Electrochimica Acta 399 (2021) 139409

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Strengthening oxygen reduction activity and stability of

carbon-supported platinum nanoparticles by fluorination
Ziheng Li a, Lijun Sui a,∗, Laura Calvillo b, Nicolas Alonso-Vante c, Jiwei Ma a,∗
a
Shanghai Key Laboratory for R&D and Application of Metallic Functional Materials, Institute of New Energy for Vehicles, School of Materials Science and
Engineering, Tongji University, Shanghai 201804, China
b
Department of Chemical Sciences, University of Padua, Via Marzolo 1, Padova 35131, Italy
c
IC2MP, UMR-CNRS 7285, University of Poitiers, 4 rue Michel Brunet, Poitiers 86073, France

a r t i c l e i n f o a b s t r a c t

Article history: By combining experimental and theoretical aspects, this study focuses on exploring and enhancing the
Received 29 June 2021 activity and stability towards oxygen reduction reaction (ORR) of fluorinated carbon supported platinum
Revised 13 September 2021
nanoparticles in the acidic electrolyte. Physical characterization results revealed that fluorinated carbon
Accepted 5 October 2021
support generates a C-F bonding. The interaction between Pt and fluorinated-carbon allows for a strong
Available online 19 October 2021
charge transfer from Pt to the support. This phenomenon is consistent with the density functional theory
Keywords: (DFT) analysis. Because of the fluorination, the electronic structure of Pt is changed, which is an advantage
Fluorinated carbon for improving the catalytic activity and stability of the catalyst towards ORR.
C-F bonding © 2021 Elsevier Ltd. All rights reserved.
Platinum nanoparticles
Interaction
Oxygen reduction reaction

1. Introduction ment of durability and activity by tuning the electronic structure

Proton exchange membrane fuel cells (PEMFCs) have made
tremendous development over the past thirty years as an
environmental-friendly power device with high energy density and
low gas-emission [1, 2]. Unfortunately, the sluggish kinetics of oxy-
gen reduction reaction (ORR) at the cathode of PEMFCs has a high
active catalyst requirement. Carbon-supported Pt, commonly used
in the cathode, makes large-scale commercial application difficult
due to its high price and degradation [3, 4]. Modified Pt and sup-
ports have been reported as an efficient way to overcome such
problem [5, 6]. Carbon black is used widely as support for elec-
trode catalysts due to its good electrical conductivity and large
specific surface area. However, carbon in acidic medium and at
an electrode potential > 0.97 VRHE , leads to loss and agglomer-
ation of Pt nanoparticles (NPs) further reducing the durability of
the cell during the operation [7, 8]. The doped carbon support is
expected to improve the durability of the nanoparticulate electro-
catalyst through interaction with the catalytic center. Carbon sup-
ports doped by B [9], N [10], F [11–13], P [14], S [15] for Pt and Pt-
based catalysts have been synthesized and induced the improve-
∗
Corresponding authors.
E-mail addresses: sui@tongji.edu.cn (L. Sui), jiwei.ma@tongji.edu.cn (J. Ma).
of Pt favorable for the ORR. In this regard, it has been reported
that nitrogen-doped reduced graphene oxide (NRGO) supported Pt
NPs showed a strong interaction between Pt and N atoms, that al-
lowed for charge transfer from Pt to the carbon support. This phe-
nomenon caused the O–O distance of the absorbed O2 species to
lengthen, promoting its dissociation [16]. Oi et al. [15] deposited Pt
NPs on S-doped carbon matrix to increase its stability. The bond
formed, C-S-C, as a result of doping, improved the corrosion re-
sistance and Pt NPs exhibited strong adhesion with the carbon
support. Obviously, the mechanisms of operation of these strate-
gies with respect to the corresponding electronic structures are
elusive. The underlying effect for the electrochemical performance
of catalysts induced by electronic effects are often different due
to their intrinsic characteristics, e.g., atomic radii and electroneg-
ativity. In the case of F-doped carbon-based supports, F-doped
graphene nanoribbon (F-GNR) is extremely advantageous as it in-
creases the carbon corrosion resistance due to the fact that F-GNR
hardly adsorbs O groups as carbon corrosion initiators [11]. Like-
wise, fluorination of the structurally-disordered carbon also has
positive effects, since the stability of carbon-based support de-
pending on “free”-dangling groups. Indeed, C-F bond is more sta-
ble than C–O bond in the acid condition [12]. Ruan et al. [13], on
the other hand, have reported that the regeneration of irreversible

https://doi.org/10.1016/j.electacta.2021.139409
0013-4686/© 2021 Elsevier Ltd. All rights reserved.
Z. Li, L. Sui, L. Calvillo et al.
Fig. 1. TEM images of Pt/C (a, b) and Pt/F-C (c, d), Pt size distribution of Pt/C (e) and Pt/F-C (f) along with the TEM-EDS mapping of Pt/F-C(g-j).
deactivation, induced by the sintering of catalytic Pt nanoparticles
(NPs). The morphology change of Pt NPs is due to the strong in-
teraction between d states of Pt and p states of fluorine. This phe-
nomenon was supported by DFT calculation using a structurally-
ordered carbon doped by F. Nevertheless, the structure-property
relationship for fluorinated carbon-supported Pt NPs for ORR has
not been clarified yet.
In this study, fluorinated carbon support has been synthe-
sized through a modified low temperature topotactic reaction
method, followed by depositing Pt on fluorinated carbon using
impregnation-gas reduction method. Our aim is clarifying, by com-
bining experimental and theoretical results, the nature of the in-
teraction between Pt NPs and fluorinated carbon in the acidic con-
dition, which is responsible for the enhanced ORR activity and sta-
bility.
2. Experimental
2.1. Fluorination of Vulcan XC-72 carbon black
The fluorination of Vulcan XC-72 carbon black (Cabot Corpora-
tion) was performed using a modified low temperature topotactic
reaction method in a pair of sealed nested nickel crucibles [17].
Briefly, a desired amount of Xenon difluoride (XeF2 , Alfa Aesar,
99.5%) was placed in the outer crucible, and 100 mg Vulcan XC-
72 carbon black was placed in the inner crucible with 1:1 mo-
lar ratio (F:C). The steps described above were carried out in an
argon-filled glove box. After sealing the outer crucible, the whole
crucibles were placed into a tube furnace under N2 atmosphere at
120 °C for 12 h. The fluorinated carbon and Vulcan XC-72R carbon
were denoted as F-C and C, respectively.
2.2. Synthesis of Pt/C and Pt/F-C catalysts
20 wt.% Pt NPs supported on C and F-C were prepared by a sim-
ple impregnation-reduction method [18]. Briefly, 410 μL of 0.25 M
2
Electrochimica Acta 399 (2021) 139409
H2 PtCl6 •6H2 O (Acros) aqueous solution with 80 mg C or F-C sup-
ports were mixed in 20 mL ethanol and ultrasonicated for 1 h.
The suspension was heated at 70 °C, under magnetic stirring, until
complete evaporation of the ethanol. The obtained black powder
was ground for 10 min in a quartz mortar and then dried in an
oven at 60 °C for 12 h, followed by gas-reduction in a tube furnace
at 300 °C under a continuous flow of 5 vol% H2 /Ar for 2 h.
2.3. Physical-chemical characterization
The crystal phase of the Pt NPs was determined by X-ray
diffraction (XRD) patterns with BRUKER D8 Advance diffractome-
ter (40 kV, 40 mA, Germany) equipped with a Cu Kα source
(λ1 = 1.5405 Å, λ2 = 1.5443 Å) at room temperature in the range
of 2θ from 10° to 90° with a scanning step of 0.02° The size dis-
tribution histograms of Pt NPs were analyzed from transmission
electron microscopy (TEM) images by counting the average par-
ticle size of 200 individual NPs. TEM images were recorded with
JEOL JEM-2100 with an accelerating voltage of 200 kV. The surface
chemical states and electronic structure of the catalysts were ex-
amined by X-ray photoelectron spectroscopy (XPS) using ESCALAB
250Xi provided with Al Kα source. The N2 adsorption and desorp-
tion measurements were done on an Autosorb iQ Quantachrome
device and the specific surface area with pore size distribution
were obtained by the Brunauer-Emmett-Teller (BET) and Barrett-
Joyner-Halenda (BJH) analyses, respectively. The Pt content was de-
termined by Thermogravimetric analysis (TGA) with TA Q50 device
from 30 °C to 800 °C at a 5 °C/min heating rate under air atmo-
sphere.
2.4. Electrochemical measurements
Electrochemical properties of the as-prepared catalysts (Pt/C,
Pt/F-C) were conducted in a three-electrode electrochemical cell
with rotating disk electrode (RDE, MSR, Pine Instruments, USA) on
a CHI760E potentiostat (Shanghai Chenhua Instrument Corporation,
Z. Li, L. Sui, L. Calvillo et al. Electrochimica Acta 399 (2021) 139409

Fig. 2. (a) XRD patterns of Pt/C and Pt/F-C. (b) High resolution C 1 s XPS spectra of C, F-C, Pt/C and Pt/F-C, and (c) Pt 4f XPS spectra of Pt/C and Pt/F-C, and (d) F 1 s XPS
spectra of F-C and Pt/F-C. The corresponding separation into single chemical components is included in the figures b-d.

China). A glassy carbon (GC) electrode (0.196 cm2 ) polished with Linear sweep voltammetry (LSV) was conducted at a scan rate
Al2 O3 polishing suspension was used as the working electrode. A of 10 mV s − 1 from 0.2 to 1.0 V (vs. RHE) at different rotation rates
graphite rod and a homemade reversible hydrogen electrode were to evaluate the transferred electrons number (n) in O2 -saturated
used as the counter electrode and the reference electrode, respec- 0.1 M HClO4 solution. The kinetic current density (jk ) can be cal-
tively. The catalyst ink was prepared by dispersing 2.4 mg cata- culated by using the Koutecky–Levich equation:
lyst in a mixture solution containing 580 μL isopropanol (Aladdin)
and 20 μL Nafion® (5 wt.%, Shanghai HESEN Corporation) and ul- 1 1 1
= +
trasonicating for 10 min. 5 μL of homogeneous catalyst ink was j jk jd
carefully coated on the working electrode and dried in air at room
temperature to form a uniform thin film. For the sake comparison, where j is the measured current density and jd is the diffusion
the commercial Pt/C (Johnson Matthey) was purchased and com- limited current density. jd can be calculated from the Levich equa-
pared with homemade Pt/C and Pt/F-C catalysts. The commercial tion:
Pt/C was referred to JM Pt/C.
jd = 0.62nF D 3 v− 6 ω 2 CO2
2 1 1

Cyclic voltammetry (CV) was firstly conducted at the scan rate

of 100 mVs−1 in N2 -saturated 0.1 M HClO4 solution (AR 70∼72%,
where n is the transferred electron number; F is Faraday’s constant
Aladdin) from 0.05 to 1.2 VRHE over 50 cycles to remove the surface
(96,485 C mol−1 ); D is the diffusion coefficient of O2 in 0.1 M
contaminants and get stable curves. Subsequently, 6 CVs were con-
HClO4 solution (1.93 × 10−5 cm2 s − 1 ); ν is the kinematic vis-
ducted at 50 mVs−1 to evaluate the electrochemical surface area
cosity of the electrolyte (1.01 × 10−2 cm2 s − 1 ); ω is the angu-
(ECSA) of the catalyst, assuming a charge of 210 μC cm−2 involved
lar frequency of rotation, ω =2π f/60, f is the RDE rotation rate
in the oxidation of a monolayer of adsorbed hydrogen on Pt, ac-
in rpm; CO2 is saturated concentration of molecular oxygen in the
cording to the following equation:
electrolyte (1.26 × 10−6 mol cm−3 ) [19].
Q Accelerated durability test (ADT) was conducted by cycling the
ECSA =
210(μC · cm−2 ) · MPt potential between 0.6 V and 1.0 V for 50 0 0 cycles in O2 -saturated
0.1 M HClO4 at a scan rate of 100 mV s − 1 . The CV and LSV curves
where Q is the integral charge collected in the hydrogen adsorp- were recorded to compare the ORR activity before and after poten-
tion/desorption region after double-layer correction and MPt is the tial cycling. All electrochemical tests were conducted at 25 °C by
Pt content of the working electrode. using a constant temperature water bath device.

3
Z. Li, L. Sui, L. Calvillo et al.
Fig. 3. (a) LSV curves of Pt/C and Pt/F-C recorded with a rotation rate of 1600 rpm at room temperature with a scanning rate of 10 mV s − 1 in O2 saturated 0.1 M HClO4
aqueous solution. (b) Koutecky-Levich plots. Inset figure shows the corresponding rotating-disk voltammograms. (c) Relative SA and MA at 0.9 VRHE for the investigated
electrocatalysts. MA and SA are given as kinetic current densities (jk ) normalized to the loading amount and ECSA of Pt, respectively. (d) Tafel plots of Pt/C and Pt/F-C in the
potential range from 0.85 to 0.9 VRHE .
2.5. DFT analyses
In order to investigate the electronic properties of the system,
we performed a DFT analysis of the interaction between carbon
black and platinum. The low concentration of fluorine was simpli-
fied using single atom of F; Ptn (n = 1 − 4) clusters were employed
as those supported Pt NPs on the non-doped carbon and the F-
doped carbon supports. All DFT calculations were performed with
the Vienna ab-initio simulation package (VASP) [20] using Perdew-
Burke-Ernzerhof (PBE) [21] of the generalized gradient approxima-
tion (GGA) and the projector augmented wave (PAW) [22] method
was used. Plane-wave cutoff energy was set to 400 eV and k-point
separation of 0.03 Å−1 was adopted. The convergence threshold
was set to 10−5 eV for electronic relaxation and 0.01 eV/Å for
forces. The vacuum thickness was set as 15 Å.
3. Results and discussion
3.1. Physicochemical characterization of Pt/C and Pt/F-C
The mass loading of Pt was determined by ICP-OES and TGA
measurements, cf. Table S1 and Fig. S1. All the catalysts presented a
similar Pt content and close to the nominal value. Fig. 1(a-d) shows
representative TEM images of the synthesized Pt/C and Pt/F-C, in
which Pt NPs are uniformly dispersed on C and F-C. The Pt par-
ticles size distribution for Pt/C (1.86±0.47 nm) is slightly smaller
than that of Pt/F-C (1.91± 0.47 nm), as shown in Fig. 1(e, f). After
fluorination, the BET surface area of carbon used as support de-
creased (Fig. S2). This phenomenon is due to the destruction of the
initial carbon texture and, consequently, the decrease of the large
pore size ratio. As a result, a slight increase of the agglomeration
of Pt NPs took place on C-F [13]. TEM-EDS mapping analyses show
4
Electrochimica Acta 399 (2021) 139409
a relatively uniform distribution of Pt and F on C, indicating the
formation of Pt/F-C catalyst, Fig. 1(g-j).
The XRD patterns of the investigated catalysts are shown in
Fig. 2(a). The positions of the diffraction peaks of Pt/F-C were al-
most identical to those of the Pt/C, located at 39.8°, 46.2°, 67.7°,
81.3°, 85.8° corresponding to the (111), (200), (220), (311) and
(222) planes of FCC (face centered cubic) diffraction peaks of Pt
NPs. The broad peaks at around 25° are attributed to the carbon
support.
XPS experiments were carried out to characterize the effects of
fluorination on the surface chemical state of carbon support and
the interaction between Pt NPs and support. The analysis of the
C 1 s region, Fig. 2(b) and Table S2, shows an increase of the
sp3 component in the F-C support after the fluorination treatment,
compared to the pristine one (C), indicating that the incorporation
of F atoms affects the sp2 structure of the carbon support [23].
In addition, a new component at 288.8 eV related to C-F bonds
confirms the introduction of F atoms into the carbon support [23,
24]. The analysis of the Pt 4f region, Fig. 2(c), shows an increase of
the Pt2+ and Pt4+ species for Pt/F-C (Table S3), compared with Pt/C,
which could be attributed to the Pt-F interaction and the conse-
quent electron donation from Pt to F. This result is confirmed by
the analysis of the F 1 s region, Fig. 2(d). For F-C, the F 1 s region
can be separated into 2 components at 286.3 eV and 287.5 eV, at-
tributed to fluorine covalently bonded to carbon in different sites
and/or with different density of F atoms [25, 26]. For Pt/F-C, the
same peaks are also observed but they are slightly shifted to lower
binding energies due to the electron transfer from Pt to F. A third
component at 288.8 eV is observed in this case. Usually, this BE is
related to CFx sites [25] that could have been formed during the
reduction treatment of Pt at 300 °C. These results confirm that the
presence of F has an important effect on the electronic properties
of Pt. Pt is more electron deficient in Pt/F-C than in Pt/C due to the
Z. Li, L. Sui, L. Calvillo et al. Electrochimica Acta 399 (2021) 139409

Fig. 4. (a) CV curves of Pt/C and Pt/F-C after each 10 0 0 cycles in ADTs (10 0 0∼50 0 0 cycles) in N2 -saturated 0.1 M HClO4 at a scan rate of 50 mV/s. (b) Normalized ECSA loss
of Pt/C and Pt/F-C. (c) LSV curves before and after ADT test in O2 saturated 0.1 M HClO4 at a scan rate of 10 mV/s. (d) Relative SA and MA of the investigated electrocatalysts
before and after ADTs. TEM images of (e) Pt/C and (f) Pt/F-C along with Pt size distribution of Pt/C (g) and Pt/F-C (h) after ADTs.

interaction with the F atoms of the support that attracts electrons
from Pt.
3.2. Electrochemical characterization of Pt/C and Pt/F-C for ORR
The electrochemical activity towards ORR was evaluated in O2
saturated 0.1 M HClO4 solution. Pt/F-C exhibits a higher half-wave
potential (0.870 VRHE ) than that of Pt/C (0.868 VRHE ), Fig. 3(a).
The kinetic current (jk ) can be extracted from the Koutecky−Levich
(K-L) equation. The linearity of the K-L plots and the near paral-
lelism or overlap of the fit lines, shown in Fig. 3(b) and Figs. S3–4,
demonstrate the first-order reaction kinetics toward the concen-
tration of dissolved oxygen and approaching a four-electron charge
transfer mechanism for ORR. In order to compare the electrocat-
alytic activity of the Pt/F-C and Pt/C systems, the relative spe-
cific activity (SA) and mass activity (MA) calculated at 0.90 VRHE
are shown in Fig. 3(c) and Fig. S5. The MA and SA of Pt/F-C
are 1.3 -fold and 1.5 -fold higher than the respective values for

5
Z. Li, L. Sui, L. Calvillo et al.
Fig. 5. (a) Bader Charge from heteroatoms (B, P, S, F, N) to host C. (b) Optimized structures of F-C and N–C (average bond length: Å). (c) Projected density of states (PDOS)
for d-orbitals of Pt atom of Pt/C and Pt/F-C. (d) The side-view of electron density difference of Pt on C and F-C (Bader charge: e).
Pt/C. As a result, Pt/F-C has higher electrocatalytic activity than
Pt/C. The Tafel plots were extracted from the mass-transfer cor-
rected LSV curves, as shown in Fig. 3(d). The Tafel slope of Pt/F-
C (65.3 mV/dec) is similar to Pt/C (69.6 mV/dec), indicating that
the rate-determining step of ORR is dominated by the ORR process
after one-electron transfer step on both catalysts [27, 28].
To investigate the durability of the catalysts in acidic envi-
ronment, accelerated durability tests (ADTs) were carried out. As
shown in Fig. 4(a), the CV curves were recorded after every
10 0 0 cycles from 0.05 to 1.20 VRHE . The carbon surface redox
peaks for Pt/C were shown around 0.6 VRHE , which corresponds
to hydroquinone−quinone formation at high electrode potential.
The loss of carbon support results in agglomeration and/or detach-
ment of Pt NPs [29]. However, the surface carbon redox peak is
not favored on Pt/F-C at 0.6 VRHE , certainly, thanks to augmented
chemical stability of C by fluorination. The ECSA evolution for Pt/C
shows a more severe degradation compared with Pt/F-C (Fig .4b),
suggesting that Pt/F-C exhibits an enhanced stability with cycling
compared to Pt/C. After 50 0 0 cycles, the Pt/C catalyst retains ca.
69% of its initial ECSA, whereas Pt/F-C retains ca. 85% of its initial
ECSA. The ECSA loss is likely caused by the dissolution and/or ag-
glomeration of Pt NPs through the electrochemical Ostwald ripen-
ing process induced by the ADTs [30]. Additionally, when com-
paring the ORR electrocatalytic activity before and after ADT, we
found that the half-wave potential of the Pt/F-C system only shows
a change of −10 mV while Pt/C system shows a change of −41 mV
(Fig .5c) after 50 0 0 cycles. The SA and MA decrease of Pt/F-C after
ADTs was smaller than that observed for Pt/C (Fig 5c). The stabil-
ity performance of the commercial JM Pt/C exists a similar trend
as homemade Pt/C catalyst, as shown in Fig. S6. Thus, the durabil-
ity of the catalyst is significantly enhanced via the fluorination of
carbon. The TEM images and Pt size distribution of Pt/C and Pt/F-
C catalysts after ADTs are shown in Fig. 4 (e-h). The aggregation
of Pt NPs is not obvious on F-C support compared with that on
C support. This phenomenon is consistent with the smaller ECSA
loss for Pt/F-C. The stability enhancement of Pt/F-C can be par-
tially ascribed to the strong metal−support interaction [31], a phe-
6
Electrochimica Acta 399 (2021) 139409
nomenon that prevents Pt migration and agglomeration. In addi-
tion, it is apparent that carbon fluorination contributes to enhance
the stability of the carbonaceous support at higher applied elec-
trode potential.
The geometrical and electronic properties of F-C and C were
compared by DFT calculation. Regarding heteroatoms bonding sit-
uation with C, there exists a substantial electron charge transfer
(e). The electron transfer from heteroatoms to the C atom are con-
sidered positive values, while the negative ones indicate an elec-
tron transfer from C to the heteroatoms, i.e., B (+1.75) > P (+1.20)
> S (+0.15) > F (−0.62) > N (−0.91), as shown in Fig. 5(a). This
indicates the formation of polarized heteroatom-C bonds, which
enables the tuning of the electronic structure of C adjacent to
the heteroatom, in which B, P and S transfer electrons to C host,
whereas F and N gain electrons from C host. N atoms get more
electrons than F, but the C-F bond length (1.36 Å) is smaller than
the C–C (1.42 Å) and C–N (1.60 Å) bonds, as shown in Fig. 5(b). This
phenomenon can be explained as F atoms can accept one elec-
tron so that they can only bond to one C atom [32]. However, B,
N, S, and P can replace sp2 and sp3 C atoms; while tertiary al-
cohols bond with 2 or 3 C atoms, as shown in Fig. 5(b) and Fig.
S7. Hence, F-C, as a superior stable support, was considered in our
case. We built a structurally-disordered carbon to simulate carbon
black, and a single Pt atom replacing Pt NPs to describe the elec-
tronic structure by simplifying the catalyst structures. As shown in
Fig. 5c, the Pt atom in Pt/F-C (1.40 eV) has a higher d-band center
than that in Pt/C (1.52 eV), shifting upward the Fermi level. This
results in a binding energy of adsorbed ∗ O2 with higher-lying d-
orbitals, which promotes the ORR activity. Fig. 5d displays the side-
view of the electron density difference in the planes of Pt atoms
on C and F-C supports, from which it is observed that the electron
density modification is induced by the fluorination, namely, Pt to
C (0.04 e) and to C-F (0.07 e) supports, respectively. It is worth
mentioning that the value of the average charge transfer is sim-
ilar on Ptn (n = 1 − 4) clusters (Table S4). The observed Pt has
a small charge density difference with F-C due to more electrons
being transferred, concomitant with XPS results.
Z. Li, L. Sui, L. Calvillo et al.
Conclusion
In summary, we have synthesized Pt/F-C catalyst using fluori-
nated carbon black as a support, which demonstrated high activity
and durability for ORR compared to Pt/C catalysts in acidic me-
dia. Therefore, the increased catalytic activity and durability of the
Pt/F-C can be generalized as follows: (i) Free dangling groups of
carbon support bond with F atom upon fluorination, resulting in
the formation of stronger C-F bonds versus the oxidation of the
original C–O bonds and C–C bonds. (ii) Charge transfer between Pt
and the support is the origin of the strong interaction of the metal-
support, modifying the local electronic structure of Pt induced by
the fluorination.
Declaration of Competing Interest
The authors declare no competing interest.
Acknowledgements
The work leading to these results has received funding from the
Fundamental Research Funds for the Central Universities.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.electacta.2021.139409.
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