coatings

Article
Composition and Structure Evolution of Bi2O3
Coatings as Efficient Photocatalysts
Lijun Cheng 1 , Liang Hao 1, * and Yun Lu 2 ID

1 Tianjin Key Laboratory of Integrated Design and On-line Monitoring for Light Industry & Food Machinery
and Equipment, College of Mechanical Engineering, Tianjin University of Science & Technology,
Tianjin 300222, China; chenglijun@tust.edu.cn
2 College of Mechanical Engineering & Graduate School, Chiba University, Chiba 263-8522, Japan;
luyun@faculty.chiba-u.jp
* Correspondence: haoliang@tust.edu.cn; Tel.: +86-22-6060-0692

Academic Editor: Charles C. Sorrell

Received: 20 November 2017; Accepted: 27 December 2017; Published: 29 December 2017

Abstract: To overcome the recovery disadvantages of Bi2 O3 photocatalyst in the form of powder,
Bi2 O3 photocatalyst coatings were developed via a ball milling, followed by the calcination method.
The composition and structure evolution rules of the as-synthesized samples were analyzed based
on XRD (X-ray powder diffraction) patterns and SEM (scanning electron microscope) observations.
XPS (X-ray photoelectron spectroscopy) and UV-Vis (Ultraviolet-visible) spectra were also employed
to characterize the samples. The results showed that monoclinic Bi2 O3 coatings were obtained after
sintering Bi coatings at 673 or 773 K for 2 h, while calcination at a higher temperature and for a
longer time resulted in monoclinic and triclinic mixed-phase Bi2 O3 coatings. Bi2 O3 coatings with a
radial growth structure assembled by nanosheets could be realized at a lower temperature lasting
for a longer time, while sintering at a higher temperature with relatively short oxidation time led to
tangential growth structure. Photodegradation of malachite green solution under simulated solar
irradiation for 180 min showed that the largest degradation efficiency of 91.49% was achieved over
the photocatalyst coatings calcined at 873 K for 5 h. Additionally, the degradation efficiency was
maintained above 80% even after three cycles.

Keywords: Bi2 O3 ; coatings; ball milling; photocatalyst

1. Introduction
Nowadays, environmental pollution and energy crisis cause extremely severe and destructive
effects for human health and society development. Fortunately, photocatalysis technology appears
as an efficient, economical, and environmental friendly technology, which can be applied in
environmental remediation, as well as solar energy conversion, since it was discovered in 1972 [1–3].
To date, various types of semiconductor photocatalysts have been explored, especially the
TiO2 -based photocatalysts which are always being ranked as the most researched ones [4–6].
However, their applications are retarded by low ultilization efficiency for solar light absorption
or a high recombination of charge carriers, thus making development of photocatalysts with visible
light responsive ability indispensable. Recently, bismuth-based semiconductor photocatalysts have
been demonstrated to exhibit superior photocatalytic activity under visible-light irradiation, and the
interest in bismuth-based semiconductors is continuing to grow [7–12].
In order to push the applications of photocatalysts in practical industry fields, such as waste water
treatment, the dispersity, recovery, and repeatability of the photocatalysts are of great significance.
Yet, it is difficult to realize such an objective with photocatalysts in powder form, which impels the
pursuit of a valid method to achieve improved recovery properties of photocatalysts. Among various

Coatings 2018, 8, 14; doi:10.3390/coatings8010014 www.mdpi.com/journal/coatings

Coatings 2018, 8, 14 2 of 10

approaches, immobilizing photocatalyst particles onto some kind of supporter is effective at achieving
such an objective. Hence, ZnO nanoparticles immobilized montmorillonite [13], Nano-TiO2 -loaded
activated carbon fiber [14], TiO2 -montmorillonite composite [15], acid-treated vermiculite supported
TiO2 [16], TiO2 supported silica nanolayers [17], TiO2 /HZSM-5 composite [18], and Ag–TiO2
photocatalyst supported on glass fiber [19] were synthesized to improve the dispersity of photocatalyst
particles and, consequently, photocatalytic performances.
With regard to bismuth-based loaded photocatalysts, there have been some reports as well.
Wang et al. [20] synthesized Bi2 O3 /HZSM-5 composite photocatalysts via a facile ion-exchange
method. The results showed that the Bi2 O3 /HZSM-5 composite photocatalyst acquires the highest
photocatalytic activity for rhodamine B degradation at the optimal loading with 18 wt % Bi2 O3
and proposed the synergistic effect between HZSM-5 and Bi2 O3 , namely, the special structure of
HZSM-5 increased the number of the active sites to adsorb more dye molecules and photodegraded
them on the Bi2 O3 photocatalyst. Zhang et al. [21] immobilized the Bi2 WO6 /Bi2 O3 composite onto
the polyurethane sponge and obtained enhanced photocatalytic activity and reusability towards
rhodamine B degradation. Jiao et al. [22] prepared the Mg/Al layered double hydroxide loaded
Pd(II)-Bi2 O3 via impregnation and calcination technique. The results displayed that the sample
possessed high crystallinity, large specific surface area, and broad absorption in the visible region,
which contributed to its excellent photocatalytic activity for methylene blue degradation.
To overcome the recycle problem thoroughly, Al2 O3 balls with an average diameter of 1 mm
were used as the substrate to prepare bismuth-based photocatalyst coatings. Metallic Bi powder was
employed as the starting material to be coated on the surface of Al2 O3 balls via a mechanical ball milling
method, and Bi2 O3 coatings were obtained by sintering the above Bi coatings. The composition and
structure evolution rules of the as-synthesized samples were analyzed based on XRD (X-ray powder
diffraction) patterns and SEM (scanning electron microscope) observations. The optical properties and
the photo-degradation performances of the samples were also studied with the aim of providing a
new type of bismuth-based semiconductor photocatalyst coating that is applicable to practical water
cleaning or other contaminants disposal.

2. Experimental

2.1. Preparation of Bi2 O3 Photocatalyst Coatings

Metallic Bi powder (purity of 99.5%) and Al2 O3 balls (purity of 98.5%, average diameter of 1 mm)
were used as the coating material and the substrate, respectively. The Bi coatings were prepared
according to the following process: 20 g Bi powder and 30 g Al2 O3 balls were poured into an Al2 O3
bowl with a volume of 250 mL, which subjected to milling in a planetary ball mill at the rotation speed
of 290 rpm for 10 h.
The series of Bi2 O3 coatings were fabricated by calcining the above Bi coatings in an electric
furnace at 673, 773, 873, and 973 K for different time (2, 5, and 10 h) and the corresponding samples
were denoted as BC-673-2, BC-673-5, BC-673-10, BC-773-2, BC-773-5, BC-773-10, BC-873-2, BC-873-5,
BC-873-10, BC-973-2, BC-973-5, and BC-973-10, respectively.

2.2. Characterization
X-ray diffraction (XRD) analysis was performed on a Bruker D8 ADVANCE unit (Bruker, Billerica,
MA, USA) using Cu Kα radiation to identify the crystalline phases of the coatings. The surface and
cross-section morphologies of the coatings were observed by scanning electronic microscopy (SEM) on
a Hitachi S-4800 microscope (Hitachi, Tokyo, Japan). The element valence state of Bi was analyzed
with X-ray photoelectron spectroscopy (XPS) on a Thermo ESCALAB 250Xi energy spectrometer
(Thermo Fisher Scientific, Waltham, MA, USA). The UV-Vis diffuse reflectance spectra of the coatings
were recorded on a Lambda 750S UV/VIS/NIR spectrometer (PerkinElmer, Waltham, MA, USA).
Coatings 2018, 1, 14  3 of 10 

Coatings 2018, 8, 14 3 of 10
spectra of the coatings were recorded on a Lambda 750S UV/VIS/NIR spectrometer (PerkinElmer, 
Waltham, MA, USA). Additionally, the absorbance of malachite green (MG) aqueous solution was 
tested  with  a the
Additionally, 722 absorbance
Vis  spectrophotometer 
of malachite (Sunny  Optical 
green (MG) Technology 
aqueous (Group) 
solution Company 
was tested with aLimited, 
722 Vis
Yuyao, China). 
spectrophotometer (Sunny Optical Technology (Group) Company Limited, Yuyao, China).

2.3. Photocatalytic Activity 
2.3. Photocatalytic Activity
The  photocatalytic
The photocatalytic  activities
activities  of
of  the
the  coatings
coatings  were
were  investigated
investigated  byby  photodegradation
photodegradation  of
of  MG
MG 
solution  with
solution with  concentration
concentration  of
of 10
10 mg/L,
mg/L,  which  was  performed
which was performed  inin  aa CEL-LAB500
CEL‐LAB500 Photocatalytic
Photocatalytic 
Reactor from CEAULIGHT (Beijing, China). In detail, 0.1 g coatings were dispersed in 50 mL MG 
Reactor from CEAULIGHT (Beijing, China). In detail, 0.1 g coatings were dispersed in 50 mL MG
Then, 500 W Xe lamp (light density was 75% ± 5% mW/cm2 ) was turned on to carry out
solution. Then, 500 W Xe lamp (light density was 75% ± 5% mW/cm²) was turned on to carry out the 
solution.
degradation experiment. During the reaction period, certain amount of MG solution was taken out, 
the degradation experiment. During the reaction period, certain amount of MG solution was taken
centrifuged to separate the photocatalyst, and the residual MG concentration was analyzed by the 
out, centrifuged to separate the photocatalyst, and the residual MG concentration was analyzed by the
spectrophotometer at regular intervals. 
spectrophotometer at regular intervals.

3. Results and Discussion

3. Results and Discussion 

3.1. XRD Patterns

3.1. XRD Patterns 
The XRD patterns of Bi and Bi22O
The XRD patterns of Bi and Bi coatings prepared at different oxidation temperature or time
O33 coatings prepared at different oxidation temperature or time 
are displayed in Figure 1. The characteristic diffraction peaks of the as-prepared Bi coatings can be
are displayed in Figure 1. The characteristic diffraction peaks of the as‐prepared Bi coatings can be 
indexed to hexagonal Bi consistent with PDF card No. 44-1246. After thermal oxidation above 673 K,
indexed to hexagonal Bi consistent with PDF card No. 44‐1246. After thermal oxidation above 673 K, 
the Bi coatings all transformed to Bi22O
the Bi coatings all transformed to Bi coatings even though the oxidation was only maintained for
O33 coatings even though the oxidation was only maintained for 
22 h. When the Bi coatings were oxidized at 673 and 773 K for 2 h, monoclinic Bi
h. When the Bi coatings were oxidized at 673 and 773 K for 2 h, monoclinic Bi22O coatings were
O33 coatings were 
prepared. With the time extending to 5 and 10 h, the as-prepared Bi2O
prepared. With the time extending to 5 and 10 h, the as‐prepared Bi 2O 3 coatings not only consisted
3 coatings not only consisted of 
of monoclinic Bi O phase (labeled by hollow square, PDF card No. 41-1449) but also triclinic
monoclinic Bi2O3 phase (labeled by hollow square, PDF card No. 41‐1449) but also triclinic Bi
2 3 Bi2 O3
2O3 phase 
phase (labeled by circle, PDF card No. 50-1088). Nevertheless, for the coatings oxidized
(labeled by circle, PDF card No. 50‐1088). Nevertheless, for the coatings oxidized at 873 and 973 K,  at 873 and
973 K, mixed-phase
mixed‐phase  Bi2 O3 always 
Bi2O3  were  were always obtained
obtained  with with the oxidation
the  oxidation  time time ranging
ranging  from
from  2  2to 
to10 
10 h. 
h.
Additionally, the diffraction peaks from triclinic Bi O became stronger with the temperature
Additionally, the diffraction peaks from triclinic Bi22O33 became stronger with the temperature or time  or time
raising. Consequently, the 
raising.  Consequently,  the coatings 
coatings composition 
composition evolved 
evolved from 
from single
single  phase
phase  to
to  mixed
mixed phases
phases with
with 
prolonged time at lower temperature or heightened temperature. Moreover, almost all
prolonged time at lower temperature or heightened temperature. Moreover, almost all the diffraction  the diffraction
peaks of the samples shifted to smaller angel with the oxidation time prolonged, which may result
peaks of the samples shifted to smaller angel with the oxidation time prolonged, which may result 
from stress release that accumulated during the ball milling process.
from stress release that accumulated during the ball milling process. 

Figure 1.
Figure 1.  XRD
XRD  patterns
patterns  of
of  the
the as-prepared
as‐prepared coatings:
coatings:  (a)
(a)  BC-673-2,
BC‐673‐2,  BC-673-5,
BC‐673‐5,  BC-673-10,
BC‐673‐10,  BC-773-2,
BC‐773‐2,   
BC‐773‐5, BC‐773‐10; (b) BC‐873‐2, BC‐873‐5, BC‐873‐10, BC‐973‐2, BC‐973‐5, BC‐973‐10. 
BC-773-5, BC-773-10; (b) BC-873-2, BC-873-5, BC-873-10, BC-973-2, BC-973-5, BC-973-10.

3.2. Microstructure Evolution of the Coatings 
3.2. Microstructure Evolution of the Coatings
Figure 2a shows the surface and cross‐section SEM images of initial Bi coatings. It could be found 
Figure 2a shows the surface and cross-section SEM images of initial Bi coatings. It could be
that continuous Bi coatings were formed by coalescence of the discrete islands on Al
found that continuous Bi coatings were formed by coalescence of the discrete islands on 2O3 ball after 
Al2 O3 ball
mechanical ball milling at 290 rpm for 10 h. The surface of Bi coatings was relatively smooth and the 
after mechanical ball milling at 290 rpm for 10 h. The surface of Bi coatings was relatively smooth
 Coatings 2018, 8, 14 4 of 10
Coatings 2018, 1, 14  4 of 10 

connection trace was obvious. From the cross‐section image, one can see Bi coatings with average 
and the connection trace was obvious. From the cross-section image, one can see Bi coatings with
thickness 
averageof thickness
30  μm  of
were  obtained. 
30 µm After After
were obtained. the  Bi 
the coatings 
Bi coatingswere 
were thermally  oxidized 
thermally oxidized at  different 
at different
temperature for different time, a series of Bi
temperature for different time, a series of Bi22O
O33 coatings with harsh surface derived from distinctly 
coatings with harsh surface derived from distinctly
different
different  oxidation
oxidation  degree
degree  weresynthesized. 
were  synthesized. As 
As a 
a typical
typical example,
example, the micromorphologies
the  micromorphologies of the
of  the   
BC-873-5 sample are displayed in Figure
BC‐873‐5 sample are displayed in Figure 2b.  2b.

 
(a)  (b)
Figure 2. The surface and cross‐section morphologies of (a) Bi coatings and (b) BC‐873‐5. 
Figure 2. The surface and cross-section morphologies of (a) Bi coatings and (b) BC-873-5.

To clarify the microstructure transformation of the Bi 2O3 coatings with calcination temperature 
To clarify the microstructure transformation of the Bi2 O3 coatings with calcination temperature
and  and
time,  the  high‐resolution  SEM  images  of  the  coatings 
time, the high-resolution SEM images of the coatings are revealed are  revealed 
in Figurein  Figure 
3. When the3. BiWhen  the  Bi 
coatings
coatings 
werewere  oxidized 
oxidized at 673 Kat for
673  K Bifor 
2 h, 2  h,  Bi2O3  crystals  grew  into  thin  nanosheets  along  the  radial 
2 O3 crystals grew into thin nanosheets along the radial direction of
direction of the ball and interwined with each other to form flower‐like shapes at some surface areas. 
the ball and interwined with each other to form flower-like shapes at some surface areas. With the
With the oxidation time prolonged to 5 h, large amounts of small nanosheets along the tangential 
oxidation time prolonged to 5 h, large amounts of small nanosheets along the tangential direction of
the ball were visibly displayed, and some nanosheets debris also existed along the radial direction.
direction of the ball were visibly displayed, and some nanosheets debris also existed along the radial 
direction. the
After oxidation
After  that lasted
the  oxidation  for lasted 
that  10h, thefor 
Bi coatings
10h,  the were oxidized were 
Bi  coatings  adequately and formed
oxidized  large and 
adequately 
staggered nanosheets along the radial direction of the ball. Elevating the temperature to 773 K resulted
formed large staggered nanosheets along the radial direction of the ball. Elevating the temperature 
in completely different growth direction of Bi2 O3 crystals. Specifically, at the first oxidation stage,
to 773 K resulted in completely different growth direction of Bi 2O3 crystals. Specifically, at the first 
the Bi2 O3 crystals appeared as irregular particles, which grew along the tangential direction of the ball.
oxidation stage, the Bi2O3 crystals appeared as irregular particles, which grew along the tangential 
Then, nanosheets along the radial direction of the ball gradually occurred with the oxidation preserved
direction of the ball. Then, nanosheets along the radial direction of the ball gradually occurred with 
for 5 h, and flower-like structure stacked by nanosheets were almost completely formed when the time
the  oxidation 
prolonged to preserved  for  5 structure
10 h. The same h,  and  evolution
flower‐like  structure 
tendency stacked  for
was observed by Bi
nanosheets  were  almost 
2 O3 coatings sintered
completely formed  when  the  time  prolonged  to 10  h. 
at 873 K, except that larger polygonal Bi2 O3 crystals scattered fine nanoparticles on its surface were was 
The  same structure  evolution  tendency 
observed for Bi
formed, and2O 3 coatings sintered at 873 K, except that larger polygonal Bi
much fewer nanosheets along the radial direction of the ball were observed, 2O3 crystals scattered 
even when
fine nanoparticles on its surface were formed, and much fewer nanosheets along the radial direction 
the time increased to 5 and 10 h. For Bi2 O3 coatings prepared at 973 K, much larger polygonal Bi2 O3
crystals similarly scattered fine nanoparticles always emerged along the tangential
of the ball were observed, even when the time increased to 5 and 10 h. For Bi 2Odirection of the ball
3 coatings prepared at 
in spite of the oxidation duration of 10 h. Hence, from the structure evolution rules
973 K, much larger polygonal Bi2O3 crystals similarly scattered fine nanoparticles always emerged  of Bi2 3 coatings,
O
it could be generally concluded that lower temperature apt to form radial growth structure with
along the tangential direction of the ball in spite of the oxidation duration of 10 h. Hence, from the 
nanosheets was interlaced, and yet higher temperature apt to generate tangential growth structure
structure evolution rules of Bi 2O3 coatings, it could be generally concluded that lower temperature 
consisted of irregular polygonal crystals and nanoparticles.
apt to form radial growth structure with nanosheets was interlaced, and yet higher temperature apt 
to generate tangential growth structure consisted of irregular polygonal crystals and nanoparticles. 

 
 of the ball were observed, even when the time increased to 5 and 10 h. For Bi2O3 coatings prepared at 
973 K, much larger polygonal Bi2O3 crystals similarly scattered fine nanoparticles always emerged 
along the tangential direction of the ball in spite of the oxidation duration of 10 h. Hence, from the 
structure evolution rules of Bi2O3 coatings, it could be generally concluded that lower temperature 
apt to form radial growth structure with nanosheets was interlaced, and yet higher temperature apt 
Coatings 2018, 8, 14 5 of 10
to generate tangential growth structure consisted of irregular polygonal crystals and nanoparticles. 

Coatings 2018, 1, 14    5 of 10 
(a)
Figure 3. Cont.   

 
(b)

 
(c)

 
(d)
Figure 3. The surface morphologies of Bi
3. The surface morphologies of Bi 2O3 coatings: (a1) BC‐673‐2; (a2) BC‐673‐5; (a3)BC‐673‐10; (b1) 
Figure 2 O3 coatings: (a1) BC-673-2; (a2) BC-673-5; (a3) BC-673-10;
BC‐773‐2; (b2) BC‐773‐5; (b3) BC‐773‐10; (c1) BC‐873‐2; (c2) BC‐873‐5; (c3) BC‐873‐10; (d1) BC‐973‐2; 
(b1) BC-773-2; (b2) BC-773-5; (b3) BC-773-10; (c1) BC-873-2; (c2) BC-873-5; (c3) BC-873-10; (d1) BC-973-2;
(d2) BC‐973‐5; (d3) BC‐973‐10. 
(d2) BC-973-5; (d3) BC-973-10.

3.3. Structure Evolution Mechanism 
3.3. Structure Evolution Mechanism
Based on the above SEM images analysis, the structure evolution mechanism was deduced as 
Based When 
follows.  on thethe above SEM images
Bi  coatings  analysis,at the
were  oxidized  structure
673  evolution
K,  Bi  and  mechanism
O2  diffusion  was deduced
first  simultaneously 
as occurred, resulting from sufficient O
follows. When the Bi coatings were oxidized at 673 K, Bi and O2 diffusion first simultaneously
2 around the coatings surface and active Bi element; then, with 
occurred, resulting from sufficient O
time  prolonged,  O2  around  the  coatings 
2 around the coatings
surface  surface
decreased  and and active Bi
therefore  Bi element;
diffusion then, with time
dominated, 
prolonged, O around the coatings
which led to overall radical growth of Bi
2 surface decreased and therefore Bi diffusion dominated,
2O3 crystals along the surface of Al2O3 ball. However, when  which led
to temperature was elevated to 773, 873, and 973 K, the oxidation rates of Bi coatings were accelerated 
overall radical growth of Bi2 O3 crystals along the surface of Al2 O3 ball. However, when temperature
was elevated
and  the  Bi2to
O3 773, 873, and
coatings  973
were  K, the oxidation
relatively  rates ofhindered 
thicker,  which  Bi coatingsthe were accelerated
Bi  diffusion  and and the Bi
thereby  O22O
  3
diffusion 
coatings weredominated 
relatively the  oxidation, 
thicker, which leading 
hinderedto thetangential  growth 
Bi diffusion of  Bi2O3O
and thereby   crystals. 
2 diffusionWhen  time 
dominated
theincreased, 
oxidation,O2leading
  around tothe  coatings’ growth
tangential surface ofdecreased.  Thus,  the 
Bi2 O3 crystals. When oxidation  was  dominated 
time increased, by  Bi 
O2 around the
diffusion and radical growth of Bi
coatings’ surface decreased. Thus, 2the O3 crystals emerged. The growth tendency of Bi
oxidation was dominated by Bi diffusion 2and O3 crystals on the 
radical growth
of surface of Al
Bi2 O3 crystals2O3emerged.
 ball with calcination time is briefly illustrated in Figure 4. Specifically, the irregular 
The growth tendency of Bi2 O3 crystals on the surface of Al2 O3 ball with
crystals  gradually 
calcination time is brieflygrew  larger  along 
illustrated the  tangential 
in Figure direction 
4. Specifically, of  the  balls 
the irregular with gradually
crystals the  oxidation 
grewtime 
larger
extended 
along and  at  appropriate 
the tangential direction oftime; 
the Bi 2O3  nanosheets  along  the  radial  of  the  balls  appeared,  which 
balls with the oxidation time extended and at appropriate time;
Bi2continued to increase and completely spread over the whole surface of the balls. Thus, Bi
O3 nanosheets along the radial of the balls appeared, which continued to increase and 2O3 coatings 
completely
with radial growth structure assembled by nanosheets could be easily realized at lower temperature 
lasting for longer time, while those with tangential growth structure could be simply achieved by 
controlling the temperature at higher level accompanied by relatively shorter oxidation time. 
Coatings 2018, 8, 14 6 of 10

spread over the whole surface of the balls. Thus, Bi2 O3 coatings with radial growth structure assembled
by nanosheets could be easily realized at lower temperature lasting for longer time, while those with
tangential growth structure could be simply achieved by controlling the temperature at higher level
accompanied by relatively shorter oxidation time.
Coatings 2018, 1, 14  6 of 10 

Coatings 2018, 1, 14  6 of 10 

 
Figure 4. The growth tendency of Bi2O3 crystals on the surface of Al2O3 ball with calcination time increasing. 
Figure 4. The growth tendency of Bi2 O3 crystals on the surface of Al2 O3 ball with calcination time increasing.
3.4. XPS   
Figure 4. The growth tendency of Bi
3.4. XPS 2O3 crystals on the surface of Al2O3 ball with calcination time increasing. 
The surface chemical composition and valence state of Bi element in BC‐873‐5 were investigated 
by XPS analysis, as illustrated in Figure 5. The binding energy was corrected by C 1s adventitious 
The surface
3.4. XPS  chemical composition and valence state of Bi element in BC-873-5 were investigated
peak. Figure 5a shows the XPS survey spectra of BC‐873‐5, in which Bi and O elements can be clearly 
identified, confirming the formation of bismuth oxide. From the high resolution spectra of Bi element 
by XPS analysis, as illustrated in Figure 5. The binding energy was corrected by C 1s adventitious
The surface chemical composition and valence state of Bi element in BC‐873‐5 were investigated 
(Figure  5b),  two  strong  peaks  located  at  158.98  and  164.28  eV  are  assigned  to  Bi  4f7/2  and  Bi  4f5/2, 
peak.by XPS analysis, as illustrated in Figure 5. The binding energy was corrected by C 1s adventitious 
Figurerespectively, 
5a shows the is XPS
which  survey with 
in  agreement  spectra of BC-873-5,
the  reported  in which
values,  indicating  Bithe 
Bi3+  in  and O elements
coating.  The  can be
clearly identified, confirming the formation of bismuth oxide. From the high resolution spectra of Bi
binding  energy  of  Bi  4f  peaks  in  BC‐873‐5  shifted  to  a  larger  value  compared 
peak. Figure 5a shows the XPS survey spectra of BC‐873‐5, in which Bi and O elements can be clearly  to  BC‐873‐2  [23], 
implying  the  local  environment  and  electron  density  surrounding  Bi  cation  changed  with  the 
element (Figure 5b), two strong peaks located at 158.98 and 164.28 eV are assigned to Bi 4f 7/2 and
identified, confirming the formation of bismuth oxide. From the high resolution spectra of Bi element 
oxidation further proceeding. Figure 5c presents the high‐resolution O 1s spectrum. The spectrum 
(Figure 
Bi 4f 5/2 5b),  two  strong 
, respectively, whichpeaks  is in located 
agreement at  158.98 
with and  164.28  eV values,
the reported are  assigned  to  Bi  4fBi
indicating 3+ in the
7/2  and  Bi  4fcoating.
5/2, 
can be deconvoluted into two peaks. The peak at 529.7 eV is characteristic of O 2− in Bi–O bonds, while 

respectively, 
that  which 
at  530.9  is 
eV  in 
is  agreement 
characteristic  with 
of  the 
surface  reported 
hydroxyl  values, 
groups,  indicating 
which 
The binding energy of Bi 4f peaks in BC-873-5 shifted to a larger value compared to BC-873-2 [23], is  very  Bi 3+  to 
closed  in  the 
the  coating. 
values  The 
binding  reported in the literature [24,25]. 
energy  of  Bi  4f  peaks 
implying the local environment andin electron
BC‐873‐5  shifted surrounding
density to  a  larger  value  compared 
Bi cation changed to  with
BC‐873‐2  [23], 
the oxidation
implying  the  local  environment  and  electron  density  surrounding  Bi  cation  changed  with  the 
further proceeding. Figure 5c presents the high-resolution O 1s spectrum. The spectrum can be
oxidation further proceeding. Figure 5c presents the high‐resolution O 1s spectrum. The spectrum 
deconvoluted into two peaks. The peak at 529.7 eV is characteristic of O2 − in Bi–O bonds, while that
can be deconvoluted into two peaks. The peak at 529.7 eV is characteristic of O2− in Bi–O bonds, while 
at 530.9 eV is characteristic of surface hydroxyl groups, which is very closed to
that  at  530.9  eV  is  characteristic  of  surface  hydroxyl  groups,  which  is  very  closed  to  the  values 
the values reported in
the literature [24,25].
reported in the literature [24,25]. 

Figure 5. (a) XPS spectrum of BC‐873‐5; High‐resolution XPS spectra of (b) Bi 4f and (c) O 1s in BC‐873‐5. 

Figure 5. (a) XPS spectrum of BC‐873‐5; High‐resolution XPS spectra of (b) Bi 4f and (c) O 1s in BC‐873‐5. 
Figure 5. (a) XPS spectrum of BC-873-5; High-resolution XPS spectra of (b) Bi 4f and (c) O 1s in BC-873-5.

 
Coatings 2018, 8, 14 7 of 10

Coatings 2018, 1, 14  7 of 10 

3.5. UV-Vis Diffuse Reflectance Spectra

3.5. UV‐Vis Diffuse Reflectance Spectra 
UV-Vis diffuse reflectance spectra were measured to learn the optical properties of the as-prepared
UV‐Vis diffuse reflectance spectra were measured to learn the optical properties of the as‐prepared 
Bi2 O3 coatings, shown in Figure 6. It can be noticed that when the calcination temperature was not
Bi2O3 coatings, shown in Figure 6. It can be noticed that when the calcination temperature was not 
higher than 773 K, the coatings sintered for 5 and 10 h showed apparently enhanced absorption abilities
higher  than  773  K,  the  coatings  sintered  for  5  and  10  h  showed  apparently  enhanced  absorption 
for visible light compared to those sintered for 2 h. However, there was no obvious difference among
abilities for visible light compared to those sintered for 2 h. However, there was no obvious difference 
the absorption spectra of the BC-873 and BC-973 samples except BC-873-5, which displayed stronger
among the absorption spectra of the BC‐873 and BC‐973 samples except BC‐873‐5, which displayed 
absorption for visible light. According to the extrapolation principle, the absorption edges for BC-673
stronger absorption for visible light. According to the extrapolation principle, the absorption edges 
and BC-773 samples ranged from 526 to 536 nm, while those for BC-873 and BC-973 samples ranged
for  BC‐673  and  BC‐773  samples  ranged  from  526  to  536  nm,  while  those  for  BC‐873  and  BC‐973 
from 532nm to 563nm, corresponding to band gaps of 2.20 to 2.41 eV according to the relationship
samples ranged from 532nm to 563nm, corresponding to band gaps of 2.20 to 2.41 eV according to 
between band gap (Eg ) and absorption edge (λ) expressed as Eg = 1240/λ.
the relationship between band gap (Eg) and absorption edge (λ) expressed as Eg = 1240/λ. 

Figure  6.  UV‐Vis  diffuse  reflectance  spectra  of  the  as‐prepared  coatings:  (a)  BC‐673‐2,  BC‐673‐5,   
Figure 6. UV-Vis diffuse reflectance spectra of the as-prepared coatings: (a) BC-673-2, BC-673-5, BC-673-10,
BC‐673‐10,  BC‐773‐2,  BC‐773‐5,  BC‐773‐10;  (b)  BC‐873‐2,  BC‐873‐5,  BC‐873‐10,  BC‐973‐2,  BC‐973‐5, 
BC-773-2, BC-773-5, BC-773-10; (b) BC-873-2, BC-873-5, BC-873-10, BC-973-2, BC-973-5, BC-973-10.
BC‐973‐10. 

3.6. Photocatalytic Activities for Organic Dye

3.6. Photocatalytic Activities for Organic Dye 
The photocatalytic activities of as-prepared coating samples were evaluated via photo-degradation
The photocatalytic activities of as‐prepared coating samples were evaluated via photo‐degradation 
of MG aqueous solution under simulated solar irradiation. The MG degradation efficiencies over
of MG aqueous solution under simulated solar irradiation. The MG degradation efficiencies over the 
the series of Bi O3 photocatalyst coatings are displayed in Figure 7a. As shown, Bi2 O3 photocatalyst
series  of  Bi2O32  photocatalyst  coatings  are  displayed  in  Figure  7a.  As  shown,  Bi2O3  photocatalyst 
coatings calcined at higher temperature (873 or 973 K) generally demonstrated higher activities for
coatings calcined at higher temperature (873 or 973 K) generally demonstrated higher activities for 
MG degradation comparable to that calcined at lower temperature (673 or 773 K). Additionally,
MG degradation comparable to that calcined at lower temperature (673 or 773 K). Additionally, the 
the coatings calcined for 5 h possessed little better performances than those obtained at 2 or 10 h
coatings calcined for 5 h possessed little better performances than those obtained at 2 or 10 h for all 
for all the series of samples. It is deduced that composition-like ratio of the two different Bi2 O3
the  series  of  samples.  It  is  deduced  that  composition‐like  ratio  of  the  two  different  Bi2O3  phases, 
phases, microstructure, and particle size, and other related properties such as light absorption ability,
microstructure,  and  particle  size,  and  other  related  properties  such  as  light  absorption  ability, 
comprehensively contributed to the activity difference among these coatings. Based on the XRD
comprehensively  contributed  to  the  activity  difference  among  these  coatings.  Based  on  the  XRD 
patterns, it can be inferred that mixed-phase Bi2 O3 coatings degraded more dye than singe-phase ones
patterns, it can be inferred that mixed‐phase Bi2O3 coatings degraded more dye than singe‐phase ones 
as triclinic Bi O possessed better activity than monoclinic Bi O , as evidenced in the literature [26].
as triclinic Bi22O33 possessed better activity than monoclinic Bi22O33, as evidenced in the literature [26]. 
Besides, appropriate ratio of triclinic Bi2 O3 and monoclinic Bi2 O3 phases also played key role for
Besides, appropriate ratio of triclinic Bi2O 3 and monoclinic Bi2O3 phases also played key role for the 
the coating photocatalytic performances. The coatings with relatively higher ratio of triclinic Bi2 O3
coating  photocatalytic  performances.  The  coatings  with  relatively  higher  ratio  of  triclinic  Bi2O3  to 
to monoclinic Bi O3 demonstrated better performances, which was confirmed by higher activities
monoclinic Bi2O32 demonstrated better performances, which was confirmed by higher activities of the 
of the BC-873 and BC-973 samples than BC-673 and BC-773 samples; yet, if the ratio of triclinic
BC‐873  and  BC‐973  samples  than  BC‐673  and  BC‐773  samples;  yet,  if  the  ratio  of  triclinic  Bi2O3  to 
Bi2 O3 to monoclinic Bi2 O3 further increased, the coating photocatalytic activities basically showed
monoclinic  Bi2O3  further  increased,  the  coating  photocatalytic  activities  basically  showed  a 
a downward trend, exactly as the BC-973 samples contrast to BC-873 samples. In addition, in our
downward trend, exactly as the BC‐973 samples contrast to BC‐873 samples. In addition, in our case, 
case, Bi2 O3 coatings with tangential growth structure and polygonal Bi2 O3 crystals showed red shift of
Bi2O3  coatings  with  tangential  growth  structure  and  polygonal  Bi2O3  crystals  showed  red  shift  of 
absorption edges, which led to much superior photocatalytic performances as well. Last, the highest
absorption edges, which led to much superior photocatalytic performances as well. Last, the highest 
activity was observed over BC-873-5 and approximately 91.49% of MG degradation efficiency was
activity was observed over BC‐873‐5 and approximately 91.49% of MG degradation efficiency was 
achieved after irradiating for 180min.The control experiments were also carried out and the results
achieved after irradiating for 180min.The control experiments were also carried out and the results 
are shown in Figure 7b, from which one can see that when the substrate was used, approximately
are shown in Figure 7b, from which one can see that when the substrate was used, approximately 
29.93% of MG was degraded. Moreover, if no catalyst was added or no light used, the degradation 
efficiencies of MG decreased to 14.66% and 6.3%, respectively, which confirmed the key role of both 
Coatings 2018, 8, 14 8 of 10

29.93% of MG was degraded. Moreover, if no catalyst was added or no light used, the degradation
Coatings 2018, 1, 14 
efficiencies of MG decreased to 14.66% and 6.3%, respectively, which confirmed the key role of 8 of 10 
both
photocatalyst and light. Besides, the reaction rate constants of the samples for MG degradation were
photocatalyst and light. Besides, the reaction rate constants of the samples for MG degradation were 
obtained according to the method described in the literature [23] and were summarized in Table 1.
obtained according to the method described in the literature [23] and were summarized in Table 1. 
The reusability of the photocatalyst coating was also investigated by selecting BC-873-5 as the
The reusability of the photocatalyst coating was also investigated by selecting BC‐873‐5 as the 
example. The repeated experimental results are shown in Figure 7c, from which it can be noticed that
example. The repeated experimental results are shown in Figure 7c, from which it can be noticed that 
the photocatalytic activity of BC-873-5 reduced by a certain extent after three cycles, in spite of this,
the photocatalytic activity of BC‐873‐5 reduced by a certain extent after three cycles, in spite of this, 
the degradation efficiency for MG was still maintained above 80%. These results evidently proved the
the degradation efficiency for MG was still maintained above 80%. These results evidently proved the 
validity of the coating as excellent and easily recycled photocatalysts for organic dye degradation.
validity of the coating as excellent and easily recycled photocatalysts for organic dye degradation. 

Figure 7. The degradation efficiencies of MG solution over the series of Bi2O3 photocatalyst coatings: 
Figure 7. The degradation efficiencies of MG solution over the series of Bi2 O3 photocatalyst coatings:
(a) after irradiating for 180 min; (b) control experiment results; and (c) the reusability of BC‐873‐5. 
(a) after irradiating for 180 min; (b) control experiment results; and (c) the reusability of BC-873-5.

Table 1. The reaction rate constants of the samples. 
Table 1. The reaction rate constants of the samples.
Samples Rate Constants (min−1)
Samples
BC‐673‐2  0.0091 (min−1 )
Rate Constants
BC‐673‐5 
BC-673-2 0.0115 
0.0091
BC‐673‐10 
BC-673-5 0.0109 
0.0115
BC‐773‐2 
BC-673-10 0.0092 
0.0109
BC-773-2
BC‐773‐5  0.0092
0.0113 
BC-773-5
BC‐773‐10  0.0113
0.0104 
BC-773-10
BC‐873‐2  0.0104
0.0125 
BC-873-2
BC‐873‐5  0.0125
0.0150 
BC-873-5 0.0150
BC‐873‐10  0.0137 
BC-873-10 0.0137
BC‐973‐2 
BC-973-2 0.0109 
0.0109
BC‐973‐5 
BC-973-5 0.0125 
0.0125
BC‐973‐10 
BC-973-10 0.0117 
0.0117

4. Conclusions 
Bi2O3 photocatalyst coatings were developed via a ball milling followed by the thermal oxidation 
method. Oxidation under different temperatures and times resulted in quite different compositions 
and structures, which affected the related performances. The results showed that monoclinic Bi2O3 
coatings were obtained at 673 or 773K for 2h, while oxidation at a higher temperature and a longer 
Coatings 2018, 8, 14 9 of 10

4. Conclusions
Bi2 O3 photocatalyst coatings were developed via a ball milling followed by the thermal oxidation
method. Oxidation under different temperatures and times resulted in quite different compositions and
structures, which affected the related performances. The results showed that monoclinic Bi2 O3 coatings
were obtained at 673 or 773 K for 2 h, while oxidation at a higher temperature and a longer time resulted
in mixed-phase Bi2 O3 coatings. Moreover, Bi2 O3 coatings with radial growth structure assembled
by nanosheets could be easily realized at a lower temperature lasting for longer time, while those
with a tangential growth structure could be simply achieved by controlling the temperature at a
higher level accompanied by a relatively shorter oxidation time. Photo-degradation of malachite
green solution under simulated solar irradiation demonstrated that the developed coatings possessed
good photocatalytic activities and cycle performances. The easily recycled coatings provide a type of
visible-light-driven photocatalyst suitable for practical water treatment application.

Acknowledgments: This work is supported by the Youth Innovation Foundation of Tianjin University of Science
& Technology (No. 2015LG11), the Innovation Team Program of Tianjin University of Science & Technology
(No. 10117), and the National Nature Science Foundation of China (No. 51404170).
Author Contributions: Lijun Cheng conducted the experiments and was the lead author. Liang Hao was the
internal guider and Yun Lu was the external consultant.
Conflicts of Interest: The authors declare no conflict of interest.

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