ORIGINAL RESEARCH

published: 03 March 2022

doi: 10.3389/fphy.2022.853179

Sm-Eu Co-Doped BiFeO3

Nanoparticles With Superabsorption
and Electrochemical Oxygen
Evolution Reaction
Yanhong Gu 1, Niu Huang 2*, Chaoyang Guo 1, Yuanxi Liang 1, Weiying Zhang 1, Jianguo Zhao 1,
Xianghui Zhang 1, Hong Jia 1* and Wanping Chen 3
1
School of Physics and Electronic Information and Key Lab Electromagnet Transformation and Detect Henan, Luoyang Normal
College, Luoyang, China, 2Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, College of
Materials and Chemical Engineering, China Three Gorges University, Yichang, China, 3Key Laboratory of Artificial Micro- and
Nano-Structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan, China

Bi0.95Sm0.05Fe1−xEuxO3 (x = 0, 0.05, 0.10, 0.15) nanoparticles were prepared via a two-

solvent sol–gel method. The X-ray diffraction (XRD) and Raman results suggested that the
main phase of the samples gradually evolved from perovskite phase R3c to orthorhombic
Edited by:
Sugata Chowdhury, phase Pbnm with increasing Eu content and that the optical band gap gradually narrowed
National Institute of Standards and from 2.09 to 1.70 eV. Along with the structural change, the ferromagnetic properties were
Technology (NIST), United States
transformed, and interesting double hysteresis loops were observed for the sample where
Reviewed by:
Rahul Kumar,
x = 0.1. All the bismuth ferrite (BFO) samples demonstrated extremely strong adsorbability,
Indian Institute of Technology Delhi, with the adsorption rate of refractory methyl orange reaching 90% in 5 min. These samples
India also exhibited superior oxygen evolution reaction (OER) performance, with a desirable
Khian-Hooi Chew,
University of Malaya, Malaysia onset potential of approximately 1.50 V vs. RHE. For the sample where x = 0.15, to support
*Correspondence: a current density of 100 mA/cm2, an overpotential of only 294 mV was required, which is
Niu Huang much better than that of pure Ni foam (330 mV). More experiments are needed to verify and
huangliu.ysxf@163.com
Hong Jia
explore the source and mechanism of the OER performance.
jiahong517@aliyun.com
Keywords: BiFeO3, energy gap, ferromagnetism, super absorption, oxygen evolution reaction (OER)

Specialty section:
This article was submitted to
Physical Chemistry and Chemical INTRODUCTION
Physics,
a section of the journal In recent years, owing to the magnetoelectric coupling effect, multiferroic materials have been widely
Frontiers in Physics applied in the fields of information storage, electronic devices, and sensors, and thus they have
Received: 12 January 2022 attracted extensive attention from researchers worldwide. Bismuth ferrite (BiFeO3, or BFO) stands
Accepted: 02 February 2022 out among multiferroic material because of its ferromagnetism and ferroelectricity at room
Published: 03 March 2022 temperature [1, 2]. BFO can also be used as a photocatalyst to degrade organic pollutants and
Citation: decompose water because it is a semiconductor material with a narrow band gap (2.2 eV) and
Gu Y, Huang N, Guo C, Liang Y, excellent chemical stability [3, 4].
Zhang W, Zhao J, Zhang X, Jia H and At present, there are two popular ways to decompose water: photocatalytic decomposition and
Chen W (2022) Sm-Eu Co-Doped
electrocatalytic decomposition. The electrocatalytic decomposition of water involves two reactions:
BiFeO3 Nanoparticles With
Superabsorption and Electrochemical
the anodic oxygen evolution reaction (OER) and the cathodic hydrogen evolution reaction (HER),
Oxygen Evolution Reaction. both of which are related to electrocatalysts. OER is the key reaction in energy storage processes, such
Front. Phys. 10:853179. as water cracking and metal–air batteries [5]. However, it is difficult to carry out because it involves
doi: 10.3389/fphy.2022.853179 four proton-coupled electron transfer processes, and so it requires a very high overpotential to

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Gu et al. Oxygen Evolution Reaction of BiFeO3

complete the process [6]. At present, IROx/RuOx and Pt/C are the
benchmark electrocatalysts for OER and HER, respectively.
Although these electrocatalysts exhibit high electrocatalytic
activity and kinetics, their high cost, scarcity, and
unsatisfactory electrochemical stability prevent them from
being widely used. In recent years, many efforts have been
made to design low-cost, high-catalytic, stable, and
environmentally friendly non-noble metal or carbon-based
electrocatalysts. Perovskite oxides (ABO3−δ) have been widely
studied as electrocatalysts owing to their composition and
structural flexibility [7–10]. Perovskite oxides (ABO3) also
have a variety of structures and physical and chemical
properties, which have attracted considerable interest for use
in OER. The perovskite oxide BFO is a multiferroic functional
material, as well as a ferroelectric semiconductor that facilitates
the separation of electrons and holes, and thus BFO is
increasingly being investigated for applications in solar energy FIGURE 1 | XRD patterns of the Bi0.95Sm0.05Fe1−xEuxO3 (x = 0.0, 0.05,
0.10, 0.15) ceramic samples, with enlarged views of the (104) and (110)
conversion and for designing desired electrocatalysts.
diffraction peaks near the diffraction angle 2θ = 32°.
BFO has made many representative achievements in catalytic
performance and energy storage of fuel cells [11–13]. The
application and development of BFO as a supercapacitor has
also achieved a lot of fruitful work [14–18]. further studied using its ferroelectric and ferromagnetic
Bi0.15Sr0.85Co0.8Fe0.2O3-δ presents a low OER overpotential properties.
(354 mV at 10 mA cm−2) and good reaction kinetics for both
OER and ORR (94.21 mV dec−1 and 72.5 mV dec−1, respectively)
[19]. The current density for the OER of Bi0.6Ca0.4FeO3 showed a EXPERIMENTAL
significantly high value of 6.93 mA/cm2 at a fixed overpotential of
0.42 V (1.65 V vs. RHE) [20]. A 15% Ca-doped Bi0.85Ca0.15FeO3 Synthesis of Sm and Eu Co-Doped BiFeO3
catalyst showed an increased kinetic current density of BiFeO3 and Bi0.95Sm0.05Fe1−xEuxO3 (BSFEO) (x = 0.0, 0.05, 0.10,
54.562 mA/cm2 at an onset potential of 2.122 (V vs. RHE) 0.15) nanoparticles, denoted as BFO, BSFO, BSFO–5Eu,
with an overpotential of 0.892 V in an alkaline electrolyte [21]. BSFO–10Eu, and BSFO–15Eu, respectively, were synthesized
All of these tests are performed on glassy carbon, but surface by the double-solvent sol–gel method. Bi(NO3)3·5H2O (99%
chemistry is an important prerequisite for advanced water pure) and Sm(NO3)3·6H2O (99.9% pure) were mixed
electrolysis. The excellent specific surface area of nickel foam stoichiometrically, dissolved in ethylene glycol (C2H6O2), and
has not been fully utilized to demonstrate the OER performance stirred for 90 min at room temperature (RT). Fe(NO3)3·9H2O
of BFO. The porous structure of the Ni foam can expose more (98.5% pure) and Eu(NO3)3·6H2O (98.5% pure) powders were
active sites of the material. dissolved in acetic acid and magnetically stirred for 1.5 h.
In this work, Sm and Eu are chosen for co-doping into the Subsequently, the two solutions were mixed and stirred
BFO host materials. Because Sm doped BiFeO3 can improve continuously for 3 h, resulting in a homogeneous, reddish-
magnetic and electric properties [12]. Eu substitution for the Fe- brown, and fine precursor solution (0.4 M). Because of the
site is expected to modulate structure and band gap width to a bismuth loss during heating, an excess of 3% bismuth was
greater extent resulting in a good water decomposition and added to the solution to compensate. To maintain the
electrocatalytic performance [22, 23]. Herein, we report a electronegativity of the iron and bismuth during the chemical
simple and feasible method for the fabrication of perovskite reactions, ethylene glycol was added as a solvent. In the synthesis
BiFeO3 photoanodes. Sm and Eu co-doped BiFeO3 process, acetic acid was used as a catalyst to control the chemical
nanoparticles were fabricated by a double sol–gel method. reaction and maintain the concentration of the solution. The
With increasing Eu content, the BFO structure changed from prepared solution was dried in an oven at 80°C for a few days to
perovskite to orthorhombic, as demonstrated by both X-ray obtain a gel, which was then ground into a fine powder and
diffraction (XRD) and Raman patterns. Interestingly, the Sm calcined in an oven at 600°C for 3 h to remove the organic matter.
and 15% Eu co-doped BiFeO3 had a strong adsorption Subsequently, it was ground again and cleaned with dilute nitric
performance, and the adsorption rate of methyl orange acid. The BSFEO samples were prepared after a few hours of
reached 95% in 5 min. The electrocatalytic performance was drying.
also superior, such that at an onset potential of 1.48 V vs.
RHE, the overpotential was merely 294 and 310 mV to Materials Characterization
support current densities of 100 mA/cm2 and 400 mA/cm2, XRD and Raman scattering spectroscopy were used to
respectively. BFO is a multifunctional composite material. It is characterize the structures of the samples. Scanning electron
therefore hoped that the electrochemical properties of BFO can be microscopy (SEM) was used to determine the morphology and

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Gu et al. Oxygen Evolution Reaction of BiFeO3

OER Characterization
The catalyst ink was prepared by dissolving 5 mg of catalyst in
1.96 ml of deionized water and ethyl alcohol in a volume ratio of
1:1, after which 40 μl of Nafion® was added. The mixture was
sonicated for 30 min to form a homogenous ink. Next, 0.4 ml of
ink was dropped onto the surface of Ni foam (NF, with surface
area of 1 cm2). After drying naturally at RT, the BSFEO/NF series
were prepared. The electrochemical OER was carried out using a
three-electrode system on an electrochemical workstation
(CHI760E) with a catalyst coated on glassy carbon (GC) or
NF as the working electrode, carbon rods, and saturated Hg/
HGO electrodes as the counter and reference electrodes,
respectively. OER tests were performed in an O2-saturated 1 M
KOH electrolyte at RT at a scanning rate of 5 mV/s. Infrared
compensation was applied for calibration in the linear sweep
voltammetry (LSV) tests, and a reversible hydrogen electrode
FIGURE 2 | Raman spectra as a function of Eu composition.
(RHE) was used to adjust the working potential.

RESULTS AND DISCUSSION

granularity of the prepared samples. The ultraviolet-visible (UV-
vis) diffuse reflectance spectra of the prepared samples were Figure 1 shows the XRD patterns of the Bi0.95Sm0.05Fe1−xEuxO3
studied using a UV-vis spectrophotometer, and the band gap (x = 0.0, 0.05, 0.10, 0.15) nanoparticles and the distorted
width was studied. The ferromagnetic properties of the samples in rhombohedral structures with an R3c space group. The doubly
the magnetic field range of −20 to 20,000 KOe were investigated split peaks of BFO in the 2θ range of 31–33° merge to a single peak
using a vibrating sample magnetometer (VSM) at RT. The N2 upon doping with Eu, and two smaller peaks formed on each side,
adsorption–desorption isotherms were measured using an ASAP which became higher as the doping proportion increased. These
2020 Plus HD88 gas adsorption and porosity meter at a liquid analyses indicate that the crystallinity of the BFO powder was
nitrogen temperature of −196°C. Before the experiment, the considerably affected by doping with Eu. In addition, at x = 0.15
sample was degassed at 140°C for 3 h. The and 0.2, the diffraction peaks in the 2θ range of 38–40° split, and
Barrett–Joyner–Halenda (BJH) method was used to obtain the there were some changes in other peaks. Previous research has
distribution curve of the pore size. All electrochemical shown that an orthorhombic structure can be transformed during
measurements were conducted using an electrochemical element substitution [24, 25], thus the unit-cell symmetry of
workstation (CHI760E, Chenhua). BSFEO shifted from R3c to Pbnm with increasing Eu content.

FIGURE 3 | SEM images of BSFO powders doped with Eu at ratios of (A) 0.0, (B) 0.05, (C) 0.10, and (D) 0.15. TEM images of BSFO–15Eu nanoparticles (E), and
(F) shows the SAED of BSFO–15Eu nanoparticles and the belt axis is [100].

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Gu et al. Oxygen Evolution Reaction of BiFeO3

FIGURE 4 | (A) UV-vis diffuse reflectance spectrum of the BSFO, BSFO–5Eu, BSFO–10Eu, and BSFO–15Eu nanoparticles, (B) the calculation of band gap.

TABLE 1 | The band gap width of BSFEO.

agglomeration and surface structure are becoming more
conspicuous and homogeneous with increasing Eu substitution
Doping content λ/nm Eg/eV concentration. Upon further increasing the Eu content, the grain
0 600 2.07 size of the samples continued to increase. The average grain size
BSFO-5Eu 652 1.90 increased from 30 to 50 μm at x = 0 to 50–70 μm at x = 0.15. More
BSFO-10Eu 689 1.80 importantly, the distance between the particles decreased with
BSFO-15Eu 675 1.84 increasing doping content. The excellent magnetic properties of
BFO are related to its surface structure. The tighter the BFO lattice
system, the more difficult it is for the O and Bi elements to escape.
For a more detailed view of the structural changes, the Raman The elevation in the potential magnetic properties of BFO can be
spectra, which confirm the XRD results, are shown in Figure 2. It is explained by the reduction in the number of oxygen vacancies and
well known that perovskite BFO has nine vibration modes, namely, the helical structure owing to the dense surface structure. TEM
four strong peaks (A1-1, A1-2, A1-3, and A1-4 modes) and six weak image of BSFO–15Eu nanoparticles are shown in Figures 3E,F. It is
peaks (E-2, E-3, E-4, E-5, E-6, and E-7 modes) [26]. It is obvious evident from TEM images that the crystallinity of the sample was
from the Raman results that with the addition of Eu, the peak of the very good and clear diffraction spots can be seen, and the diffraction
main vibration mode of the perovskite structure gradually weakened. patterns of these spots agree well with the orthorhombic phase
In contrast, a new mode at 310 cm−1 became gradually more Pbnm of BFO, which is also consistent with the XRD results. The
pronounced, which was caused by the A-site vibration and the axial direction of the diffraction spot is [1 00].
oxygen sloping of the Pbnm orthorhombic structure [26, 27]. The Figure 4 shows the UV-vis peaks of BSFEO nanoparticles with
Raman results again proved that the Sm and Eu co-doped BFO various doping contents. It is clear that a spectrum shift occurred
system evolved from an R3c to a Pbnm structure. It is noted that for when BSFO was doped with Eu, which increased the band gap.
BSFEO nanoparticles with doping contents of 0.10 and 0.15, the According to the data in Table 1, the cut-off absorption
peak at 310 cm−1 was very pronounced. wavelength of BSFEO nanoparticles in this experiment was
To fully understand the properties and morphological approximately 1.90 nm and the minimum was 1.80 eV. By
characteristics of the Eu and Sm co-doped BFO nanoparticles, comparing the data, it was found that as the doping ratio
SEM images of BSFEO powders with various doping contents are increased, the band gap width decreased. This increase in
shown in Figure 3. It can be seen that the characteristics of band gap may result in improved magnetic and electrocatalytic

TABLE 2 | OER performances of NF and BSFEO coated on NFs.

Sample Onset ηj = 10 mA cm−2 (mV) ηj = 100 mA cm−2 ηj = 400 mA cm−2 Tafel

potential (mV) (mV) slope
(V vs. (mV dec−1)
RHE)

NF 1.48 282 332 366 52

BSFO-5Eu 1.47 276 322 352 43.4
BSFO- 1.47 262 306 328 42
10Eu
BSFO- 1.46 254 295 316 38
15Eu

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Gu et al. Oxygen Evolution Reaction of BiFeO3

FIGURE 5 | N2 adsorption–desorption isotherms and the corresponding pore-size distribution curves (inset) of the as-prepared samples: (A) BSFO-5Eu, (B)
BSFO-10Eu, and (C) BSFO-15Eu. (D) Adsorption effect of methyl orange of BSFO-5Eu.

FIGURE 6 | (A) Polarization curves and (B) corresponding Tafel plots of NF and Bi0.95Sm0.05Fe1−xEuxO3 (x = 0.05, 0.10, 0.15) samples deposited on NFs, with their
digital photos inserted in (A).

performance of the BSFEO nanoparticles. Our results indicate As an important structural parameter, the surface area may
that the BSFEO band gap can be tuned by increasing the doping affect the OER. The specific surface areas of the prepared samples
ratio to increase the range of electrocatalytic and magnetic were determined by N2 adsorption–desorption isotherms. The
properties. isotherms and pore-size distribution curves of the BSFO-5Eu,

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Gu et al. Oxygen Evolution Reaction of BiFeO3

TABLE 3 | Comparison of OER activity for different.

Catalyst Electrolytes ηj = 10 mA cm−2 (mV) Tafel slope Substrate Reference

(mV dec−1)

BiSm0.05Eu0.15FeO3 1.0 m KOH 254 38 Ni foam This work

LaCoO3-80 nm 1.0 m KOH 490 69 GCE [8]
Ba0.5Sr0.5Co0.8Fe0.2O3 1.0 m KOH 500 94 GCE [17]
SrNb0.1Co0.7Fe0.2O3 1.0 m KOH 500 76 GCE [17]
NiFe LDH@NiCoP 1.0 m KOH 220 48.6 Ni foam [18]
NiCo2O4 NPs 1.0 m KOH 240 50 Ni foam [19]
Mn3N2 1.0 m KOH 270 101 Ni foam [20]
CoFe2O4 nanorod array 1.0 m KOH 240 45 Ni foam [21]
CoFe LDHs nanosheets 1.0 m KOH 232 36 Ni foam [22]

FIGURE 7 | Magnetic hysteresis loops of the nanoparticles at RT: (A) BSFO–5Eu, (B) BSFO–10Eu, and (C) BSFO–15Eu. (D) Eu-substituted concentration
dependencies of Mr and Ms.

BSFO-10Eu, and BSFO-15Eu samples are shown in Figure 5. OER superior to that of NF. It is worth noting that the onset
The Brunauer–Emmett–Teller (BET) results demonstrated potential was small at 1.46 V vs. RHE (Figure 6A). To achieve a
that the specific surface areas for the powder samples were current density of 100 mA cm2, the corresponding
2.47, 3.26, and 0.90 m2/g for the BSFO–5Eu, BSFO–10Eu, and overpotentials were 295, 306, 322, and 332 mV for
BSFO–15Eu samples, respectively, indicating that the surface BSFO–15Eu, BSFO–10Eu, BSFO–5Eu and NF, respectively.
area did not directly affect the OER performance. It therefore To achieve a current density of 400 mA cm2, the
seems that the specific surface area did not play a decisive role corresponding required overpotentials were 316, 328, 352,
in OER. However, the average pore size of the three samples and 366 mV for BSFO–15Eu, BSFO–10Eu, BSFO–5Eu, and
were 6.8, 24, and 31 nm for the BSFO–5Eu, BSFO–10Eu, and NF, respectively. Figure 6B shows the corresponding Tafel
BSFO–15Eu samples. Generally speaking, large pores are plots, wherein all BSFEO samples exhibit fast OER kinetics
conducive to the transmission of media in the absence of with extremely small Tafel slopes. In particular, the slope of
stirring. The larger the pore, the more conducive to mass BSFO–15Eu is 38 mV dec−1 and relatively small, indicating that
transfer results in the improvement of OER performance in its OER dynamic process was the fastest and most powerful.
electrocatalysis. Detailed data on OER are shown in Table 2. These results
The OER performance of the Sm and Eu co-doped BFO series suggest that BSFEO possesses excellent OER performance,
was measured via LSV. As shown in Figure 6A, the BSFEO comparable to those of LaCoO3 series [8, 10],
samples all exhibited favorable electrocatalytic activity toward Ba0.5Sr0.5Co0.8Fe0.2O3-δ [28], NiFe-LDH [29], NiCo2O4 [30],

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Gu et al. Oxygen Evolution Reaction of BiFeO3

Mn3N2 [31], CoFe2O4 [32] and CoFe-LDH [33] nanosheets, as response efficiency of OER using a magnetic field as a new
shown in Table 3. regulatory approach has recently attracted widespread
There are two theories about the OER origin of perovskite attention. Ren et al. showed the spin-polarized kinetics of the
ABO3. One is that an oxygen vacancy is the active site, and the OER [37, 38].
other is B-site transition metal ions. In our system, because both
Sm and Eu elements are trivalent, there is no tendency to introduce
oxygen vacancies according to the principle of defect chemical CONCLUSION
equilibrium. In other words, all samples contain the same amount
of oxygen vacancies. Therefore, the transition metal at the B site In summary, BSFEO powders with various doping contents
serves as the active site in our system, and it can be seen from the were synthesized using sol–gel technology. With increasing Eu
above experimental results that Eu or Fe is the active site. The content, the XRD spectra showed that the structure transitioned
specific OER reaction process is as follows: from the R3C phase to the Pnma phase. The diameters of the
Eu-doped particles increased and the distances between them
OH− + M%MOH + e−
significantly decreased. The peak of the Raman spectra at
MOH + OH− %MO + H2 O + e−
136 cm−1 clearly decreased, and the peak at 310 cm−1
MO + OH− %MOOH + e−
significantly increased. The band gap width was in the range
MOOH + OH− %O2 + H2 O + e− + M
of 1.80–2.07 eV. A comparison of the data showed that the Ms
The magnetic hysteresis (M-H) loops of the samples are and Mr values for the Eu-doped samples improved.
shown in Figure 7, where both the remanent magnetization Simultaneously, all the samples exhibited superior OER
(Mr) and saturation magnetization (Ms) increased significantly performance, with a desirable onset potential of
with increasing Eu substitution content. The values of Ms for approximately 1.50 V vs. RHE. For the sample in which x =
BSFO–5Eu, BSFO–10Eu, and BSFO–15Eu were 0.29, 0.31, and 0.15, to support a current density of 100 mA/cm2, an
0.308 emu/g, respectively. The values of Mr for BSFO, BSFO–5Eu, overpotential of only 294 mV was required, which is much
BSFO–10Eu, and BSFO–15Eu were 0.004, 0.021, and 0.0256 emu/ better than that of pure NF (330 mV). The reason and
g, respectively. This comes from the substitution-driven mechanism of OER performance are being systematically
modification of the spiral G-type antiferromagnetic ordering, studied.
which is characteristic of BFO, to the collinear G-type
antiferromagnetic structure, in which the canted component of
the antiferromagnetically ordered spins becomes measurable. DATA AVAILABILITY STATEMENT
That is to say, this enhancement of the ferromagnetism was
attributed to the structural distortion, which modulates the The original contributions presented in the study are included in
canted spin structure and change the Fe–O–Fe angle. It was the article/Supplementary Material, further inquiries can be
expected that this structural distortion could lead to suppression directed to the corresponding authors.
of the spin spiral and hence enhanced the magnetization [12].
Interestingly, double ferromagnetic hysteresis loops were
observed in the Sm and Eu co-doped samples. In particular, AUTHOR CONTRIBUTIONS
the BSFO–10Eu sample had the most obvious double
ferromagnetic hysteresis loop, which is located at the CG and YL implementation of samples preparation; JZ and WZ
coexistence phase of the R3C and Pnma phases. The double implementation of resource and suggestion; WC implementation
ferromagnetic hysteresis loop of BFO systems has rarely been of modifying and editing.
reported or observed. In general, double hysteresis loops are
caused by the coexistence of hard/permanent magnets and soft
magnets or antiferromagnetic and ferromagnetic phases [34–36]. FUNDING
In the Eu and Sm co-doped BFO system, the two different
magnetic phases may be associated with the ferromagnetic This work was supported by the Program for Young Teachers of
Pnma phase and antiferromagnetic R3C phase. Increasing the Higher School in Henan Province (2019GGJS197).

4. Vishwakarma AK, Tripathi P, Srivastava A, Sinha ASK, Srivastava ON.

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Frontiers in Physics | www.frontiersin.org 8 March 2022 | Volume 10 | Article 853179