Role of maze like structure and Y2O3 on Al-based amorphous ribbon surface in MO solution degradation

Article abstract of DOI:10.1016/j.molliq.2020.114318

The Al₈₅Co₁₀Y₅ (Co10) amorphous ribbon exhibits an excellent degradation performance in polluted water treatment for the first time by degrading methyl orange (MO) dye. Compared with the Al₈₅Fe₁₀Y₅ (Fe10) amorphous ribbon for degradation MO solution, the Co10 ribbon has a higher degradation efficiency, a higher TOC removal rate, a lower reaction activation energy, a stronger reusability and a higher corrosion resistance. The Co10 ribbon is not only applicable for acidic MO solution, but also has high degradation efficiency in alkaline MO solution. Compared with the spherical particles on the surface of Fe10 ribbon, the maze like structure on the surface of Co10 ribbon can increase the reaction surface area and improve the degradation efficiency of MO solution. And more [rad]O₂^? radicals by supplying photo catalytic Y₂O₃ under visible light irradiation and then enhance the degradation of MO solution. This work not only provides a new method with high efficiency and low cost for the degradation of MO solution, but also provides a new research direction for the degradation mechanism of Al-based alloys.

Full text of DOI:10.1016/j.molliq.2020.114318

Journal of Molecular Liquids 318 (2020) 114318
Contents lists available at ScienceDirect
Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Role of maze like structure and Y O on Al-based amorphous ribbon
2
3
surface in MO solution degradation
a
a
a
a
b
a,
Qi Chen , Zhicheng Yan , Lingyu Guo , Hao Zhang , Lai-Chang Zhang , Weimin Wang ⁎
a
Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, China
School of Engineering, Edith Cowan University, 270 Joondalup Drive, Joondalup, Perth WA6027, Australia
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 30 June 2020
Received in revised form 9 September 2020
Accepted 12 September 2020
Available online 14 September 2020
The Al85Co10Y5 (Co10) amorphous ribbon exhibits an excellent degradation performance in polluted water treat-
ment for the first time by degrading methyl orange (MO) dye. Compared with the Al85Fe10Y (Fe10) amorphous
5
ribbon for degradation MO solution, the Co10 ribbon has a higher degradation efficiency, a higher TOC removal
rate, a lower reaction activation energy, a stronger reusability and a higher corrosion resistance. The Co10 ribbon
is not only applicable for acidic MO solution, but also has high degradation efficiency in alkaline MO solution.
Compared with the spherical particles on the surface of Fe10 ribbon, the maze like structure on the surface of
Keywords:
Co10 ribbon can increase the reaction surface area and improve the degradation efficiency of MO solution. And
Al-based alloys
Methyl orange dye
Maze like structure
−
more •O
2
radicals by supplying photo catalytic Y
O
2 3
under visible light irradiation and then enhance the degra-
dation of MO solution. This work not only provides a new method with high efficiency and low cost for the deg-
radation of MO solution, but also provides a new research direction for the degradation mechanism of Al-based
alloys.
2 3
Y O
©
2020 Elsevier B.V. All rights reserved.
1
. Introduction
thermodynamic instability, high residual stress and a large number of
unsaturated sites on the surface of amorphous alloy are the reasons
for its excellent degradation performance [40].
Azo dyes have been widely used in textile industry. However, they
have teratogenic and carcinogenic properties, chemical stability and
non-decomposition [1–3]. The treatment of sewage containing this syn-
thetic dye has caused serious environmental problems and has become
one of the major environmental problems in the world [4–7]. In the past
few decades, people have made great efforts to reduce their harmful ef-
fects, including physical adsorption using activated carbon and clay
At present, the amorphous alloys used to catalyze the degradation of
synthetic dyes are mostly ribbon [41–43] and powder shapes
[13,44–47]. Among all the amorphous alloys used for dye degradation,
Al-based amorphous alloys have attracted much attention due to their
low material cost, corrosion resistance, good repeatability and high de-
composition efficiency. Wang et al. studied the degradation of Al91-
[8,9], biodegradation using microorganisms [10], chemical degradation
x 9 x
Ni Y (x = 0, 3, 6 and 9 at.%) metallic ribbons on azo dyes at different
using advanced oxidation processes [11,12] and degradation by specific
alloy [13–17], etc. However, these methods have obvious defects such as
low efficiency, high cost and short service life. Thus, we should actively
explore advanced materials for better degradation of synthetic dyes in
polluted water [18].
Amorphous alloys have attracted more and more attention due to
their unique metastable structure, excellent corrosion resistance and
oxidation resistance [19,20]. At present, there are many researches on
the degradation of azo dyes by amorphous alloy, including Fe-based
pH values [38]. The results showed that the reactivity of Al-based metal-
lic glass in alkaline and acidic azo dye solutions was about 1.5 and 189
times higher than that in neutral solutions, respectively. The low activa-
tion energy and network structure on the surface of Al-based amor-
phous ribbon make it have higher reactivity in acidic and alkaline
solutions, which shows that Al-based amorphous ribbons have good po-
tential in degrading azo dye solutions.
2 3
In recent years, some scholars have studied the ability of Y O -based
materials to degrade organic compounds under visible light irradiation
[
21–29], Mg-based [30–33], Co-based [34–36] and Al-based [37–39]
[48–52]. Karunakaran et al. conducted photocatalytic degradation of
ribbons, powders and nanoporous structures, have been proved to
have good degradation performance in the wastewater for removing
synthetic dyes and organic pollutants. It is generally believed that the
formic, oxalic, acetic and citric acids on the surface of Y
that the order of photodegradation was as follows: formic acid > oxalic
acid > acetic acid > citric acid, indicating that Y has a good degrada-
tion performance for organic compounds [53]. Magdalane et al. synthe-
sized CeO /Y materials with layered nanostructures by chemical
precipitation assisted hydrothermal method, and generated reactive
2 3
O and found
2 3
O
2
2 3
O
⁎
Corresponding author.
E-mail address: weiminw@sdu.edu.cn (W. Wang).
https://doi.org/10.1016/j.molliq.2020.114318
167-7322/© 2020 Elsevier B.V. All rights reserved.
0

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
1
oxygen species with organic dye degradation performance under visible
(1.0 g L− if not noted) was added to the solution, upon visible light ir-
−1
light. As CeO
one-dimensional nanostructures that can increase the reaction surface
areas, the CeO /Y shows higher photocatalytic performance in the
/Y O
2 2 3
binary metal oxide nanostructure has hierarchical
radiation, the solution was stirred at a fixed speed (200 r min ) during
the degradation process, and the temperature (298 K if not noted) of the
solution was maintained using a water bath. The initial pH (pH = 1 if
2
2 3
O
−1
degradation of Rhodamine-B dye [54]. The role of transition metals of
Al-based glasses in the glass formation and dye degradation is still un-
clear and valuable to be further studied.
not noted) of the solution was adjusted using 12 mol L HCl, as well
as 1 M NaOH. At selected time intervals, 3 mL of the solution was ex-
tracted using a syringe and filtered with a 0.45 μm membrane, and the
concentration of real-time MO solution was monitored using a UV–Vis
spectrophotometer (UV-4802) to obtain the absorbance spectrum of
the solution. For cyclic tests, the ribbons were extracted from the solu-
tion after each degradation test and stir washed with deionized water
for 60 s before putting them into the next reaction batch.
In this paper, we report the degradation of synthetic dyes by using
Al85Co10
dation processes using Al85Fe10
Y
5
(Co10) amorphous ribbon for the first time, and the degra-
(Fe10) amorphous ribbon are investi-
Y
5
gated for comparison. Methyl orange (MO) is a common synthetic dye
used for acid-base titration indicator and dyeing textile, and is used as
degradation object in this paper. Through cyclic tests, it is revealed
that Co10 ribbon has a longer service life than Fe10 ribbon. The Co10
amorphous ribbons have high degradation efficiency and reusability
when degrading MO solution, and degradation pathways under acidic
and alkaline conditions have been investigated. Our research not only
provides a new research idea for polluted water treatment, but also ex-
tends the application field of Al-based amorphous alloy.
2
.4. Electrochemical tests
The electrochemical properties including polarization curves and
impedance spectra (EIS) were measured using an electrochemical mea-
suring instrument (CHI 660E) in the 25 mL DW or MO solutions
−
1
(
10 mg L MO) at 298 K. The three-electrode cell was used for mea-
surement, with saturated calomel electrode (SCE) as reference elec-
trode, platinum as counter electrode and as-spun ribbon as working
electrode. The polarization curves were recorded at a potential sweep
speed of 1 mV s after the open circuit potentials were stabilized. EIS
was conducted under static states with scanning frequencies from
2
. Experimental
−1
2.1. Materials and reagent
5
The alloy ingots with nominal compositions of Al85Fe10Y (Fe10, at.
1
00 kHz to 0.01 Hz and the amplitude was ± 10 mV.
%
5
) and Al85Co10Y (Co10, at.%) were prepared by arc melting of high-
purity (99.5 wt%–99.9 wt%) Al, Fe, Co and Y metals in an arc melting sys-
3
. Results
−3
tem, which was vacuumed to 5 × 10 Pa first and then filled with pu-
rified argon (99.999%). Ribbons with a thickness of ~20 μm and a width
of ~2 mm were prepared in a single roller melt-spinning system in the
5
3.1. Microstructure of Al85(Fe/Co)10Y amorphous ribbons
−1
air, with a speed of 44 m s . The ribbons were cut into 5 cm long strips
for degradation tests. The ribbons were then annealed at 579 K (Fe10)
and 550 K (Co10) in Ar atmosphere. Commercially available methyl or-
A. XRD and DSC analysis
ange (MO, C14
H
14
N
3
NaO
3
S, AR grade) was purchased from Tianjin
Fig. 1 shows the XRD patterns and DSC curves of as-spun Al85Fe10
Y
5
Tianxin Fine Chemical Development Center. Hydrochloric acid (HCl,
AR grade) was purchased from Sinopharm Chemical Reagent Co., Ltd.
Sodium hydroxide (NaOH, AR grade) was purchased from Tianjin
Hengxing Chemical Reagent Manufacturing Co., Ltd. 1,4-benzoquinone
(Fe10) and Al85Co10 (Co10) ribbons. For comparison, the XRD pat-
Y
5
terns of the annealed Fe10 and Co10 ribbons at 579 K and 550 K for
5 min are added. Here the annealed temperature is 30 K below the crys-
tallization peak TP1 in DSC curves. As shown in Fig. 1(a) the XRD pattern
of as-spun Fe10 ribbon has only a typical diffuse scattering peak at about
2θ = 40 degree, indicating that the as-spun Fe10 ribbon owns a fully
amorphous structure. This diffuse scattering peak can be decomposed
into P1 and P2 peaks and the area fraction AP2/(AP1 + AP2) of P2 is
40%. The crystalline peaks in the XRD pattern of annealed Fe10 ribbon
(
BQ, C
Technology Co., Ltd. Tertiary butanol (TBA, C
chased from Sinopharm Chemical Reagent Co., Ltd.
6
H
4
O
2
, CP grade) was purchased from Shanghai dingfen Chemical
4
H10O, CP grade) was pur-
2.2. Characterization
2 2
can be identified as α-Al, Al Fe and Fe Y crystalline phases, indicating
The amorphous structure of the as-spun ribbons was characterized
the ribbon experiences the crystallization transformation in annealing.
by X-ray diffraction (XRD, Bruker D8 Discover) with Cu-Kα radiation
and transmission electron microscopy (TEM, JEM-2100). The amor-
phous structure of the ribbons was also certified by differential scanning
calorimetry (DSC, NETZSCH-404) at a heating rate of 20 K/min. The sur-
face morphology of the ribbons was observed using a scanning electron
microscope (SEM, JSM-7800F) equipped with an energy dispersive X-
ray spectrometer (EDS). The binding states of elements on the surfaces
of the as-spun and reacted Fe10 and Co10 ribbons were investigated by
X-ray photoelectron spectroscopy (XPS, AXIS Supra) with a monochro-
matic Al Kα X-ray source (hv = 1486.6 eV). The total organic carbon
Apparently, the P1 is locating at the position of Al (111) peak and
P2 at the position of Fe Y (222) peak. Based on the heredity between
2
the amorphous state and the crystalline state [55], the decomposed P1
in Fig. 1(a) is associated with A l\ \Al clusters, and P2 with Fe\\Y clusters.
The as-spun Co10 ribbon also has a typical diffuse scattering peak,
which can also be decomposed into P1 and P2 peaks (Fig. 1(b)). In addi-
tion, the area fraction AP2/(AP1 + AP2) of P2 is 27.6%, which is lower than
40% for as-spun Fe10 ribbon. Moreover, P1 stands at the left side of Al
(111), while P2 locates at the same position of P2 in as-spun Fe10 ribbon
2
XRD pattern, i.e., the position of Co Y (222) peak. Hence, the P1 repre-
(
TOC) of the MO solution was determined with a TOC-L analyzer. The
sents A l\ \Al and A l\ \Y clusters, and P2 represents Co\\Y clusters. The
XRD pattern of annealed Co10 ribbon still has diffuse scattering peak
at 38 degree, indicating that a fully amorphous structure after anneal-
ing. Moreover, the position of main peak in annealed Co10 ribbon is cor-
responding to Al (111) peak and the corresponding atomic distance is
shorter than is as-spun state, which may be ascribed to the oxidation
of the abundant Y atoms in A l\ \Y clusters in annealing. Nevertheless,
at the temperature below crystallization, the as-spun Co10 ribbon is
more stable than the as-spun Fe10 ribbon.
specific surface area (SSA) of the as-spun and reacted Fe10 and Co10
ribbons were measured by surface area and porosimetry analyzer (V-
Sorb 2800P).
2
.3. Degradation tests
First, 500 mL MO solution (10 mg L− MO if not noted) has been pre-
1
pared in a volumetric flask using deionized water (DW) and MO pow-
ders. Then, 50 mL MO solution was poured in a 100 mL beaker in
preparation of the degradation test. A specific amount of ribbons
Fig. 1(c) shows the DSC curves of as-spun Fe10 and Co10 ribbons. In
the DSC curve of Fe10 ribbon, there are three crystallization peaks TP1
,
2

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
Fig. 1. XRD patterns of the as-spun and annealed (a) Al85Fe10
Y
5
(Fe10) and (b) Al85Co10
Y
5
(Co10) ribbons, (c) the DSC curves of the as-spun Fe10 and Co10 ribbons.
T
P2 and TP3 in the heating scan, the TP3-TP1 is 217 K, indicates a wide
508 nm, as shown in Fig. 3(c). In reacting with both ribbons, the solution
crystallization temperature range and a heterogeneous structure in
the as-spun Fe10 ribbon, this is consistent with the high P2 area fraction
decomposed from the main peak in its XRD pattern. The crystallization
peaks in the XRD pattern of Fe10 ribbon annealed at 30 K below crystal-
lization peak temperature also confirm the heterogeneous structure of
Fe10 ribbon. In the DSC curve of Co10 ribbon, there are two crystalliza-
tion peaks TP1 and TP2, the crystallization range is much shorter than
concentration stays almost unchanged during the first 5 min, and then
declines rapidly. With increasing t , the absorption peak at 508 nm de-
r
cays gradually, suggesting that the chromophore groups of MO disap-
pear gradually. The degradation kinetics after the first 5 min are
usually described by the pseudo-first-order equation as follows [58]:
Ct ¼ C0 expð−ktrÞ
ð1Þ
Fe10 ribbon. The exothermic heat △H
C
of the crystallization of Co10 rib-
where k is the reaction rate constant (min−1), C
is the initial concentra-
0
bon is higher than the △H of Fe10 ribbon, indicating that the as-spun
C
−1
t
tion of MO solution (mg L ), and C is the instant concentration of MO
Co10 ribbon has the glass formability, stability and homogeneity,
which are higher than Fe10 ribbon and these characteristics are consis-
tent with the XRD patterns (Fig. 1(a) and (b)).
−1
solution (mg L ) at t
be derived as follows:
r
. Then the degradation reaction rate constant can
ꢀ
ꢁ
C0
Ct
B. TEM investigation
k ¼ ln
=tr
ð2Þ
In order to further characterize the microstructure and morphology
of the as-spun Fe10 and Co10 ribbons, we carried out TEM investiga-
tions, which are shown in Fig. 2. There is mainly maze shape pattern
without crystallites in the high resolution bright field images of the
as-spun Fe10 and Co10 ribbons (Fig. 2(a) and (b)). Here, the amount
of the ordered zone in diameter of 20 Å in Fe10 ribbon inside the circle
is higher than in Co10 ribbon. The corresponding SAED patterns have
two typical diffraction halos (Fig. 2(c) and (d)), confirming that the
as-spun Fe10 and Co10 ribbons own a fully amorphous structure. And
the light intensity of the inner diffraction halo in the as-spun Fe10 and
Co10 ribbons can be decomposed into P1 and P2 peaks (inset in Fig. 2
According to the ln (C
0 t r
/C ) − t curves shown in Fig. 3(d), the reac-
tion rate constant of Co10 ribbon in this degradation reaction is
−1
−1
0
.069 min , which is larger than 0.049 min for Fe10 ribbon, with
2
the goodness of fit R being 0.96 and 0.97, respectively. Thus, the as-
spun Co10 ribbon exhibit a higher degradation ability for MO solution
with pH = 1 than the as-spun Fe10 ribbon.
In order to further analyze the mineralization of MO solution during
degradation with as-spun Fe10 and Co10 ribbons, their TOC removal
rates are shown in Fig. 3(e). It is observed that the mineralization rate
of as-spun Co10 (82.4%) ribbon for MO solution is higher than that of
as-spun Fe10 (75.1%) ribbon at 45 min, which is corresponding to the
degradation efficiency of as-spun Co10 (94.4%) and Fe10 (86.7%) rib-
bons for MO solution in Fig. 3(c). However, the mineralization rate of
as-spun Fe10 and Co10 ribbons for MO solution is lower than the corre-
sponding degradation efficiency, which is due to the fact that in the pro-
cess of degradation and mineralization, the degrading radicals first
attack the chromophoric groups and make the MO solution decolorize
quickly. Afterward, the initial degradation products are generated,
(
c) and (d)). Here, the P2 area fraction of the as-spun Fe10 ribbon is
higher than that of Co ribbon. Thus, the results of TEM are agreeing
with the XRD patterns (Fig. 1(a) and (b)). Hence, the P1 and P2 peaks
in SAED of Fe10 ribbon represent Al\\Al and Fe\\Y clusters, respec-
tively. The P1 of Co10 ribbon represents A l\ \Al and A l\ \Y clusters and
P2 stands for Co\\Y clusters. The TEM bright field images and light in-
tensities of SAED patterns also indicate that the homogenous degree
of the as-spun Co10 ribbon is higher than Fe10 ribbon.
which are further mineralized into the final products as H
2
O, CO
2
,
−
2−
NO and SO . Thus, completing mineralization process takes longer
3 4
5
3.2. Degradation performance of Al85(Fe/Co)10Y amorphous ribbons
time than degradation [24].
Fig. 3(f) shows the MO dye equilibrium dark adsorption on as-spun
Fe10 and Co10 ribbons at pH = 7 and MO solution concentration of
A. UV–Vis absorbance analysis and degradation performance
−
1
1
0 mg L . The quantity of adsorption q (mg/g) of the MO dye is
The UV–Vis absorbance spectra of the filtered methyl orange (MO)
solution with pH = 1 after processing with as-spun Fe10 and Co10 rib-
shown as the following equation [26]:
q ¼ ðC0−CtÞV=M
ð3Þ
is the
r
bons for a series of time intervals (t = 0– 45 min) are presented in Fig. 3
is the initial concentration of MO solution (mg L−1), C
(
a) and (b). The spectra of MO solution have a major absorption peak at
where C
0
t
−1
about 508 nm, which represents MO chromophore group,
i.e., nitrogen‑nitrogen double bond (-N=N-) [56,57]. The normalized
concentration of the MO solution is obtained with the peak values at
instant concentration of MO solution (mg L ) at t , V is the volume of
r
the MO solution (L) and M is the mass of as-spun Fe10 and Co10 ribbons
(g). Fast MO dye adsorption is observed on as-spun Fe10 and Co10
3

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
(
(
a)
(b)
5
nm
5 nm
P1
P2
P1
c)
(d)
P2
A
B
A
B
Reciprocal distance
Reciprocal distance
A
B
A
B
5
nm
5 nm
5 5
Fig. 2. The TEM images of the as-spun (a) Al85Fe10Y (Fe10) and (b) Al85Co10Y (Co10) ribbons, the SAED patterns of the as-spun (c) Fe10 and (d) Co10 ribbons. The insets in (c) and (d):
light intensity of SAED patterns along AB line.
ribbons from initial q = 0 to q = 0.31 and 0.40 mg/g at t
followed by slower equilibrium adsorption with q = 0.47 and
.56 mg/g at t = 45 min, respectively. In the degrading process, the
MO dye molecules are initially adsorbed on the as-spun Fe10 and
Co10 ribbon surfaces, and then are further degraded and mineralized.
The q of the as-spun Co10 ribbon for MO dye is higher than that of as-
spun Fe10 ribbon. Thus, from the q, we think that as-spun Co10 ribbon
is more conducive to degradate and mineralize the MO solution than
the as-spun Fe10 ribbon.
r
= 15 min
Co10 ribbon. The specific surface areas (SSA) of the as-spun Fe10 and
Co10 ribbons are basically the same (Table 1), which corresponds to
the typical smooth surface in SEM images (Fig. 4(a) and (b)). After the
reaction, the specific surface areas of Fe10 and Co10 ribbons increased
0
r
2
to 0.131 and 0.172 m /g, which was related to the round corroding
spots formed on the surface of Fe10 ribbon and the maze like network
structure formed on the surface of Co10 ribbon (Fig. 4(c) and (d)), re-
spectively. In other words, the network structure on the surface of
Co10 ribbon greatly increased its specific surface area and provided
more reactive sites for the degradation of MO solution, and thus improv-
ing the degradation efficiency.
B. SEM images of surface morphology
C. XPS analysis
To understand the MO degradation process with Al-based amor-
phous ribbons, it is very important to study the structure evolution of
the ribbon surfaces after the reaction. The SEM images on the surface
of the as-spun and reacted Fe10 and Co10 ribbons are displayed in
Fig. 4, the EDS and specific surface area (SSA) results are listed in
Table 1. A typical smooth surface of amorphous ribbons is observed on
the as-spun Fe10 and Co10 ribbons (Fig. 4(a) and (b)). After reacting
with MO solution the Fe10 ribbon surface has many round corroding
spots, which are related to the A l\ \Al cluster (Fig. 4(c)). After the reac-
tion, the Co10 ribbon surface has a maze like network structure, shows a
spinodal decomposed characteristic (Fig. 4(d)). After reaction for
It is known that the surface elements especially their electronic
structure of an amorphous ribbon have a great influence on the degra-
dation efficiency. Figs. 5 and 6 show the XPS analysis on the surface of
the as-spun and reacted Fe10 and Co10 ribbons to measure Al 2p, Fe
2p3/2, Co 2p3/2, Y 3d and O 1s, and the XPS parameters are listed in
Table 2.
In Fig. 5(a), the Al 2p spectra of as-spun Fe10 ribbon can be
deconvoluted into 3 peaks P1, P2 and P3 at 72.8, 74.9 and 76.0 eV,
which are assigned to the metallic Al , Al
[59]. Similar to the as-spun Fe10 ribbon, the Al , Al
0
2
O
3
and Al(OH)
3
, respectively
and Al(OH)
3
0
4
5 min, the Fe10 and Co10 ribbons have decreased cAl and c
creased cFe and cCo (Table 1). After degradation, the c increment in Fe10
ribbon surface is apparently larger than that in Co10 ribbon surface.
Moreover, the c of Fe10 ribbon before and after degradation is higher
than that of Co10 ribbon, indicating a lower anti-oxidation ability than
Y
, and an in-
2
O
3
O
peaks of the reacted Fe10 ribbon locate at 72.6, 75.1 and 76.1 eV, respec-
tively. Generally, the area of each peak is related to the relative content
of element in the sample. The fraction of Al peak on the surface of the
0
O
as-spun Fe10 ribbon is about 45.8% of the total Al 2p spectrum, and
4

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
(
a)
Fe10
(b)
Co10
0 min
5 min
1
1
0
0
.5
.0
.5
1.5
1.0
0.5
0.0
0
5
1
1
2
2
3
min
min
0 min
5 min
0 min
5 min
0 min
10 min
15 min
20 min
25 min
30 min
35 min
40 min
45 min
35 min
4
4
0 min
5 min
.0
4
00
450
500
550
600
400
450
500
550
600
Wavelength (nm)
Wavelength (nm)
3
2
1
0
(
c)
(
d)
1
0
0
0
0
0
.0
Fe10
Fitting
Co10
k
k
= 0.049 min-1
= 0.069 min-1
.8
.6
.4
.2
.0
Fe10
Co10
Fitting
0
10
20
30
40
0
10
20
30
40
tr
(min)
t
r (min)
0
.6
(
e)
(f)
8
6
4
2
0
0
0
0
0
0.4
Fe10
Co10
0
0
.2
.0
Fe10
Co10
0
10
20
30
40
0
10
20
30
40
t
r
(min)
tr (min)
Fig. 3. UV–Vis absorbance spectra of the as-spun (a) Al85Fe10
Y
5
5 r
(Fe10) and (b) Al85Co10Y (Co10) ribbons after reacted with MO solution with time t = 0– 45 min, (c) normalized
concentration change of MO solutions during the degradation process, (d) the ln (C
0
/C )-t
t
r
curves for the as-spun Fe10 and Co10 ribbons, (e) TOC removal rate of MO solution during
the degradation process, (f) quantity of MO dye adsorption on as-spun Fe10 and Co10 ribbons.
decreases to 29.7% after degradation, indicating that α-Al phase precip-
itates from the amorphous matrix and dissolves in the degradation of
MO solution. In Fig. 5(b) both of the Fe 2p3/2 spectra from the as-spun
Fe10 ribbons consist of 3 peaks P1, P2 and P3 at 707.3, 709.5 and
consists of 2 peaks P1 and P2 at 529.8 and 531.1 eV, respectively. After
reaction, P1 and P2 locate at 529.8 and 531.1 eV. Here, P1 and P2 are
assigned to the Y
area of the as-spun Fe10 ribbon is about 35.6%, and decreases to 27.5%
after degradation. This result indicates that Y is continuously con-
2 3 2 3
O and Al O , respectively [63]. The fraction of P1
7
7
12.0 eV, with P1, P2 and P3 from the reacted Fe10 ribbon at 707.5,
09.3 and 711.3 eV, respectively. According to Ref [60], P1, P2 and P3
2 3
O
sumed during degradation, which is consistent with the result in Fig. 5
(c).
0
2+
3+
are assigned to the metallic state Fe , oxidized Fe and Fe ions, re-
spectively. The Fe /Fetotal area ratio of the as-spun ribbon decreases
0
The electronic structure of the as-spun and reacted Co10 ribbons is
also obtained using XPS for comparison as shown in Fig. 6. Contrast to
from 67.2% to 58.4% after degradation. Meanwhile, the absolute area
0
0
of Fe in reacted Fe10 ribbon is much higher than as-spun Fe10 ribbon.
the as-spun and reacted Fe10 ribbons, in Fig. 6(a) the Al /Altotal area
The Y 3d spectrum exhibits a doublet due to the spin-orbit splitting
ratio of the as-spun Co10 ribbon is 37.5%, and decreases to 37.0% after
reaction. It indicates that the oxide film on the surface of the Co10 rib-
bon has been thinned in the reaction of degrading MO solution. Similar
into Y 3d5/2 and Y 3d3/2, and both Y0 and Y
[
O
have 3d5/2 and 3d3/2
61,62]. In Fig. 5(c) both of the Y 3d spectra from the as-spun Fe10 rib-
bons consist of 4 peaks P1, P2, P3 and P4 at 154.7, 156.9, 157.9 and
2
3
0
to the Fe peak in the as-spun and reacted Fe10 ribbon, the absolute area
0
1
1
59.7 eV, with P1, P2, P3 and P4 from reacted Fe10 ribbon at 154.6,
56.8, 157.7 and 159.7 eV, respectively. And the P1, P2, P3 and P4 are
of Co of Co10 ribbon increases apparently after reaction (Fig. 6(b)),
confirming the thinning of oxide film in the reaction.
0
0
assigned to Y 3d5/2, Y 3d3/2, Y
O
2 3
3d5/2 and Y
2
O
3
3d3/2, respectively.
2 3
In Fig. 6(c), similar to the Fe10 ribbon, the content of Y O on Co10
0
The area fraction of Y peaks for as-spun ribbon is 3.7% and increases
to 44.8% after reaction. This is because the Y
ions in the MO solution, which exposes the Y on the ribbon surface.
In Fig. 5(d), the O 1s spectrum of the as-spun Fe10 ribbon surface
ribbon surface decreased from 95.7% to 47.3% in the degradation of
+
0
2
O
3
is consumed by H
MO solution, while the content of Y increased from 4.3% to 52.7%. Com-
0
pared with the Fe10 ribbon, Co10 ribbon has a higher consumption of
Y O exposed during the reaction with MO solution. In Fig. 6(d), unlike
2 3
5

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
(
a)
(b)
1
1
μm
μm
1 μm
(c)
(d)
1 μm
2
00 nm
200 nm
Fig. 4. SEM micrographs of (a) the as-spun Al85Fe10
Y
5
(Fe10) ribbon, (b) the as-spun Al85Co10
Y
5
(Co10) ribbon, (c) reacted Fe10 ribbon and (d) reacted Co10 ribbon. The insets in (c) and
(d): the high-magnification images.
Fe10 ribbon, the area fraction of Y
9.8%, and increases to 38.1% after degradation. Meanwhile, the fraction
of Al peak decreases from 70.2% to 61.9%. However, according to the
peak of Al 2p spectra of Co10 ribbon decomposition before and after the
reaction, the content of Al did not change much. The increase of Y
2
O
3
peak of the as-spun Co10 ribbon is
In both DW and MO solutions (Fig. 7(c) and (d)), the Nyquist semi-
2
circle diameter of the as-spun Co10 ribbon is larger than that of Fe10
ribbon. The equivalent circuit consisting of R(C(R(Q(R(CR))))) is used
to fit the EIS data in DW and MO solution. In the equivalent circuit, the
constant phase element (CPE) Q is defined as [64]:
2 3
O
O
2 3
2 3
O
content was probably due to the increase of surface area supplied by the
network structure of Co10 ribbon surface.
−
n
Q ¼ ðjwÞ =Y0
ð4Þ
D. Electrochemical analysis.
The polarization curves and electrochemical impedance spectra
The fitting results like resistances of solution (R
s
), charge transfer
(
EIS) of the as-spun Fe10 and Co10 ribbons in DW and MO solutions
with pH = 1 were shown in Fig. 7. In DW, the corrosion potential
corr) of the as-spun Co10 ribbon is −0.87 V (Fig. 7(a)), which is higher
than Fe10 ribbon (−0.97 V). Besides, the corrosion current densities
(R
double layer (Cdl) and reaction (C
summarized in Table 3. Both ribbons in MO solution have lower R
, and higher Cdl, Y , R , C and Rtotal than in DW, which may be due to a
t
), film (R
f
), reaction (R
a
) and total circuit (Rtotal), capacities of electric
), and CPE parameters (Y and N ) are
and
a
f
f
(E
s
R
t
f
f
a
−6
−2
+
(i
corr) of Co10 ribbon is 1.76 × 10 A cm , being lower than Fe10 rib-
certain amount of methyl orange molecules and H in MO solution.
Moreover, the Rtotal of Co10 ribbon is higher than that of Fe10 ribbon
in both DW and MO solution. Thus, the EIS results are also in good
agreement with the results of polarization curves (Fig. 7(a) and (b)).
−6
−2
bon (2.64 × 10 A cm ). In MO solution, the Ecorr value of the as-spun
Co10 ribbon is −0.54 V (Fig. 7(b)), being higher than Fe10 ribbon
−5
−2
(−0.70 V); in addition, the icorr of Co10 ribbon is 1.55 × 10 A cm
,
−5
−2
which is lower than Fe10 ribbon (1.81 × 10 A cm ). In addition, as
f
In MO solution, the Co10 ribbon has a higher Cdl and N than Fe10 rib-
E = 0 V vs SCE, the pitting curve of Fe10 ribbon in DW can be divided
bon, indicating that on Co10 ribbon surface area is larger than Fe10 rib-
bon surface.
1
2
into two stages (denoted E
P
and E
P
), while that of Co10 ribbon has one
1
stage started at E
P
. Similar phenomenon occurs in MO solution. These
polarization curves indicate that the as-spun Co10 ribbon has a higher
corrosion resistance than as-spun Fe10 ribbon in DW and MO solution,
and confirm that the as-spun Co10 ribbon has a more stable and homog-
enous structure than Fe10 ribbon.
3.3. Effect of temperature, pH on ribbon's degradation and reusability
A. Effect of temperature
In order to further compare the MO solution degradation efficiency
of the as-spun Fe10 and Co10 ribbons, both ribbons reacted with MO so-
lution at different temperatures (T
k and thermal activation energy E
r
), as shown in Fig. 8. And we deduced
of MO solution degradation. The re-
Table 1
5 5
EDS and specific surface area (SSA) analysis of the Al85Fe10Y (Fe10) and Al85Co10Y
r
(
Co10) ribbons before and after degradation.
action conditions are set as follows: initial pH = 1, ribbon dosage
−1
−1
0
.5 g L , and CMO = 10 mg L . The normalized MO solution concen-
tration C /C shows that temperature has a positive effect on the degra-
dation process, as the degradation process takes less time with a
increasing T (Fig. 8(a) and (b)). Meanwhile, the k of the Fe10 and
Co10 ribbons increases with T (Fig. 8(c)). Since k (T ) is dependent on
, the thermal activation energy E of the MO solution degradation
Alloy Before degradation
After degradation
t
0
c
Al
c
Fe
c
Co
c
Y
c
O
SSA
c
Al
c
Fe
c
Co
c
Y
c
O
SSA
(m /g)
2
2
(m /g)
r
Fe10 77.7 14.9
Co10 78.3
–
5.4 2.0 0.111
76.6 15.5
–
5.0 2.9 0.131
r
r
–
14.3 5.5 1.9 0.117
78.1 14.6 5.1 2.2 0.172
–
T
r
r
6

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
before degradation
before degradation
b)Fe 2p3/2
Fe0
(
a)0 Al 2p
Al
(
Al2
O
3
2+
Fe
Al(OH)
3
P1
P1
P2
3+
Fe
P3
P3
P2
after degradation
after degradation
7
8
76
74
72
714
712
710
708
706
Binding Energy (eV)
Binding Energy (eV)
before degradation
before degradation
P1
(
c)Y 3d
(d)O 1s
P3
P2
Y
2
O
3
P4
Al2
O
3
P1
P2
0
after degradation
after degradation
Y
3d5/2
0
Y
Y
Y
3d3/2
3d5/2
3d3/2
2
2
O
O
3
3
1
62
160
158
156
154
534
532
530
528
Binding Energy (eV)
Binding Energy (eV)
5
Fig. 5. XPS spectra of (a) Al 2p, (b) Fe 2p3/2, (c) Y 3d and (d) O 1s in binding energy regions for the Al85Fe10Y (Fe10) ribbons before and after degradation.
reaction with Fe10 and Co10 ribbons can be deduced through the
Arrhenius-type equation [22]:
(84.3%) and Co10 (91.5%) ribbons is still lower than the η of their coun-
terparts at pH =1 (Fig. 9(c) and (d)). The deduced η values of both rib-
bons at various pH also suggest that the degradation efficiency of Co10
ribbon is higher than Fe10 ribbon.
Er
RTr
lnkðTrÞ ¼ −
þ lnA
ð5Þ
C. Reusability and stability of Fe10 and Co10 in degradation MO
solution
where R is the gas constant and A is a constant. According to lnk(T
r
)
vs − 1/RT curves (inset in Fig. 8(c)), the E values of Fe10 and Co10 rib-
r
r
−
1
The reusability and stability of amorphous ribbon are important in-
dexes to evaluate the potential of polluted water remediation. We
tested the degradation efficiency η of the Fe10 and Co10 ribbons in
MO solution with pH = 1 by reusability test as shown in Fig. 10. The η
of the Fe10 ribbon in MO solution, increases gradually from the 1st to
bons are 23.8 and 21.3 KJ mol , respectively, being opposite to the
varying tendency of their k at 298 K (Fig. 8(d)) and indicating that
Co10 ribbon has a better performance in the MO degradation reaction.
B. Effect of pH
3
rd cycle, and decreases gradually from the 4th to 7th cycle (Fig. 10
Fig. 9 shows the pH effect on the degradation ability of the as-spun
Fe10 and Co10 ribbons against MO solution, with other reaction condi-
tions unchanged. When pH increases from 1 to 5, the degraded MO con-
(a) and (b)). The η variation of Co10 ribbon from the 1st to 3rd cycle
is similar to that of Fe10 ribbon, but the η in the 4th cycle decreased to
the lowest value, and then increased gradually from the 5th to 7th
cycle, showing a better reusability than Fe10 ribbon (Fig. 10(c) and
(d)). It can be noted that the η of the Fe10 and Co10 ribbons in the
2nd and 3rd degradation cycle is higher than in the 1st cycle (Fig. 10
centration C
However, as pH rises from 5 to 9, the C
changed, i.e., it is basically not degraded. As pH rise from 9 to 13, the C
of MO solution drastically increases, indicating that the degradation
t
/C
0
by the as-spun Fe10 ribbon drastically decreases.
t
/C of MO solution is basically un-
0
t
/
C
0
t 0
(b) and (d)). And normalized concentration C /C of the solution
effect of Fe10 ribbon is enhanced again (Fig. 9(a)). Meanwhile, similar
to the as-spun Fe10 ribbon, the as-spun Co10 ribbon has a similar MO
solution degrading behavior as pH increases from 1 to 13 (Fig. 9(b)).
reacting with both kinds of ribbons stays almost unchanged during
the first 5 min (Fig. 10(a) and (c)). This may be because it takes certain
time to consume the thin oxide layer on the ribbon during the 1st test,
while the 2nd and 3rd runs can react with the truly fresh surfaces of
the Fe10 and Co10 ribbons.
The degradation efficiency (η = (1- C
as-spun Fe10 and Co10 ribbons with T
are shown in Fig. 9(c) and (d). As pH = 1, the η of the as-spun Fe10
86.7%) and Co10 (94.4%) ribbons is maximum. As pH rises from 5 to
, the η of the as-spun Fe10 and Co10 ribbons is basically zero, respec-
t 0 r
/C × 100%, t = 45 min) of the
r
= 298 K at different pH values
(
9
4. Discussion
tively. As pH rises from 9 to 13, the η of the as-spun Fe10 and Co10 rib-
bons is drastically increases. As pH = 13, the η of the as-spun Fe10
Under different pH conditions, the degradation efficiency and degra-
dation mechanism of the as-spun Al85Fe10Y (Fe10) and Al85Co10Y
5 5
7

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
before degradation
before degradation
Co 2p3/2
(
a) Al 2p
Al
(b)
0
0
Co
Al
Al(OH)
2
O
3
2+
3+
P2
Co
Co
P1
3
P1
P3
P2
P3
after degradation
after degradation
7
8
76
74
72
784
782
780
778
776
Binding Energy (eV)
Binding Energy (eV)
before degradation
before degradation
(
c)Y 3d
(d)O 1s
P3
P2
Y
2
O
3
P4
Al2
O
3
P1
P1
P2
after degradation
0
after degradation
Y
3d5/2
0
Y
Y
Y
3d3/2
3d5/2
3d3/2
2
O
3
3
2O
1
62
160
158
156
154
534
532
530
528
Binding Energy (eV)
Binding Energy (eV)
5
Fig. 6. XPS spectra of (a) Al 2p, (b) Co 2p3/2, (c) Y 3d and (d) O 1s in binding energy regions for the Al85Co10Y (Co10) ribbons before and after degradation.
(
Co10) ribbons in MO solution are different. As pH ≤ 3, hydrogen ions
low to effectively react and produce [H] or •OH radicals. When pH =
+
are dominant in MO solution. The H ions can react with Al or other
metals on the ribbon surface to produce the reduced initial hydrogen
1, there exists a transient platform before degradation of MO solution;
while in the condition of pH = 13, there doesn't exist any transient plat-
form (Fig. 9(a) and (b)). It is due to the fact that oxides on the surface of
[H] radicals, which have certain reducibility and can degrade MO solu-
−
−
tion [65–69]. As pH ≥ 11, the dominant OH ions can react with Al
the as-spun Fe10 and Co10 ribbons are easier to react with OH , which
and other metals on the surface of the ribbon to produce hydroxyl
can accelerate the degradation rate. However, when the reaction had
lasted for 30 min, the degradation rate of pH = 13 was gradually de-
creased and became lower than that of pH =1 (Fig. 9(a) and (b)),
which should be due to the decrease of OH in the solution and the de-
crease of the rate of generating •OH radical.
•
OH radicals, which have strong oxidibility and can degrade MO solution
69,70]. However, in the condition where 5 ≤ pH ≤ 9, MO solution is
more stable and does not undergo any degradation, which may be due
[
−
+
−
to the fact that the concentration of H or OH in MO solution is too
Table 2
XPS analysis of the Al 2p, Fe 2p3/2, Co 2p3/2, Y 3d and O 1s of the Al85Fe10
Y
5
5
(Fe10) and Al85Co10Y (Co10) ribbons before degradation (BD) and after degradation (AD).
Alloy
Fe10
Spectrum
P1
A
P2
A
P3
A
P4
A
%
%
%
%
BD
AD
BD
AD
Al 2p
Fe 2p3/2
Y 3d
13,522
45.8
67.2
1.9
11,638
1803
39.4
21.7
1.8
4378
921
61,910
–
5912
3619
4377
–
5997
596
63,133
–
7190
4783
4305
–
14.8
11.1
54.6
–
19.1
14.7
36.2
–
20.4
7.9
54.3
–
–
–
–
–
41.7
–
–
–
19.0
–
–
–
41.4
–
–
–
18.5
–
5577
2209
2023
47,210
–
–
–
2294
–
–
–
48,035
–
–
–
2759
–
O 1s
110,723
9198
14,339
2757
80,048
10,983
5520
35.6
29.7
58.4
22.8
27.5
37.5
73.1
2.4
29.8
37.0
70.6
27.7
38.1
200,070
15,857
6607
64.4
51.2
26.9
22.0
72.5
42.1
19.0
1.9
70.2
45.2
19.1
25.0
61.9
Al 2p
Fe 2p3/2
Y 3d
2654
O 1s
210,635
12,329
1438
Co10
Al 2p
Co 2p3/2
Y 3d
2800
2223
O 1s
90,251
14,921
32,800
4149
212,441
18,253
8847
Al 2p
Co 2p3/2
Y 3d
17.8
10.3
28.8
–
3744
O 1s
120,586
195,558
8

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
Fig. 7. Polarization curves of the as-spun Al85Fe10
Y
5
(Fe10) and Al85Co10
Y
5
(Co10) ribbons in (a) DW and (b) MO solutions and their Nyquist curves in (c) DW and (d) MO solutions. The
upper insets in (c) and (d): the general fitted circuit. Symbols show the experimental data while solid lines are fitting results.
Through XPS results of the as-spun and reacted surface elements of
Fe10 and Co10 ribbons, we found that consumption of Al and Fe on
the surface of Fe10 ribbon during reaction was higher than the loss of
solution decreased to different degrees after adding BQ and TBA, indi-
cating the produced •O and •OH radicals play an important role in
2
the degradation of the MO dye molecules. When pH = 1, the addition
of BQ resulted the η of Co10 ribbon on MO solution decreased to
0
0
−
0
0
Al and Co on the surface of Co10 ribbon. Compared with Fe
Co , the Y occupy a higher fraction on the Fe10 and Co10 ribbons
surface in as-spun and reacted states (Figs. 5 and 6). Upon visible light
irradiation, the electron from the valence band of Y can be excited
and then accelerate
the degradation of MO solution [49,54]. Through XPS analysis, we
know that the relative content of Y on the surface of Co10 ribbon is
2
O
3
and
O
2 3
O
2 3
75.5%, being 18.9% lower than the original result, and confirming that
−
the added BQ can quench the produced •O
2
(Fig. 11(a)). However, the
O
2 3
present η is still high (75.5%), owing to the [H] generated in the reaction,
which plays a dominant role in the degradation of MO solution under
acid conditions [38,69]. When pH = 13, the addition of BQ and TBA re-
−
2 2
to conduction band react with O to generate •O
O
2 3
duced the η of Co10 ribbon to 70.1% and 41.6%, respectively, indicating
−
higher than that of Fe10 ribbon, leading to the fast degradation MO so-
lution, which explains the better degradation performance of the Co10
amorphous ribbon.
that the addition of BQ and TBA could respectively quench the •O
2
and •OH generated in the reaction, and the •OH was the dominant spe-
cies for degradation of alkaline MO solution (Fig. 11(b)). Moreover, the
simultaneous addition of BQ and TBA significantly reduced the MO solu-
tion degradation efficiency from 91.5 to 26.4%.
The degradation efficiency η of MO solution is increased from the 1st
to 3rd cycle. This is due to the fact that various metal oxide films are re-
moved in the 1st cycle, so that the degradation of MO solution can begin
directly in the 2nd and 3rd cycles, which can be confirmed by the non-
transient platform of the 2nd and 3rd cycles in Fig. 10(a) and (c). The η
In order to explore the degradation mechanism of MO solution
under different pH conditions and clarify the contribution of reactive
oxygen species during the degradation process, we investigated the
degradation efficiency η change of MO solution after adding quenching
−1
agents of 1,4-benzoquinone (BQ 0.1 mol L ) and tertiary butanol (TBA
−1
−
0
.1 mol L ), which are normally used for quenching the produced •O
2
and •OH radicals, respectively [71,72]. As shown in Fig. 11, the η of MB
Table 3
s t f f a a
Parameters from EIS measurements: R , solution resistance; Cdl, resistance of electric double layer; R , resistance of transfer charge; Q and R , resistance of passivation film; C and R , re-
sistance of electrochemical reaction; Rtotal, total resistance.
2
dl (10−7 Ω−1·cm−2
2
4
2
(10−6 Ω−1·cm−2
2
2
Solution Alloy
R
s
(Ω·cm )
C
)
R
t
(Ω·cm )
Q
f
R
f
(10 Ω·cm )
C
a
)
R
a
(Ω·cm )
Rtotal (Ω·cm )
(10− Ω−1s-n·cm−2
6
)
N
f
Y
f
3
−3
−3
DW
MO
Fe10 1.63
Co10 1.29
Fe10 0.07
Co10 0.03
7.0 × 10−
6.2 × 10−
1.74
566
521
21.56
31.93
4.6 × 10
8.1 × 10
4.69
0.97 0.69
0.93 0.85
0.93 1.86
0.95 2.08
9.4 × 10
2.4 × 10
4.85
0.05
1.3 × 10
0.07
7467
3
−3
−3
3
3
10,322
18,621
22,232
5.34
3.46
4.39
1.4 × 10
9

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
Fig. 8. The normalized concentration C
/C
t 0
change of MO solution during the degradation process of the as-spun (a) Al85Fe10
Y
5
5
(Fe10) and (b) Al85Co10Y (Co10) ribbons at different
temperatures (T
ribbons. (d) The reaction activation energy E
r
). (c) Derived reaction rate constants k at different reaction temperatures, the bottom right inset in (c): lnk(T
and reaction rate constants k for the as-spun Fe10 and Co10 ribbons.
r
) vs − 1/RT curves for the as-spun Fe10 and Co10
r
r
of Fe10 ribbon dropped sharply from the 4th cycle, while Co10 ribbon
increased (Fig. 10(b) and (d)). After three degradation cycles, the
amount of available zero-valent metals on the ribbon surface decreases
and the degradation efficiency decreases [68]. However, since the iron
element in the Fe10 ribbon forms iron oxide on the surface to prevent
zero-valent metals from participating in degradation reactive [22], the
cobalt element in the Co10 ribbon is easy to combine with other metal
elements to form a network structure and increase the specific surface
area of the reaction, thus slowing down the degradation rate [73].
The homogeneity of the Co10 ribbon is higher than Fe10 ribbon
(Figs. 1 and 2). According to free energy with concentration is binary
x
A B1-x system, the spinodal occurs in the x = 0.5 adjacent and the
Fig. 9. The normalized concentration C
t
/C
0
5 5
change of MO solution during the degradation process of (a) Al85Fe10Y (Fe10) and (b) Al85Co10Y (Co10) ribbons at different pH values. The
degradation efficiency (η = (1- C /C × 100%, t
t
0
r
= 45 min) of the degradation process vs. pH values for (c) Fe10 and (d) Co10 ribbons.
10

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
Fig. 10. The normalized concentration C
t
/C
0
5 5
change of MO solution during the degradation process of (a) Al85Fe10Y (Fe10) and (b) Al85Co10Y (Co10) ribbons from the 1st to the 7th
degradation cycles. The degradation efficiency (η = (1- C
t
/C × 100%, t = 45 min) of the degradation process vs. reaction cycles for (c) Fe10 and (d) Co10 ribbons.
0
r
deviated zone from x = 0.5 can occurs metastable decomposition (nu-
cleation and growth) [55,74]. Hence, the maze like structure and
spinodal characteristic structure formed on Co10 ribbon surface (Fig. 4
the alkaline MO solution, the electrons produced by the ionization of
the metal element combine with the OH to form a strong oxidizing
−
•OH radical. Upon visible light irradiation, the Y
2 2
combines with O and electron to generate •O and then accelerate the
2
O
3
on the ribbon surface
−
(d)), while the spherical particles formed on the Fe10 ribbon surface
Fig. 4(c)). Apparently the depth of the groove in reacted Co10 ribbon
(
degradation of MO solution. And the surface of Co10 ribbon has a maze
surface is deeper than Fe10 ribbon surface, and the specific surface
area of Co10 ribbon to join reaction is larger than Fe10 ribbon
like network structure, which can increase the specific surface area of
−
reaction and provide more Y
O
2 3
to generate •O
2
. By magnetic stirring
−
(Table 1). Hence, the stability and degradation efficiency of Co10 ribbon
2
force, the [H] or •OH or •O radicals are dispersed into the MO solution,
are higher than Fe10 ribbon.
and MO dye molecules are then degraded and mineralized into small
molecules, including H O, CO , NO and SO . According to Ref [74],
2 2 3 4
the higher homogeneity and stability of Co10 ribbon can form a maze
like surface to increase the specific surface area of the reaction, and
may improve the MO solution degradation efficiency and reusability
in MO solution.
−
2−
Based on the thorough analyses of the elemental information, sur-
face morphology and electronic structure of the Fe10 and Co10 ribbons
during MO solution degradation, we have drawn the schematic diagram
is illustrated in Fig. 12. The as-spun Fe10 ribbon in the acidic and alka-
line MO solutions showed some spheroid particles on the surface of
the ribbon, while the as-spun Co10 ribbon formed a developed maze
like network structure on the surface, and through XPS analysis, the
5. Conclusions
2 3
as-spun and reacted surfaces consist of Y and Y O . Upon visible light ir-
radiation, after adding as-spun Fe10 and Co10 ribbons into the acidic
MO solution, metallic elements are ionized and generate electrons,
which combine with H on the ribbon surface to generate [H]. And in
5 5
In this work, we have prepared Al85Fe10Y (Fe10) and Al85Co10Y
(Co10) amorphous ribbons with melt spun method and we studied
the microstructure, MO degradation behavior with various techniques.
+
(
a)
(b)
1.0
0.8
0.6
0.4
0.2
0.0
1.0
0.8
0.6
0.4
Original
BQ
Original
BQ
TBA
BQ+TBA
0.2
0.0
0
10
20
30
40
0
10
20
30
40
tr
(min)
tr (min)
Fig. 11. Comparable results of degradation efficiency of as-spun Co10 ribbon with and without adding quenching agents of 1,4-benzoquinone (BQ) and tertiary butanol (TBA) at (a) pH = 1
and (b) pH = 13.
11

Q. Chen, Z. Yan, L. Guo et al.
Journal of Molecular Liquids 318 (2020) 114318
Fig. 12. Schematic illustration of the degradation mechanism of MO dyes using the Al85Fe10
Y
5
(Fe10) and Al85Co10
Y
5
(Co10) amorphous ribbons.
[
[
[
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MO solution than Fe10 ribbon at pH = 1. The maze like structure on
Co10 surface and spherical particles on the Fe10 surface can improve
the degradation efficiency of MO solution especially at pH = 1. The
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Y O on the as-spun and reacted ribbon surfaces can also catalyze the
[
MO solution under visible light irradiation. The higher degradation effi-
ciency of Co10 ribbon than Fe10 ribbon can be ascribed to the larger
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1
[
[
[
[
[
[
[
[
CRediT authorship contribution statement
(
2018) 10686.
Qi Chen wrote the article. Zhicheng Yan, Lingyu Guo and Hao Zhang
did the help in the experiments. Laichang Zhang gave the key advices in
organizing the article. Weimin Wang designed the experiment.
[
[
23] C.Q. Zhang, Z.W. Zhu, H.F. Zhang, Q.L. Sun, K.G. Liu, Results Phys. 10 (2018) 1.
24] Z. Jia, J. Kang, W.C. Zhang, W.M. Wang, C. Yang, H. Sun, D. Habibi, L.C. Zhang, Appl.
Catal., B 204 (2017) 537.
25] Z. Jia, S.X. Liang, W.C. Zhang, W.M. Wang, C. Yang, L.C. Zhang, J. Taiwan Inst. Chem.
Eng. 71 (2017) 128.
[
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26] Z. Jia, W.C. Zhang, W.M. Wang, D. Habibi, L.C. Zhang, Appl. Catal., B 192 (2016) 46.
Declaration of competing interest
[27] J.Q. Wang, Y.H. Liu, M.W. Chen, G.Q. Xie, D.V. Louzguine Luzgin, A. Inoue, J.H.
Perepezko, Adv. Funct. Mater. 22 (2012) 2567.
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29] Y.J. Li, Y.G. Wang, B. An, H. Xu, Y. Liu, L.C. Zhang, H.Y. Ma, W.M. Wang, PLoS One 11
(2016), e0146421, .
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
[30] J.Q. Wang, Y.H. Liu, M.W. Chen, D.V. Louzguine-Luzgin, A. Inoue, J.H. Perepezko, Sci.
Rep. 2 (2012) 418.
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31] Y.F. Zhao, J.J. Si, J.G. Song, Q. Yang, X.D. Hui, Mater. Sci. Eng. B 181 (2014) 46.
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Cryst. Solids 529 (2020), 119802, .
Acknowledgements
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33] Q. Chen, Z.C. Yan, L.Y. Guo, H. Zhang, L.C. Zhang, K. Kim, X.Y. Li, W.M. Wang, J. Alloys
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This work was financially supported by the National Key Research
Program of China (2016YFB0300501), National Natural Science Founda-
tion of China (51471099, 51571132, 51511140291 and 51771103).
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