. L. Wang
College of Chemical Engineering
Guangdong University of Petrochemical Technology
Maoming 525000, China
[
Prof. W. X. Chen
Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications
School of Materials Science and Engineering
Beijing Institute of Technology
Beijing 100081, China
[
e]
f]
Dr. H. Q. Chu
School of Chemistry and Chemical Engineering
Harbin Institute of Technology
Harbin 150001, China
[
Prof. Y. D. Li
Department of Chemistry
Tsinghua University
Beijing 100084, China
Supporting information for this article is given via a link at the end of the document.
Abstract: Design of single site catalysts with catalytic sites at atomic-
scale and high atom utilization, provides new opportunities to gain
superior catalytic performance for targeted reactions. In this
contribution, we report a one-pot green approach for in-situ implanting
single tungsten site (up to 12.7 wt.%) onto the nodes of defective UiO-
energy source.[1,2] Oxidative desulfurization (ODS) is of great
significance for producing fuel oil with ultra-low sulfur content due
to its capability to eliminate refractory sulfur compounds with no
hydrogen consumption and simple operation.[3-6] To date,
considerable research has been devoted to prepare efficient ODS
catalysts for obtaining clean fuel, however most of them needed
high reaction temperature to meet efficient activity.[7-9] Several
works have focused on the fabrication of ODS catalyst based on
66(Zr) structure via forming Zr-O-W bonds under solvent-free
condition. The catalysts displayed extraordinary activity for the
oxidative removal of sulfur compounds (1000 ppm S) at room
temperature within 30 min. The turnover frequency (TOF) value can
ionic liquid,[
10,11]
metal-organic frameworks (MOFs),
[12,13]
-
1
polyoxometalates,[4,14] metal oxide[3,15] or metal cluster[16] for
removing sulfur compounds at low temperature. Unfortunately,
the unevenly dispersed large pieces of active species easily block
the pore of supports thus preventing contact with reactant or can
only remove dibenzothiophene (DBT), which limit their ODS
performance.[17,18] For this, the development of highly active ODS
catalysts with rich porosity and atomic scale active sites at
ambient temperature has been strongly pursued.
reach 44.0 h at 30°C, which is 109.0, 12.3 and 1.2 times higher than
that of pristine UiO-66(Zr), WO , and WCl (homogeneous catalyst).
3
6
Theoretical and experimental studies show that the anchored W sites
can react with oxidant readily and generate W(VI)-peroxo
intermediates that determine the reaction activity. Our work not only
manifests the application of SSCs in the field of desulfurization of fuel
oil but also opens a new solvent-free avenue for fabricating MOFs
based SSCs.
Single site catalysts (SSCs) with desired coordination
environments and unique catalytic performance have become
excellent candidates for various applications.[19-22] SSCs with
catalytic sites at atomic-scale and higher atom utilization, provide
Introduction
new opportunities to develop rational catalyst design for targeted
reactions.[23-26] Owing to the remarkable stability, large surface
area and rich coordination unsaturated sites, pristine MOFs are
With increasingly stringent environmental regulations,
desulfurization of fuel oil becomes indispensable to obtain clean
1
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Angewandte Chemie International Edition
10.1002/anie.202107018
RESEARCH ARTICLE
the prominent candidates for synthesizing SSCs.[27-30] Importantly,
defect sites on the nodes of MOFs allow for introduction of
heterogeneous metal ions without protection, which is highly
desirable for the systematic investigation of catalytic activity.[31,32]
Therefore, the introduction of more active single-site into MOFs
Potentiometric acid-base titration has been confirmed to be an
accurate approach to quantify the number of defects in UiO-
66(Zr).[
36,37]
On the basis of the potentiometric acid-base titration
measurement (Figure S13 and Table S3 and S4), UiO-66(Zr) was
determined to exhibit a missing linker number of 1.91 per Zr-oxo
cluster. Comparatively, the number of missing linkers in W/UiO-
66(Zr)-0.12 was lowered to 1.65 due to the occupation of defect
would be expected as
a solution to enhance the ODS
performance. To the best of our knowledge, no work on the use
of MOFs based SSCs as ODS catalysts has been reported.
Herein, we presented a new one-pot approach to decorate W
sites into UiO-66(Zr) framework without addition of solvent. The
obtained SSCs exhibited extraordinarily high ODS activity for
removing DBT (1000 ppm) within 30 min and 4,6-
dimethyldibenzothiophene (4,6-DMDBT, 500 ppm) within 20 min
at room temperature, which can be ascribed to the hyperactive
single W sites anchored on node of UiO-66(Zr). The experimental
and theoretical results revealed that the introduction of W sites
easily combine with oxidant and generate W(VI)-peroxo
intermediates that efficiently oxidize sulfur compounds.
2
sites (-OH/OH ) by W (the W loading corresponds to 0.56 per Zr-
oxo cluster).
Results and Discussion
W/UiO-66(Zr) was pioneeringly prepared through a one-pot
solvent-free route, where ZrOCl
ground, then added into autoclave and crystallized at 130 C for
h (Figure 1a). The powder XRD patterns of UiO-66(Zr) and
2 2 6
·8H O, BDC and WCl were
o
8
W/UiO-66(Zr) are almost identical to that of the simulated one,
confirming that the structure was maintained (Figure 1b). A new
o
broad diffraction peak started to appear at 2θ = 6.0 and became
prominent with gradually introduced tungsten content, indicating
that cluster missing defects could be generated in these W/UiO-
6
6(Zr) structures.[33-35] Further increase of W content beyond 12.7
wt.% (based on ICP measurement, Table 1) led to destruction of
the pristine MOF structure of UiO-66(Zr) (Figure S1). N
adsorption isotherms of W/UiO-66(Zr) display an abrupt increase
in the region of 0 < P/P < 0.1 and second jump with hysteresis
loops at P/P of 0.4~0.95 (Figure 1c), indicating that all of them
2
0
0
possess hierarchical porosity (Figure 1c inset and Figure S2),
which is consistent with the appearance of cluster missing defects
as shown by XRD results. The BET surface areas for UiO-66(Zr)
Figure 1. (a) Schematic illustration of the synthetic process of W/UiO-66(Zr), (b)
XRD patterns, (c) N sorption isotherms and the pore size distribution curves
inset) of different samples, (d) TEM image, (e) HR-TEM image, (f) HAADF
2
(
image and (g) elemental mapping images of W/UiO-66(Zr)-0.12.
2
2
and W/UiO-66(Zr) gradually decrease from 1157 m /g to 762 m /g
with the W content increased from 0% to 12.7% (Table 1 and S1).
The SEM and TME images of UiO-66(Zr) present a morphology
of sheet shape but of inhomogeneous particle size. The average
particle size of W/UiO-66(Zr) increased with W content while the
sheet-like morphology was retained (Figure 1d and S3-6). W/UiO-
Table 1. Textural properties and W, Zr contents of various samples.
BET
W
Zr
content
(wt.%)
Micropore
volume
(mL/g)
Mesopore
volume
(mL/g)
surface
area
Samples
content
6
6(Zr)-0.12 was further investigated by HRTEM and HAADF-TEM
wt.%)[
a]
[a]
[b]
[c]
(
2
based on its superior catalytic property, as will be shown later.
There were scattered dark areas present in HRTEM image, but
no lattice spacing of W-containing species were found (Figure 1e
and S7). The dispersion of isolated bright dots was identified in
HAADF images (Figure 1f and S8), which can be attributed to Zr-
oxo nano-clusters formed by the destruction of UiO-66(Zr)
structure under illumination of high-intensity electron beam. The
element mappings display that Zr, W, O, C and Cl elements are
homogeneously distributed in W/UiO-66(Zr)-0.12, which is similar
to that of pristine UiO-66(Zr) (Figure 1g and S9 and S10). The
exact element content of W/UiO-66(Zr)-0.12 is listed in Table S2
(m /g)
UiO-66(Zr)
0
2
33.1
1157
967
0.52
0.43
0.31
0.35
W/UiO-
66(Zr)-0.03
.7
32.7
W/UiO-
4.6
32.5
32.3
32.0
952
924
874
0.42
0.40
0.38
0.37
0.39
0.41
66(Zr)-0.06
W/UiO-
6(Zr)-0.12
6
.1
.8
6
W/UiO-
6(Zr)-0.19
8
(
0
Figure S11 and S12). The molar ratio of BDC, Zr and W was
.69 : 1 : 0.094 based on calculation. The results can confirm that
missing linker defects are present in W/UiO-66(Zr)-0.12.
6
2
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
W/UiO-
12.7
31.5
762
0.33
0.43
66(Zr)-0.25
[
a] Measured by ICP. [b] HK method. [c] BJH method.
FT-IR was conducted to monitor the bonding characteristics
of the samples. The new emerging absorption band at 970 cm-1
in FT-IR spectra of W/UiO-66(Zr) can be attributed to a W=O
stretching vibration (Figure 2a and S14 and S15).[38-40] The broad
Raman band of W/UiO-66(Zr) between 960-990 cm-1 can be
[
41]
assigned to the starching mode of terminal W=O bands. The
-1
emergent band at 910-950 cm is related to the weak vibrations
[
42,43]
The additional band around 770 cm-1 in the
of Zr-O-W bonds.
Raman spectra of W/UiO-66(Zr) compared to that of UiO-66(Zr)
Figure 2b), which is corresponding to the asymmetric stretching
(
[41]
of the W-O bond, also confirmed the presence of W-O bond.
XPS spectra show that Zr in all the samples can be assigned to
Zr4+ oxidation state. Moreover, the Zr 3d peaks slightly shift to
higher binding energies with increasing W content, which
indicates the flow of electron density from Zr center to W center
via the Zr-O-W linkages (Figure 2c and S16).[44-46] The charge
transfer also can be confirmed by XPS spectra of O 1s, C 1s, Cl
2
p and UV-vis spectroscopy (Figure S17-20). The two peaks
around at 36.0 and 38.0 eV corresponded to W 4f7/2 and W 4f5/2
signaling 6+ oxidation state of W in all the W/UiO-66(Zr) samples
Figure 2d and S21).[47] To further identify the atomic local
,
(
structure, Fourier transform (FT) extended X-ray absorption fine
structure (EXAFS) of W element was measured (Figure 2e). The
FT-EXAFS spectrum of W/UiO-66(Zr)-0.12 exhibited one sharp
peak at a distance that accounts for the W-O bond length and W-
W coordination was not detected, which give forthright evidence
for the formation of single W sites (Figure S22). The local
structural parameters of W/UiO-66(Zr)-0.12 (Table S5) was
obtained by fitting the EXAFS curve (Figure 2f). The fitting result
indicated that the first shell coordination number of W atom was
Figure 2. (a) FT-IR spectra, (b) Raman spectroscopy, (c) and (d) XPS spectra
for Zr 3d and W 4f of different materials, (e) k -weight FT-EXAFS curves of
W/UiO-66(Zr)-0.12 at W L -edge, (f) FT-EXAFS fitting curve of W/UiO-66(Zr)-
3
0.12 at R space (insert, the corresponding structure model).
3
The catalytic activities of as-synthesized samples for ODS
o
reactions were assessed at 30 C. UiO-66(Zr) exhibited poor
activity, only 51.8% sulfur can be removed after a reaction time of
25 min. The GC-MS result further shows that only a total of 16.4%
sulfur was oxidized as most of the DBT removed from the model
fuel phase was in fact due to the extraction by acetonitrile. Notably,
the removal of sulfur over W/UiO-66(Zr)-0.03, W/UiO-66(Zr)-0.06,
W/UiO-66(Zr)-0.12, W/UiO-66(Zr)-0.19 and W/UiO-66(Zr)-0.25
reached 94.9%, 96.6%, 99.9%, 99.7% and 99.8% respectively
after the same reaction time (Figure 3a). Moreover, only
4
.[26] Combined with above structural characterization results, the
atomic local structure of W in W/UiO-66(Zr)-0.12 can be
ascertained, as shown in the inset in Figure 2f. Meanwhile, a good
fit has been achieved between the measured XANES (X-ray
absorption near edge structure) spectrum and the calculated one
based on this atomic local structure model (Figure S23).
According to potentiometric acid-base titration analysis, the
reduction of the measured number of missing linkers in W/UiO-
dibenzothiophene sulfone (DBTO ) could be detected in both the
2
6
6(Zr)-0.12 relative to UiO-66(Zr) is 0.26 (corresponding to 1.04 -
model fuel phase and the extraction phase by GC-MS after the
ODS reaction over W/UiO-66(Zr)-0.12 and W/UiO-66(Zr)-0.19,
confirming that DBT has been completely oxidized into DBTO2.
W/UiO-66(Zr)-0.03, W/UiO-66(Zr)-0.06 and W/UiO-66(Zr)-0.25
exhibited slightly inferior oxidation performance as slight DBT
could be detected in their both phases (Figure S27). Thus, among
the W/UiO-66(Zr) samples, W/UiO-66(Zr)-0.12 showed the
highest catalytic activity per active site for complete oxidation
OH/OH defect sites) per Zr-oxo cluster, in agreement with the
number of W-occupied defect sites (1.12 per Zr-oxo cluster). The
result further verified the identified location of single-atom W sites
2
(
See Figure S13 for details). DFT calculation results also indicate
that the replacement of Zr by W is thermodynamically highly
unfavorable (Figure S24). Similar to the case of W/UiO-66(Zr)-
0
W coordination (Figure S25), indicating a loading of single W sites
up to 12.7 wt.%. All the as-prepared W/UiO-66(Zr) samples
exhibits good thermal stability until 500°C, which shows the
potential to act as a single-site heterogeneous catalyst for a wide
range of reactions (Figure S26).
.12, the EXAFS curve of W in W/UiO-66(Zr)-0.25 shows no W-
o
within 25 min at 30 C (Figure S28). It was worth noting that the
DBT adsorption capacity of W/UiO-66(Zr)-0.12 is below 2%
(Figure S29), and proved that the adsorption has little effect on
ODS reaction. The removal efficiency of sulfur over W/UiO-66(Zr)-
0.12 reached 99.0%, 99.8%, 99.8%, 97.3% and 95.6% at a
reaction time 25 min when 1 mL, 2.5 mL, 5 mL, 7.5 mL and 10 mL
acetonitrile were used as extraction phase (Figure 3b). The
results indicated that very small amount of extractant can meet
the requirement of ODS activity (Figure S30). The influence of
O/S (oxidant/sulfur) molar ratio was studied. As shown in Figure
3
c, the ODS performance of W/UiO-66(Zr)-0.12 increased with
3
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RESEARCH ARTICLE
(
reusability insert) on catalytic activities of W/UiO-66(Zr)-0.12 and (f) TOF
O/S molar ratio from 2 to 8. When the O/S molar ratio was 2,
oxidation efficiency could reach 92.8% after a reaction time of 30
min. The removal efficiency of sulfur reached 99.2% within 30 min
with the O/S molar ratio of 3, which indicated that W/UiO-66(Zr)-
number of different samples. Reaction conditions: 30 mg catalyst, 10 mL model
fuel, 5 mL acetonitrile (except for b), H as oxidant, O/S molar ratio of 4
2 2
O
o
(except for c), 500 ppm S (e 1000 ppm), 30 C (except for e).
0
.12 can offer high catalytic efficiency with exceptionally diluted
oxidant. The tests with varied DBT concentration (from 250 ppm
sulfur to 1500 ppm sulfur) show that DBT with a sulfur
concentration of up to 1000 ppm can be removed within 30 min at
To further comprehend the catalytic activity of W/UiO-66(Zr)-
.12, the ODS reactions for DBT with several representative MOF,
0
POM/MOF and W-containing porous materials are summarized in
Table S7. It is shown that most reported catalysts were active in
ODS reaction of DBT when the reaction temperature was above
3
6
0°C (Figure S31). The influence of sulfur substrate over W/UiO-
6(Zr)-0.12 was also tested by ODS of BT, DBT and 4,6-DMDBT
(
Sulfur content was 500 ppm for all the three tests). It is shown
0°C. Ti-BDC-A,[12] W-KIT-6,[48] and W-IL-G-h-BN[49] were active
5
that 4,6-DMDBT, which is difficult to eliminate by industrial
hydrodesulfurization, could be completely removed after a
reaction time of 20 min at 30 C (Figure 3d), indicating that W/UiO-
at lower temperature, but need longer reaction time or organic
oxidant to achieve the ideal desulfurization efficiency. Importantly,
the TOF numbers of these catalysts were lower than that of
W/UiO-66(Zr)-0.12. Comparatively, the TOF number over W/UiO-
o
6
6(Zr)-0.12 possess great potential in future use for deep ODS of
fuel oil. BT was the most difficult to oxidize due to the lower
electron density on its sulfur atom (5.739) compared to DBT
6(Zr)-0.12 could reach 44.0 h-1 at 30°C, and is 109.0 and 12.3
and 1.2 times higher than pristine UiO-66(Zr), WO and WCl
Figure 3f and S36), and up to 132.0 h at 50°C, which is higher
than most reported ODS catalysts. It is important to note that the
6
3
6
(
5.758) and 4,6-DMDB (5.760), displaying 65.3% removal within
-1
(
3
0 min.
The effect of reaction temperature on ODS over W/UiO-
ODS activity of W/UiO-66(Zr)-0.12 even beats that of WCl
is a homogeneous catalyst in this reaction system.
6
which
6
1
6(Zr)-0.12 is investigated with the sulfur content of DBT fixed at
000 ppm. As shown in Figure 3e, the catalytic activity increased
DFT calculation was conducted to better understand the role
of the implantation of W single sites in UiO-66(Zr). The optimized
structures of UiO-66(Zr) and W/UiO-66(Zr) were displayed in
Figure S37. To show the different reaction activity between them
with reaction temperature, and the sulfur could be completely
removed within 10 min at 50°C. Based on the temperature-
dependent results, the activation energy (Ea) of W/UiO-66(Zr)-
0
.12 was calculated to be 32.4 kJ/mol, which is low compared with
2 2
and H O , the frontier molecular orbitals (the highest occupied
[11,17]
the data from the previous reports (Figure S32, Table S6).
molecular orbital: HOMO and the lowest unoccupied molecular
orbital: LUMO), which play key roles in chemical reactions, were
calculated. The HOMO and LUMO of UiO-66(Zr) distributed
uniformly and symmetrically throughout the whole molecule, while
the HOMO of W/UiO-66(Zr) is mainly distributed on the W-O
group, which is constituted by dx2-y2 and p orbitals of W and O
atoms (Figure 4a). According to the frontier orbital theory, when
The W/UiO-66(Zr)-0.12 catalyst also shows good reusability.
Almost no visible efficiency decrease after four cycles was noticed
(
0
(
Figure 3e insert and S33. The structural stability of W/UiO-66(Zr)-
.12 after reuse was confirmed by XRD and N sorption technique
Figure S34 and S35).
2
UiO-66(Zr) and W/UiO-66(Zr) react with H
HOMO of UiO-66(Zr) and W/UiO-66(Zr) flow to the LUMO of H
As shown by the calculation, the HOMO of W/UiO-66(Zr) (-3.78
eV) are obviously closer to the LUMO of H (-0.23 eV)
compared with UiO-66(Zr) (HOMO: -6.75 eV). Therefore, W/UiO-
6(Zr) has a higher tendency to react with H than UiO-66(Zr),
thus endowing it with superior catalytic activity.
2 2
O , the electrons in the
2
2
O .
2
O
2
6
2 2
O
Figure 3. Influence of different (a) W content of various catalysts, (b) acetonitrile
dosage, (c) the O/S molar ratio, (d) sulfur substrate, (e) reaction temperature
4
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
Figure 4. (a) Energies (in eV) and isosurfaces of HOMOs and LUMOs of UiO-
Acknowledgements
66(Zr) and W/UiO-66(Zr)-0.12 at theoretical level. (b) Leaching and quenching
experiments over W/UiO-66(Zr)-0.12 in the ODS reaction of DBT. (c) Proposed
reaction mechanism. Reaction conditions: catalyst (30 mg), model oil (10 mL),
This work was supported by National Natural Science Foundation
of China (22022508), Science and Technology Key Project of
Guangdong Province of China (2020B010188002), and China
Postdoctoral Science Foundation (2020M672806).
o
acetonitrile (5 mL), DBT (500 ppm), oxidant (H
2 2
O ), O/S molar ratio (4:1), 30 C,
p-benzoquinone (0.9 mmol) or tertiary butanol (1.8 mmol).
According to previous reports, the oxidation mechanism of
sulfur compounds by H O over W-based catalysts was known to
2 2
Keywords: Single site • Tungsten • UiO-66(Zr) • Solvent-free •
Oxidative desulfurization
execute via a peroxo-metal pathway referred to W(VI) without
changing the oxidation state of W.[4,11,48,50] To confirm the above
hypothesis, leaching and quenching experiments were carried out.
When W/UiO-66(Zr)-0.12 was filtered out of the reaction system
at a reaction time 5 min, the catalytic activity was almost
completely inhibited, and confirmed that no leaching had occurred
and that no plentiful radicals had been produced (Figure 4b). The
catalytic performance was not strongly affected, when tertiary
butanol (TBA, scavenger for HO•), p-benzoquinone (BQ,
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[
[
3]
[4]
[5]
[6]
•
−
scavenger for O
2
) or TBA and BQ added into the reaction
system.[
4,12]
The results suggested that HO• and O
•−
L. D. Hao, M. J. Hurlock, G. D. Ding, Q. Zhang, Topics Curr. Chem. 2020,
2
, as
378, 17.
confirmed by EPR experiment (Figure S38),[12,13,51] play a minor
role. The leaching and quenching experiments confirmed that
W(VI)-peroxo intermediates should play the key role in ODS
reaction. It has been reported that defective UiO-66(Zr) can
[
7]
8]
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6
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10.1002/anie.202107018
RESEARCH ARTICLE
Entry for the Table of Contents
A one-pot green approach for in-situ implanting single tungsten site (up to 12.7 wt.%) onto the nodes of defective UiO-66(Zr) structure
via forming Zr-O-W bonds under solvent-free condition. The W/UiO-66(Zr) SSCs display extraordinary ODS activity under very mild
condition, achieving complete oxidation of sulfur compounds (1000 ppm S) at room temperature within 30 min by using diluted H
as oxidant.
2 2
O
7
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