Confining Free Radicals in Close Vicinity to Contaminants Enables Ultrafast Fenton-like Processes in the Interspacing of MoS2 Membranes

Article abstract of DOI:10.1002/anie.201903531

Heterogenous Fenton-like reactions are frequently proposed for treating persistent pollutants through the generation of reactive radicals. Despite great efforts to optimize catalyst activity, their broad application in practical settings has been restricted by the low efficiency of hydrogen peroxide or persulfate decomposition as well as ultrafast self-quenching of the activated radicals. Theoretical calculations predicted that two-dimensional (2D) metallic 1T phase MoS₂ materials with exposed (001) surfaces and (100) edges should have remarkable affinity towards crucial intermediates in the peroxymonosulfate (PMS) activation process. X-ray photoelectron spectroscopy and in situ Raman spectroscopy were used to show that the exposed metallic Mo sites accelerate the rate-limiting step of electron transfer. A lamellar membrane made from a stack of 2D MoS₂ with tunable interspacing was then designed as the catalyst. The non-linear transport between the MoS₂ nanolayers leads to high water diffusivity so that the short-lived reactive radicals efficiently oxidize contaminants.

Full text of DOI:10.1002/anie.201903531

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Accepted Article
Title: Ultrafast Fenton-like Process in Interspacing of MoS2 Membrane
Enabled by Confining Sufficient Free-Radicals in Close Vicinity to
Contaminants
Authors: Yu Cheng, Gong Zhang, Huijuan Liu, and Jiuhui Qu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201903531
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10.1002/anie.201903531
Angewandte Chemie International Edition
COMMUNICATION
Ultrafast Fenton-like Process in Interspacing of MoS2 Membrane
Enabled by Confining Sufficient Free-Radicals in Close Vicinity to
Contaminants
Yu Chen,[a, b, c] Gong Zhang,*[b] Huijuan Liu,[b] and Jiuhui Qu*[a, b, c]
Abstract: Heterogenous Fenton-Like reactions are frequently
proposed for treating persistent pollutants through the generation of
reactive radicals. Despite great efforts to optimize catalyst activity,
broad application in practical settings has been restricted by the low
efficiency of hydrogen peroxide or persulfates decomposition as well
as ultrafast self-quenching of the activated radicals. Here, theoretical
calculations were carried out which predicted that two-dimensional
(2D) metallic 1T phase MoS2 materials with extensive exposure of
(001) surface and (100) edges should have remarkable affinity
toward crucial intermediates in peroxymonosulfate (PMS) activation
process. X-ray photoelectron spectroscopy and in-stiu Raman
spectra demonstrated that abundant exposed metallic Mo active
sites with reducing properties had significant potential to accelerate
rate-limiting step of electron transfer, whereby radical generation
was ~ 12 times as high as that using the bulk counterpart as an
activator. A new kind of lamellar membrane made from a stack of 2D
MoS2 with tunable interspacing was then designed as the catalytic
platform. The key feature of this structure is that non-linear transport
between MoS2 nanolayers enabled high water diffusivity, which
enabled the reactive radicals with short longevity to efficiently oxidize
contaniments (~100% degradation of Bisphenol A within 100 ms).
resulting in inefficient usage of the as-activated ROS.
In principle, the cleavage of peroxyl bonds in AOPs involving
chemical oxidants (PMS, H2O2) occurs due to electron transfer
from polyvalent metals (Fe, Mn or Co).[4] Nevertheless, the free
radical yield efficiency is primarily restricted by the adsorption
ability towards the active ingredients. Molybdenum disulfide
(MoS2), a type of layered transition metal dichalcogenide, has
been widely applied in the fields of catalysis and energy
conversion applications.[5] In particular, the strong bonding
energy and high effective electron transfer induced by the S-Mo-
S bonds are crucial for its outstanding catalytic performance.[6]
Remarkably, theoretical calculations predict that the (001) edges
and (100) surface of 1T phase MoS2 should exhibit strong
adsorption energy (Eads, eV) toward PMS molecules. Thus,
theoretically, MoS2 with abundance of active sites (Mo2+→Mo6+)
should be an ideal activator for radical generation. However, the
gallery height of bulk MoS2 is too narrow (~0.298 nm) to admit
reactants to the interior surface where the abundant active sites
are located.[7] Achieving high exposure of the active surface and
edges is the key issue for efficient activation of PMS. Two-
dimensional (2D) materials with their considerable specific
surface area, should realize high exposure of surfaces and
edges.
Heterogeneous advanced oxidation processes (AOPs) have
been implemented in the water purification to successfully to
degrade organic pollutants via the generation of reactive oxygen
species (ROS), which exhibit unselective oxidation toward a
wide range of aqueous organic pollutants.[1] As core materials
for ROS generation, heterogenous activators can overcome the
inherent drawback of secondary pollution which typically
encountered with homogeneous AOPs.[2] However, the
performance of AOPs using heterogenous activators is currently
hindered by low ROS activation efficiency, which is derived from
insufficient exposure of actives sites for ROS generation.[3]
Additionally, ultrashort radical lifetimes (10-6~10-9 s) restrict the
effective diffusion of ROS to the target organics in solution,
In order to avoid their negative effect on water safety,[8] the
recycling of 2D materials remain a major concern for their
application. Assembling the 2D nanosheets into a lamellar
membrane is an alternative potential approach,[9] where active
sites on the 2D surface can be well-preserved. In comparison
with conventional AOP configuration, the diffusion distance of
aqueous organic molecules in nano-sized interspacing should
be significantly decreased. Moreover, Fick’s Law indicates that
the steep concentration gradient (perpendicular to flow direction,
Scheme 1) in the nano-sized interspacing have the potential to
propel both of small organic molecules and PMS from center to
boundaries. The rapid mass transportation primarily strengthens
the activation efficiency between PMS and activators, resulting
in the high concentration of ROS. At the meantime, as-activated
radicals in close vicinity to contaminants have more chance to
attack to these molecules (Figure S1).[10] Thus, a nanofluidic
AOP platform using an MoS2 lamellar membrane as a free
radical activator was here constructed for highly effective water
purification. Based on the combined results of in-situ Raman and
X-ray photoelectron spectroscopy (XPS) analysis, the superior
radical generation achieved by the MoS2 membrane was mainly
attributed to the firm fixation of oxidant molecules and efficient
charge transfer induced by polyvalent Mo (Mo4+/Mo5+).
Furthermore, the lamellar MoS2 membrane with tunable
interspacing was obtained by an etching a Fe(OH)3 nanoparticle
template, where the confinement of fluids between nanolayers
boosted the molecule diffusion to take advantage of the radicals’
oxidation capacity. In the platform with MoS2 membrane
thickness of ~1 μm and interspacing of ~1.5 nm, only a retention
[a]
Dr. Y. Chen, Pro. J. H. Qu
Key Laboratory of Drinking Water Science and Technology
Research Centre for Eco- Environmental Sciences
Chinese Academy of Sciences
Beijing 100085, China
E-mail: jhqu@rcees.ac.cn
[b]
Dr. G. Zhang, Pro. H. J. Liu
Center for Water and Ecology, State Key Joint Laboratory of
Environment Simulation and Pollution Control, School of
Environment,
Tsinghua University
Beijing 100084, China
E-mail: gongzhang@mail.tsinghua.edu.cn
Dr. Y. Chen, Pro. J. H. Qu
[c]
University of Chinese Academy of Sciences
Beijing 100049, China
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201903531
Angewandte Chemie International Edition
COMMUNICATION
time of ~100 ms was needed for total degradation the aqueous
Bisphenol A (BPA).
obvious shift of Mo 3d XPS peaks give further evidence for the
phase change (Figure 1e). Notably, the deconvoluted XPS
spectra of the Mo 3d and S 2p regions indicate that almost total
transformation to the 1T phase (~95%) can be achieved by the
Li intercalation method. The intense phase restructuring results
in the formation of sulfur vacancies, as evidenced by the
broadened and intensified EPR signals at g=2.00 (Figure S4).[6b]
The weak signal located at g=1.93 represents the unpaired Mo
4d electrons derived from sulfur vacancies,[15] which is favorable
for absorbing PMS molecular in contrast to pristine MoS2 (001)
surface in 1T-MoS2 (Table S1).
Theoretical calculations predict the superior activation of PMS in
the presence of the ultrathin metallic 1T phase MoS2 (ce-MoS2).
Herein, the mild Eads (-0.50~-0.63 eV) of PMS adsorption using
MoS2 indicated the reaction can proceed spontaneously. More
importantly, the charge density difference illustrated the obvious
charge accumulation in PMS molecular and depletion on MoS2
surface, which confirmed rapidly electron transfer for triggering
the PMS activation (Figure S2). Additionally, The O-O bond (lo-o
)
of adsorbed PMS is lengthened from 1.346 Å to 1.403 Å,
indicating that PMS molecules are activated and ready to cleave
to generate ROS. Thus, we prepared ultrathin MoS2 nanosheets
with a majority of metallic 1T phase via a chemical intercalation
method.[11] The intercalated Li destroy the van der Waals force
between pristine MoS2 layers with the generation of S-Li-S
bonds (LixMoS2),[12] which enlarges the interspacing (Figure 1a)
and regulates electronic structure (Figure 1f). The as-prepared
MoS2 nanosheets consist of single layers with a thickness of
~1.5 nm (Figure 1b, 1c). The Fast Fourier Transform (FFT)
images (inset of Figure 1b, Figure S3) indicate that the
nanosheets are single-layered with a characteristic 1T phase.
The in-situ Raman spectra were used to further analyze the
affinity between PMS molecules and active sites. As shown in
-
Figure 2a, the peak at 886 cm-1 and 1060 cm-1 represent HSO5
of PMS, while the peak at 982 cm-1 is associated with the
2− [16]
symmetric stretching vibration mode of S=O bonds in SO4
.
After activation of PMS, a new peak was recorded at 835 cm-1,
which was most probably the consequence of strong affinity
between active sites (sulfur vacancies) and PMS. The change in
the ratio, I1060/I982, could evaluate the PMS consumption to some
extent.[1c] The original I1060/I982 of pure PMS was 1.46. However,
I1060/I982 decreased to 1.04 and 0.96 in the corresponding
-
2−
MoS2/PMS systems, which suggests that the HSO5 to SO4
transformation was accelerated by the synergistic effects
between PMS and ce-MoS2. Notably, the lower I1060/I982 in the
ce-MoS2/PMS system manifests the faster PMS consumption.
Figure 1. (a) XRD patterns of bulk MoS2 and LixMoS2, (b) HRTEM image of
ce-MoS2. Inset: the corresponding fast Fourier transform (FFT) pattern of ce-
MoS2, (c) AFM images of ce-MoS2, (d) Raman spectra of bulk MoS2 and ce-
MoS2, (e) high-resolution XPS spectra of Mo 3d and S 2p of bulk MoS2/ce-
MoS2, (f) diagrammatic representation of 2H phase and 1T phase.
Scheme 1. (a) The scheme of the strengthened diffusion and the ultra-short
distance of mass transfer. (b) PMS adsorption free energy on surface and
edge of 1T phased MoS2. The red, yellow, white, and blue spheres are O, S, H,
and Mo atoms.
The route of radical generation was further investigated by high-
resolution XPS and EPR spectroscopy. Generally, the reduction
of polyvalent metals (Men+→Men+1) is an important factor, which
induces the one-electron route, triggering the cleavage of PMS
and subsequent efficient generation of free radicals. High-
resolution XPS spectra of fresh/used ce-MoS2 were applied to
identify the charge transport during PMS activation. As shown in
Figure 2b, four peaks with bonding energies of 228.5, 229.2,
231.8 and 232.7 eV were assigned to Mo(IV), and the peak
located at 230.0 eV represented the Mo(V).[17] After the reaction,
the area of Mo(V) increased slightly from 5% to 8%. The results
showed that the partially filled Mo 4d orbitals (Mo4+) of ce-MoS2
are highly active and prone to transfer electrons to PMS for
Additionally, Raman and XPS spectroscopies were employed to
further identify the phase change occurring during the
preparation of as-prepared ce-MoS2. Raman signals (Figure 1d)
at 383 cm-1 (E2g modes) and 409 cm-1 (A1g modes) correspond to
the typical phonon vibrations of 2H phase MoS2.[13] However, for
intercalated MoS2 layers, the phase restructuring weakens the
strength of 2H signals and generates new ones located at 154
cm-1, 225 cm-1and 327 cm-1, which represent the typical 1T
phase vibrations of J1, J2 and J3 mode, respectively.[14] The
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10.1002/anie.201903531
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generation of ROS. This feature was identified by combination of
5,5-dimethyl-1-pyrroline-N-oxide (DMPO) spin-trapping electron
paramagnetic resonance (EPR) analysis as well as a series of
quenching experiments (Figure 2c, S5).[1a, 18] Both DMPO-SO4·-
and DMPO-·OH signals were detected in ce-MoS2/ PMS system.
The signal intensity in ce-MoS2/PMS system after 1 min was ~12
times stronger than that for the bulk counterpart (Figure 2c). The
intensity of EPR signal rose to a peak after ~5 min, then
decreased by half at 10 min, and finally decreased to near
disappearance at 15 min. In this period, the amount of SO4·- and
·OH produced were then quantified using p-hydroxybenzoic acid
(p-HBA) and salicylic acid, respectively. As reflected by the as-
produced p-BQ concentration, ~4.25 μmol·L-1 of SO4·- has been
produced in ce-MoS2/PMS system (Figure S6).[19] Furthermore,
oxidation of salicylic acid to 2,3-DHBA by ·OH was previously
applied as the probe reaction for quantifying [·OH]. However, the
probe molecules were below the detection, which was due to
low ·OH concentration.
to [·OH] was ~30 (Equation S2, 3), so that [·OH] was cacualted
as ~0.14 μmol·L-1. The BPA degradation pathway was further
identified by GC-MSD with ECD detector. The BPA contaminant
was primarily split into the monomer, which was thereafter
converted into various matters with low molecular weight
through attacking the benzene ring (Figure S10). After that, the
newly formed organic matters were mineralized into CO2 and
H2O (Figure S11), with a mineralization rate of ~34% after 20
min (Figure S12).
Figure 3. (a) Schematic illustration of exfoliating MoS2 from bulk to monolayer
and membrane preparation process. SEM images of (b) MS membrane and
(c) MSF-0.5 membrane surface. High magnification of SEM images of the
cross-sectional view of (d) MS and (e, f) MSF-0.5 membranes. Elemental
maps of g) molybdenum, sulfur, oxygen, and iron from the same area with the
same scale bar in the MSF-0.5 membrane.
Although fast degradation of organics was achieved by
application of the ce-MoS2/PMS system, the highly dispersed
suspension is hard to reuse and may induce secondary pollution.
Herein, using the vacuum filtration approach, the 2D MoS2
nanosheets were assembled into a lamellar MoS2 membrane
(MS membrane). At the same time, the lamellar membrane can
Figure 2. (a) in-situ Raman spectra of PMS, bulk MoS2/PMS and ce-
MoS2/PMS, (b) Mo valence evaluation of ce-MoS2 before and after reactions:
High-resolution XPS spectra of Mo, (c) EPR spectra of PMS activation system
using PMS only, bulk MoS2 and ce-MoS2, (d) Degradation and first-order
reaction kinetics of BPA removal by catalytic PMS using bulk MoS2/ce-MoS2.
preserve the active surface/edges to a large extent compared
[9c, 21]
with the original 2D structure.
The MS membrane can be
prepared by direct filtration of as-prepared ce-MoS2 on a PVDF
substrate with a pore size of 100 nm (Figure 3a). The FE-SEM
image in Figure 3b, d shows the smooth surface and compact
stack of layers in the MS membrane with a thickness of ~400 nm.
In order to create the abundant nanochannels in the interspacing
between 2D layers, Fe(OH)3 nanoparticles with diameter around
4~5 nm were applied as supports (Figure S13).[11, 21b, 22] The
positively charged Fe(OH)3 nanoparticles readily bonded to the
negatively charged ce-MoS2 surface (Figure S14), resulting in a
dense sandwich structure with rougher surface and stronger
hydrophilicity (Figure 3c, Figure S15). Fe(OH)3 template could
be successfully removed by diluted HCl (Figure 3g, Figure S16),
and the remaining trace amount of Fe ions almost has no effect
to PMS activation process (Figure S17). The etching process
retain abundant nanochannels, which was evidenced by the
uniform interspacing of the thicker membrane (referred to as
MSF-x in the following discussion) illustrated in Figure 3e, f.
This tunable interspacing is favorable for establishing a confined
The degradation of bisphenol A (BPA) was investigated to
evaluate the oxidation performance in AOP using ce-MoS2 as
activator. As depicted in Figure S7, in contrast to the negligible
BPA removal achieved by physical adsorption, only 20 min was
required for nearly total degradation of BPA in the ce-MoS2/PMS
based AOP system (Figure 2d). A modified kinetic model (k-
value) based on degradation rate (Text S1) was used to
evaluate the activation of PMS.[20] It can be seen that the k-value
of the ce-MoS2/PMS system is 3.672 µmol-1gcat-1s-1, almost 150
times higher than that of the bulk MoS2/PMS system, this value
is also much higher compared with other activators in recent
reports (Table S2, Figure S8). As shown in Figure S5a, it was
confirmed that the BPA oxidation in this ce-MoS2/PMS system is
·-
·-
a dual-radical (·OH and SO4 ) attacking process, whereby SO4
play the dominate role with a fraction of ~68%. (Figure S9). By
comparing BPA degradation kinetic parameters, the quenching
·-
experiments also confirmed that the concentration ratio of [SO4 ]
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10.1002/anie.201903531
Angewandte Chemie International Edition
COMMUNICATION
fluid, which provides
generation and utilization of ROS.
a
nanofluidic platform for efficient
enrichment of radicals as well as the molecular diffusion
between solid-liquid interface.
The stability was further investigated by pressure-dependent
continuous flow experiments, and a comprehensive Raman and
XPS spectra. As illustrated in Figure S21, with increasing gas
pressure from 0.1 to 0.8 bar, no obvious change of permeance
was observed in the MSF membrane, indicating the stable layer
structure of MSF membranes under harsh working conditions. A
series of characterization technologies were performed to gain
insight into structural and chemical states changes of MS
membrane after long-term activation. As depicted in the Figure
S22, benefited from the high exposure of available active sites
on ce-MoS2, the as-used MSF-0.5 exhibited a superior chemical
stability as evidenced by Raman spectra and XPS analysis, and
MSF-0.5-membrane-based reactor remained high BPA removal
efficiency (>90%) even after 3.8×105 BV (Figure 4c). Moreover,
Mo leaching was less than 70 μg L-1 after 1.3 × 105 BV, which is
even below Guidelines for dringking water quality 4th edition
(World Health Organization). Making the comprehensive
consideration of high removal efficiency, stability and cost, we
propose that MSF/PMS configuration should be ideal oxidation
process to low concentration organic pollutant or microorganism
sterilization in the end of water treatment.
In summary, we have developed a nanofluidic platform using a
lamellar MoS2 membrane for efficient advanced oxidation
processes. The ultrathin, conductive MoS2 nanosheets are
beneficial to firmly anchor PMS and subsequently trigger
efficient electron transport to boost the yield of ROS, whereby
the degradation rate of BPA is about 3.672 L·m-2·h-1·bar-1,
which is much greater than that of other activators in current
reports. Owing to the presence of an ordered layer structure with
tunable interlayer distance, which was derived by etching a
Fe(OH)3 nanoparticle template after vacuum filtration of MoS2
nanosheets, the as-prepared MSF-0.5 membrane maximized
the exposure of active surface and edges as well as generating
Figure 4. (a) Photograph of the experimental facility, with schematic of the
configuration of the flow-through device (right). (b) BPA removal performance
using MS membranes loading with various amount of Fe(OH)3 under pressure
of 0.2 bar. Working conditions: [BPA]0= 2 ppm, [PMS]0= 50 ppm, pH 4, T=25
oC. (c) Bed volume tests (BV) and Mo leaching of MSF-0.5 membrane.
The lamellar membrane was sealed in a miniaturized and
integrated stainless-steel filter holder, in which all the following
continuous permeance experiments were carried out (Figure
4a). Gas pressure was used to force water mixed with BPA and
PMS to flow through the nanochannels of the membrane. As
shown in Figure S18, the MS membrane with thickness of ~400
nm showed a low average permeance of ~55 L·m-2·h-1·bar-1,
which was probably due to the crowded layer structure (Figure
S19). After the introduction of Fe(OH)3 nanoparticles, the
average permeance in MSF-0.5 remarkably increased to ~154 L
· m-2 · h-1 · bar-1. The degradation of BPA in this system
maintained a level over 90% for 6 hours at relatively high
permeance (Figure 4b). This superior removal performance
should be primarily ascribed to high exposure of active surface
and edges in this lamellar structure, thereby generating
considerable amounts of radicals via rapid decomposition of
PMS. Additionally, the confined nanofluids in the interspacing
have the feature of ultra-low mass transfer resistance, thereby
providing an ideal platform for the reaction between
instantaneously produced radicals (ultrashort life-time of 10-6
s~10-9 s) and the target organics. The retention time (rt) was
measured to quantitatively analyze the performance of the
membrane (Figure S20). Only ~60.4 ms was required for total
degradation of BPA in this configuration, which was much faster
than traditional AOP processes. Greater introduction of Fe(OH)3
was able to increase the permeance of MSF-1 and MSF-2
membranes by factors of 3.4 and 4.2 to 186 and 231 L·m-2·h-1·
bar-1 (Figure 4b). However, these two membranes failed to
achieve full BPA degradation and showed leakage of BPA at
even less than 60 min. Widening the spacing between the layers
breaks the confinement of the nanofluids, which hinders the
a
non-linear nanofluidic platform with low mass transfer
resistance, which enabled high yields and efficient utilization of
instantaneously produced free radicals. The MSF-0.5 membrane
showed superior permeance of 154 L·m-2·h-1·bar-1 with durable
degradation of BPA (>90%) within the retention time of only 60.4
ms, which is considerably faster than that of traditional
treatments. As an outstanding approach for AOPs, the MoS2
membrane featured highly exposed active sites and tunable
confinement of inner fluids, constructing a platform for both
boosting free radical yields and strengthening mass transfer.
The increased generation of radicals coupled with their close
contact with contaminants enabled the rapid and stable
degradation of pollutants. The results may motivate the further
application of confined fluids in boosting radical yields and guide
the rational design of 2D membranes for Fenton-like reactions.
Acknowledgements
Financially supported by the National Natural Science Research
Fund of China (No. 51708543 and 51738013) and Major
Science and Technology Program for Water Pollution Control
and Treatment of China (2017ZX07402001).
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COMMUNICATION
Zhang, X. Cao, B. Song, S. Jin, J. Am. Chem. Soc. 2016, 138, 7965-
7972.
Keywords: Fenton-like reactions • MoS2 nanosheets •
Membranes • Density functional calculations • Confined
nanofluids
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This article is protected by copyright. All rights reserved.

10.1002/anie.201903531
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Yu Chen, Gong Zhang,* Huijuan Liu, and
Jiuhui Qu*
Fenton-like reactions were applied as
an efficient process for removing
organics. An ultrafast BPA removal
was achieved by catalytic PMS via
MoS2 membrane with tuneable
interspacing. The forced nanofluids
among interlayers give birth to a
kinetic enhanced ROS generation, as
well as a strengthened mass diffusion
which lead to a high utilization of
instantaneous ROS.
Page No. – Page No.
Ultrafast Fenton-like Process in
Interspacing of MoS2 Membrane
Enabled by Confining Sufficient Free-
Radicals in Close Vicinity to
Contaminants
This article is protected by copyright. All rights reserved.