materials

Article
Effective Capture of Carbon Dioxide Using Hydrated
Sodium Carbonate Powders
Yuanhao Cai 1 , Weilin Wang 1,2,3 , Liang Li 1 , Zhaofeng Wang 2,3 , Suying Wang 1 ID
, Hao Ding 2,3 ,
Zhengguo Zhang 1 ID , Luyi Sun 2,3,4, * ID and Weixing Wang 1, * ID
1 School of Chemistry and Chemical Engineering, China Key Laboratory of Enhanced Heat Transfer and
Energy Conservation of the Ministry of Education, South China University of Technology,
Guangzhou 510640, Guangdong, China; ceyhcai@163.com (Y.C.); weilinwang92@gmail.com (W.W.);
liliang628.scut@gmail.com (L.L.); cewangsuying@mail.scut.edu.cn (S.W.); cezhang@scut.edu.cn (Z.Z.)
2 Polymer Program, Institute of Materials Science, University of Connecticut, Storrs, CT 06269, USA;
zhfwang@licp.cas.cn (Z.W.); hao.2.ding@uconn.edu (H.D.)
3 Department of Chemical and Biomolecular Engineering, University of Connecticut, Storrs, CT 06269, USA
4 Department of Biomedical Engineering, University of Connecticut, Storrs, CT 06269, USA
* Correspondence: luyi.sun@uconn.edu (L.S.); cewxwang@scut.edu.cn (W.W.);
Tel.: +86-0486-6895 (L.S.); +86-20-8711-3171 (W.W.)

Received: 27 December 2017; Accepted: 20 January 2018; Published: 24 January 2018

Abstract: The emission of CO2 has been considered a major cause of greenhouse effects and global
warming. The current CO2 capture approaches have their own advantages and weaknesses. We found
that free-flowing hydrated sodium carbonate (Na2 CO3 ) powders with 30 wt % water can achieve a
very high CO2 sorption capacity of 282 mg/g within 60 min and fast CO2 uptake (90% saturation
uptake within 16 min). The results suggest that the alkaline solution resulting from the dissolution of
partial Na2 CO3 can freely attach onto the hydrated Na2 CO3 particles, which provides an excellent
gas–liquid interface for CO2 capture, leading to significantly enhanced CO2 sorption capacity
and kinetics.

Keywords: hydrated sodium carbonate; CO2 capture; free-flowing powders

1. Introduction
Emission of CO2 is identified as the main contributor to global climate change. Reducing the levels
of CO2 in the atmosphere has become a pressing issue worldwide, and capturing and sequestrating
CO2 as an option to decrease levels of CO2 has been widely explored [1–4].
A number of promising materials for CO2 capture were reported [5–10]. The best developed are
probably aqueous amines [11,12], including monoethanolamine (MEA) [13,14] and diethanolamine
(DEA) [15,16]. However, liquid amines have some serious disadvantages, including amine
evaporation [17,18], corrosion to equipment [19], and high energy cost for regeneration [20,21].
A feasible way to reduce the corrosivity and the regeneration energy is to use supported amine
adsorbents [22–26], but the raw materials are currently too expensive to be applied in large-scale
industrial settings [27].
As an alternative to supported amine sorbents, alkali metal carbonates such as K2 CO3 and
Na2 CO3 as solid sorbents have received wide attention with both high sorption capacity and low
cost [28–32]. However, the main problem of using carbonates is their slow reaction kinetics [33–35].
Cooper and co-workers reported that dry K2 CO3 solution (K2 CO3 aqueous solution coated with
hydrophobic silica powders) exhibited significantly increased CO2 uptakes [36], but the recyclability
of this sorbent was poor. It has been generally accepted that K2 CO3 is superior to Na2 CO3 in terms of
both CO2 uptake capacity and kinetics [37–39]. However, using Na2 CO3 will be more competitive for

Materials 2018, 11, 183; doi:10.3390/ma11020183 www.mdpi.com/journal/materials

Materials 2018, 11, 183 2 of 10

large-scale industrial applications because of its lower cost, especially if one can dramatically promote
the rate of the key reaction:
Na2 CO3 + H2 O + CO2
2NaHCO3 (1)

One of the most common approaches to tackle this problem is to disperse Na2 CO3 powders on
solid supports [40,41], but such a strategy also reduces CO2 sorption capacity because the inclusion of
the supports greatly decreases the amount of active components per unit mass [42].
In this report, we demonstrate that support-free hydrated sodium carbonate powders (HSCPs)
prepared by simply mixing a certain amount of water and Na2 CO3 powders exhibit effective CO2
capture. The alkaline solution resulting from the dissolution of partial Na2 CO3 can freely attach into
hydrated Na2 CO3 particles, which provides an excellent gas–liquid interface for CO2 capture, leading
to significantly enhanced CO2 sorption capacity and kinetics. The elimination of supports not only
reduces the overall cost of raw materials, but also increases the CO2 sorption capacity, both of which
are critical for large-scale applications.

2. Experimental

2.1. Preparation of HSCPs

Na2 CO3 (99.8%) was purchased from Tianjin Qilun Chemical Technology Co. Ltd., Tianjin,
China. Na2 CO3 ·H2 O (99%) was purchased from Aladdin Co. Ltd., Shanghai, China. MEA (99%) was
purchased from Jiangsu Yonghua Chemical Technology Co. Ltd., Changshu, China. CO2 (99.9%) was
supplied by Zhuozheng Gas Co. Ltd., Guangzhou, China. All the chemicals were used as received
without further purification. A series of HSCPs with different Na2 CO3 contents were prepared by
thoroughly mixing an appropriate amount of Na2 CO3 and deionized water at room temperature.

2.2. Characterization
X-ray diffraction (XRD) patterns of the samples were recorded using a Bruker D8 diffractometer
(Bruker, Karlsruhe, Germany) with Bragg–Brentano θ−2θ geometry (20 kV and 5 mA), using a graphite
monochromator with Cu Kα radiation.
To measure the CO2 capture capacity of the HSCP samples, 5.0 g HSCP was charged into a 50 mL
container, which was exposed to CO2 using a balloon containing a sufficient amount of CO2 gas (ca. 5 L
with a pressure of ca. 1.05 bar). The amount of CO2 captured by each HSCP sample was measured
using a balance. A muffle furnace (Luoyang BSK Electronic Materials Co. Ltd., Luoyang, China) was
used to regenerate the sorbents at 250 ◦ C for 1 h, which was mixed with water to reform HSCPs.

3. Results and Discussion

Figure 1a shows the CO2 uptake kinetic curves using various HSCPs (labelled as HSCP-X, where X
is the mass percentage of Na2 CO3 in the mixture) as a sorbent at 30 ◦ C. It was found that HSCP-10 to
HSCP-60 had a very low CO2 sorption capacity (<32 mg/g of HSCP). The CO2 uptake capacity rapidly
rose to 156 mg/g when the mass fraction of Na2 CO3 was increased to 65 wt %, i.e., HSCP-65, but it
still suffered from low sorption kinetics. Further increasing mass fraction of Na2 CO3 led to another
significant increase in term of both sorption capacity and kinetics. At the optimum concentration of
70 wt % (i.e., HSCP-70), the CO2 uptake capacity reached 282 mg/g within 60 min, and the t90 (the time
to achieve 90% of this capacity) was only 16 min. This capacity is much higher than that of other
Na2 CO3 -based CO2 sorbents reported in the literature, which varies between 32 and 140 mg/g [43,44].
Although HSCP-75 achieved the highest capacity (286 mg/g), its CO2 sorption rate was relatively slow
and t90 was about 45 min.
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Materials 2018, 11, 183 3 of 10

Figure 1.1. (a)

Figure (a) CO
CO22 sorption
sorption kinetics
kinetics of
of various
various HSCPs
HSCPs at 30 ◦°C;
at 30 (b)conversion
C; (b) conversionratio
ratioofofNa
Na2 CO
2CO33 in
in
variousHSCPs
various HSCPsand anddifferent
differentreaction
reactiontime.
time.

ItIt was
was found
found that
thattoo
toohigh
highaaconcentration
concentrationofofNa NaCO
2
2CO3 in HSCP would actually lower the CO2
3 in HSCP would actually lower the CO2
uptake capacity. When the concentration of Na 2CO3 in HSCP reached 80 and 85 wt %, the CO2
uptake capacity. When the concentration of Na2 CO3 in HSCP reached 80 and 85 wt %, the CO2
uptakecapacity
uptake capacitydecreased
decreasedtoto124 124and
and4646mg/g,
mg/g,respectively.
respectively.Theoretically,
Theoretically, thethe
COCO 2 sorption capacity
2 sorption capacity is
is directly related to the amount of Na 2CO3 in HSCPs when the content of water is more than 14.5 wt
directly related to the amount of Na2 CO3 in HSCPs when the content of water is more than 14.5 wt %
% according
according to Equation
to Equation (1). Thus,
(1). Thus, the conversion
the conversion ratio ofratio
Na2 COof Na 2CO3 is a good indicator of the CO2
3 is a good indicator of the CO2 sorption
sorption behaviour. As shown in Figure 1b, with
behaviour. As shown in Figure 1b, with an increasing mass fraction an increasing mass
of Nafraction of Na2CO3, the
2 CO3 , the conversion
conversion ratio of Na 2CO3 decreased initially, then dramatically increased to a maximum value
ratio of Na2 CO3 decreased initially, then dramatically increased to a maximum value close to 100%
close to
before 100% before
declining again.declining
After 60 again.
min ofAfter 60 min
reaction, of reaction,
HSCP-70 exhibitedHSCP-70 exhibited
the highest the highest
conversion rate
conversion rate (97.1%), which suggested that most of Na 2CO3 was consumed. The HSCPs with a
(97.1%), which suggested that most of Na2 CO3 was consumed. The HSCPs with a low mass fraction
low
of Namass fraction of Na2CO3, such as HSCP-10, also showed a high conversion ratio, in which
2 CO3 , such as HSCP-10, also showed a high conversion ratio, in which Na2 CO3 dissolved in
Na2CO
water to3 dissolved in water
form a solution, duetotoform a solution,
its high degree ofdue to its high
hydrolysis [45].degree of hydrolysis
However, [45]. However,
their corresponding CO2
their corresponding CO 2 uptake capacity is low because of the limited amount of Na2CO3 presented
uptake capacity is low because of the limited amount of Na2 CO3 presented (Figure 1a). The other two
(Figure
sets of data1a).in The other1btwo
Figure sets of the
represent dataconversion
in Figure 1b represent
ratios of Na2 CO the conversion ratios of Na2CO3 after
3 after five and 15 min of reaction.
five and 15 min of reaction. For HSCP-70, its conversion ratio
For HSCP-70, its conversion ratio increased rapidly from 5 to 15 min, but changed increased rapidly fromlittle
5 to 15 min,
from 15but
to
changed little from 15 to 60 min, which suggested that most of Na
60 min, which suggested that most of Na2 CO3 was consumed within 15 min, thus showing a high 2CO3 was consumed within 15

min, thus
reaction showing a high reaction rate.
rate.
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Overall, the above results show show that

that the
the concentration
concentration of of Na
Na22CO3 in in HSCPs
HSCPs has a great
great influence
on CO22 capture,
capture, which
which can
can be explained
explained by the fact that the morphology of HSCPs varies from
aqueous solution and slurry,slurry, to
topowders
powderswithwithananincreasing
increasingNa Na2 CO
2CO33 concentration.
concentration. At
At low
lowNaNa22CO
CO33
concentrations, the
concentrations, the HSCPs
HSCPsexist
existas
asananaqueous
aqueoussolution
solutionororslurry
slurryasasshown
shownininFigure 1b1b
Figure (inset), which
(inset), which is
not ideal for CO
is not ideal for CO capture because of the low gas–liquid contact surface area. However,
2 2 capture because of the low gas–liquid contact surface area. However, HSCP-70 is HSCP-70 is a
asample
sample of of
free-flowing
free-flowingpowders
powders (Figure 2) with
(Figure a much
2) with higherhigher
a much gas–liquid contactcontact
gas–liquid surfacesurface
area. This
area.is
why it has a rapid reaction rate and a high
This is why it has a rapid reaction rate and a high CO 2 uptake capacity.
CO2 uptake capacity.

Figure
Figure 2.
2. Free-flowing
Free-flowing HSCP-70
HSCP-70 from
from aa glass
glass funnel.
funnel.

In order to better understand the mechanism of CO2 sorption by HSCPs, the XRD patterns
In order to better understand the mechanism of CO2 sorption by HSCPs, the XRD patterns
(Figure 3) of various Na2CO3-based compounds were collected, including the reaction products of
(Figure 3) of various Na2 CO3 -based compounds were collected, including the reaction products
HSCP-70 after 0, 5, 15, and 60 min of sorption reaction at 30 °C. The XRD pattern of HSCP-70 was
of HSCP-70 after 0, 5, 15, and 60 min of sorption reaction at 30 ◦ C. The XRD pattern of HSCP-70
very close to the standard pattern of Na2CO3·H2O, which contains only 14.5 wt % water. This
was very close to the standard pattern of Na2 CO3 ·H2 O, which contains only 14.5 wt % water.
indicates that HSCP-70 contains extra water. As such, we also studied the CO2 sorption by pure
This indicates that HSCP-70 contains extra water. As such, we also studied the CO2 sorption by
Na2CO3·H2O, but it exhibited a low CO2 sorption capacity and rate (Figure 4). This suggests that the
pure Na2 CO3 ·H2 O, but it exhibited a low CO2 sorption capacity and rate (Figure 4). This suggests
extra water contained in the sorbent plays a significant role in CO2 sorption. It indicates that the
that the extra water contained in the sorbent plays a significant role in CO sorption. It indicates
reaction proceeds most rapidly and effectively when Na2CO3, H2O, 2and CO2 are present
that the reaction proceeds most rapidly and effectively when Na2 CO3 , H2 O, and CO2 are present
simultaneously. Based on the above results, we propose that the extra water on the surface of HSCPs
simultaneously. Based on the above results, we propose that the extra water on the surface of HSCPs
helps to form a basic alkaline aqueous environment. When CO2 diffuses to the surface of HSCPs, it
helps to form a basic alkaline aqueous environment. When CO2 diffuses to the surface of HSCPs,
reacts with the basic aqueous media. Since the reaction is exothermic, the generated heat triggers the
it reacts with the basic aqueous media. Since the reaction is exothermic, the generated heat triggers
decomposition of sodium carbonate hydrates, meanwhile releasing water to drive the reaction to
the decomposition of sodium carbonate hydrates, meanwhile releasing water to drive the reaction
proceed continuously. In addition, along the reaction of HSCP-70 and CO2, we also found that the
to proceed continuously. In addition, along the reaction of HSCP-70 and CO , we also found that
characteristic peaks of Na2CO3 disappeared gradually, then intermediate2 structures, such as
the characteristic peaks of Na CO3 disappeared gradually, then intermediate structures, such as
Na3H(CO3)2·2H2O (i.e., Na2CO32·NaHCO 3·2H2O) and Na2CO3·3NaHCO3, appeared after reacting for
Na H(CO3 )2 ·2H2 O (i.e., Na2 CO3 ·NaHCO3 ·2H2 O) and Na2 CO3 ·3NaHCO3 , appeared after reacting
five3 and 15 min, respectively. Eventually, virtually pure NaHCO3 formed after 60 min of reaction,
for five and 15 min, respectively. Eventually, virtually pure NaHCO3 formed after 60 min of reaction,
which is expected.
which is expected.
Materials
Materials 2018, 11, x183
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Figure 3.
Figure 3. XRD
XRD patterns
patterns of
ofvarious
variousNaNa2CO
CO3 based
based compounds
compounds and
and the
the reaction
reaction products
products of
of HSCP-70
HSCP-70
2 3
after 0, 5, 15, and 60 min of CO 2 sorption reaction at 30 ◦°C.
after 0, 5, 15, and 60 min of CO2 sorption reaction at 30 C.

The amine-based CO2 capture system is a proven technology that is already commercialized. To
The amine-based CO2 capture system is a proven technology that is already commercialized.
prevent excessive corrosion, typically 30 wt % MEA aqueous solution is used [11]. As shown in
To prevent excessive corrosion, typically 30 wt % MEA aqueous solution is used [11]. As shown in
Figure 4, a 30 wt % MEA aqueous solution showed similar CO2 uptake kinetics initially, but its
Figure 4, a 30 wt % MEA aqueous solution showed similar CO2 uptake kinetics initially, but its overall
overall sorption capacity was relatively low (111 mg/g versus 282 mg/g for HSCP-70). We also
sorption capacity was relatively low (111 mg/g versus 282 mg/g for HSCP-70). We also studied
studied the CO2 sorption capacity of pure water as a control, whose CO2 uptake capacity was ca. 0.7
the CO2 sorption capacity of pure water as a control, whose CO2 uptake capacity was ca. 0.7 mg/g
mg/g (Figure 4).
(Figure 4).
Materials 2018, 11, 183 6 of 10
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Figure 4.
Figure 4. COCO 2 sorption
sorptionkinetics
kineticsof of
HSCP-70, pure
HSCP-70, water,
pure 30 wt
water, % MEA
30 wt aqueous
% MEA solution,
aqueous and
solution,
Figure 4. CO2 2sorption kinetics of HSCP-70, pure water, 30 wt % MEA aqueous solution, and
Na 2 CO 3 ·H 2 O at 30 °C.
and Na2 CO3 ·H2 O at 30 C. ◦
Na2CO3·H2O at 30 °C.

We also studied the CO2 uptake kinetics at different temperatures and the recyclability of
We
Wealso
alsostudied
studiedthethe
CO2CO uptake
2 uptakekinetics at different
kinetics temperatures
at different and the and
temperatures recyclability of HSCP-70.
the recyclability of
HSCP-70. The suitable temperature range for CO2 capture was determined to◦ be 30–50 °C (Figure 5).
The suitable temperature range
HSCP-70. The suitable temperature range for CO 2 capture was determined to be 30–50 C (Figure 5).
for CO2 capture was determined to be 30–50 °C (Figure 5). A higher
A higher temperature will cause excessive evaporation of water in HSCP-70, and a lower
temperature will cause excessive
A higher temperature will cause evaporation
excessiveof water in HSCP-70,
evaporation and a lower
of water temperature
in HSCP-70, andwill
a cause
lower
temperature will cause the formation of Na2CO3·7H2O (as shown in Figure 6), both of which lead to a
the formationwill
temperature of Na
cause
2 COthe
3 · 7H O (as
formation
2 shown
of Na 2in
COFigure
3 ·7H 2 O6),
(asboth
shownof which
in lead
Figure 6),to a
bothlower
of CO
which 2 uptake
lead to a
lower CO2 uptake of HSCP-70. HSCP-70 also exhibited excellent recyclability with little deterioration
of HSCP-70.
lower HSCP-70
CO2 uptake also exhibited
of HSCP-70. HSCP-70 excellent recyclability
also exhibited with recyclability
excellent little deterioration in CO
with little 2 sorption
deterioration
in CO2 sorption capacity and reaction rate after recycling (Figure 7).
capacity and reaction
in CO2 sorption rateand
capacity afterreaction
recycling (Figure
rate 7).
after recycling (Figure 7).
300
300
250
250
(mg/g)

200
uptake(mg/g)

200
10 °C
10 °C
20 °C
150
150 20 °C
30 °C
uptake

30 °C
40 °C
100 40 °C
100 50 °C
50 °C
2 2
CO

50
CO

50
0
0
0 10 20 30 40 50 60 70 80
0 10 20 30 40 50 60 70 80
Time (min)
Time (min)
Figure 5. CO2 sorption kinetics of HSCP-70 at different temperatures.
Figure5.5.CO
Figure CO22 sorption kinetics of HSCP-70 at different
different temperatures.
temperatures.
Materials 2018,
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11,x183
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FORPEER
PEERREVIEW
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Figure6.
Figure
Figure 6.6.XRD
XRDpatterns
patternsof
patterns ofHSCP-70
of HSCP-70at
HSCP-70 at10
at 10and
10 and30
and 30◦°C.
30 °C.
C.

300
300

250
250
(mg/g)
uptake(mg/g)

200
200
CO2 2uptake

150
150 cycle11
cycle
cycle22
cycle
100
100 cycle33
cycle
CO

50
50

00

00 10
10 20
20 30
30 40
40 50
50 60
60
Time (min)
Time (min)

Figure7.
Figure
Figure 7.7.Recycling
Recyclingperformance
Recycling performanceof
performance ofHSCP-70
of HSCP-70after
HSCP-70 afterregeneration
after regenerationat
regeneration at 250◦°C.
at250
250 °C.
C.

4.4.Conclusions
Conclusions
Insummary,
In
In summary,we
summary, wehave
we havedemonstrated
have demonstrated
demonstrated that
that
that support-free
support-free
support-free HSCPs
HSCPs
HSCPs can
cancan be used
be be
used used as effective
effective
as effective
as sorbents
sorbents for
sorbents
for
CO CO
capture
for 2CO 2 capture
2 capturewith with a
a high
with high capacity
capacity
a high (282
(282
capacity (282 mg/g)
mg/g)
mg/g)andand fast
andfast sorption
fastsorption rate
sorptionrate (90%
rate(90% saturation
(90%saturation uptake
saturationuptake within
uptake within
within
16min).
16
16 min).The
min). The
The elimination
elimination
elimination of support
of support
of support
and theand
andlow the
cost
the low
of Na
low cost
2 CO
cost of Na22CO
3 make
of Na COthis make this
this technology
3 technology
3 make
technology
more more
competitive
more
competitive
for large-scalefor
competitive for large-scaleapplications.
applications.
large-scale applications.
In Inaddition,
addition, based
In addition, basedon
on the reaction
based on thereaction
reaction
principles,
the HSCPsprinciples, HSCPs
should HSCPs
principles, also haveshould
high
should
also have
potential
also havein high potential
capturing
high potential in
other capturing other
acid gases,other
in capturing acid
including gases, including
SOx, NOx,
acid gases, SOx,
H2 S,SOx,
including and Cl NOx, H S, and
2 . H2S, and Cl2.
NOx, 2 Cl 2.

Acknowledgments:This
Acknowledgments:
Acknowledgments: This research
Thisresearch isissponsored
research sponsored
is sponsoredbythe
by the National
byNational Natural
the National
Natural ScienceScience
Natural
Science Foundation
Foundation ofChina
China(21176093
Foundation
of (21176093
of China
(21176093
and and 21676107).
21676107). L.S. L.S. acknowledges
acknowledges the thesupport
partial partial support
by the by the
Air AirOffice
Force Force of
Office of Scientific
Scientific ResearchResearch
(Grant
and 21676107). L.S. acknowledges the partial support by the Air Force Office of Scientific Research (Grant
(Grant FA9550-12-1-0159).
FA9550-12-1-0159). The The authors
authors acknowledgeacknowledge
Pinzhen Pinzhen
Lin, Lin, Huang,
Haoxin Haoxin and
Huang, andTan
Zhuyan Zhuyan
for Tanassistance
their for their
FA9550-12-1-0159).
assistance The authors acknowledge Pinzhen Lin, Haoxin Huang, and Zhuyan Tan for their assistance
for this research.
forthis
for thisresearch.
research.
Author Contributions: Weixing Wang and Luyi Sun conceived and designed the experiments. Yuanhao Cai,
Author
Liang
Author Contributions:
Li,Contributions: WeixingWang,
Weilin Wang, Weixing
Suying Wangand
Wang andHao
and LuyiDing
Luyi Sun conceived
Sun conceived and
performed and designed
thedesigned
experimentsthe experiments.
the experiments.
and/or Yuanhao
analyzed Cai,
the data.
Yuanhao Cai,
Liang
Zhaofeng Li, Weilin
Wang, Wang,
Zhengguo Suying
Zhang,Wang,
and and
Hao Hao
Ding Ding
discussedperformed
the the experiments
experiments and data.
Liang Li, Weilin Wang, Suying Wang, and Hao Ding performed the experiments and/or analyzed the data. and/or
Weixing analyzed
Wang, the
Luyi data.
Sun,
Yuanhao
ZhaofengCai, Weilin
Wang, Wang, Zhaofeng
Zhengguo Zhang, andandWang,
HaoandDingHao Ding wrote
discussed the manuscript.
the experiments
experiments All authors
and data.
data. Weixing discussed the
Wang, Luyi
Luyi
Zhaofeng Wang, Zhengguo Zhang, Hao Ding discussed the and Weixing Wang,
results and
Sun, Yuanhao commented
YuanhaoCai, on
Cai, Weilin the
Weilin Wang,manuscript.
Wang, Zhaofeng
ZhaofengWang, Wang, andand Hao
Hao Ding
Dingwrote
wrotethethe manuscript.
manuscript.All Allauthors
authorsdiscussed
discussed
Sun,
the results
Conflicts ofand commented
Interest: The on
authorsthe manuscript.
declare
the results and commented on the manuscript. no conflict of interest.
Conflictsof
Conflicts ofInterest:
Interest:The
Theauthors
authorsdeclare
declareno
noconflict
conflictof
ofinterest.
interest.
Materials 2018, 11, 183 8 of 10

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