Journal of Physics and Chemistry of Solids: Trung-Dung Dang, Arghya Narayan Banerjee, Quang-Tung Tran, Sudipta Roy
Journal of Physics and Chemistry of Solids: Trung-Dung Dang, Arghya Narayan Banerjee, Quang-Tung Tran, Sudipta Roy
Journal of Physics and Chemistry of Solids: Trung-Dung Dang, Arghya Narayan Banerjee, Quang-Tung Tran, Sudipta Roy
School of Chemical Engineering, Hanoi University of Science and Technology, 1st Dai Co Viet, Hai Ba Trung, Hanoi, Vietnam
School of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749, South Korea
c
Department of Chemical Engineering and Processing, University of Strathclyde, Glasgow, United Kingdom
b
art ic l e i nf o
a b s t r a c t
Article history:
Received 2 February 2016
Received in revised form
24 April 2016
Accepted 3 June 2016
Available online 6 June 2016
By a simple wet-chemical procedure using a permanganate in the acidic medium, diatomite coated with
amorphous manganese oxide nanoparticles was synthesized. The structural, microstructural and morphological characterizations of the as-synthesized catalysts conrmed the nanostructure of MnO2 and its
stabilization on the support - diatomite. The highly efcient and rapid degradation of methylene blue and
methyl orange over synthesized MnO2 coated Diatomite has been carried out. The results revealed
considerably faster degradation of the dyes against the previously reported data. The proposed mechanism of the dye-degradation is considered to be a combinatorial effect of chemical, physicochemical
and physical processes. Therefore, the fabricated catalysts have potential application in waste water
treatment, and pollution degradation for environmental remediation.
& 2016 Elsevier Ltd. All rights reserved.
Keywords:
Diatomite
Permanganate
Manganese oxide
Methylene blue
Methyl orange
Rapid degradation
1. Introduction
Dye from textile, printing industries and other commercial
activities have been a focus of environmental remediation in the
last two decades [13]. Dye-containing waste has been considered
as an important source of water pollution because dyes are highly
toxic, and colored water is undesirable. In addition, some synthetic
dyes are carcinogenic, and difcult to degrade [2].
Methylene Blue (MB) and Methyl Orange (MO) are two of the
normal and popular dyes which were used in industry. MB belongs
to the thiazine class of dyes. It has many uses in a range of different elds and used as a photosensitizer, an antioxidant, an antiseptic, a stain for xed and living tissues. It is also used as an
organic dye to color cotton, wool, acrylic bers and silk. However,
it can result in permanent burns to the eyes of human and animals,
nausea, vomiting, profuse sweating, mental confusion and methemoglobinemia [4].
MO is a good representative of aromatic azo (N N), dyes,
which constitute about half of the total world dye market. Azo
dyes are also a major class of synthetic organic compounds released by many industries such as paper, plastic, leather, food,
cosmetic and pharmaceutical industries. Among environmental
n
Corresponding authors.
E-mail addresses: [email protected] (T.-D. Dang), [email protected],
[email protected] (A.N. Banerjee), [email protected] (S. Roy).
1
Equal contribution.
http://dx.doi.org/10.1016/j.jpcs.2016.06.006
0022-3697/& 2016 Elsevier Ltd. All rights reserved.
pollutants, azo dyes including MO make up a signicant component of organic pollutants in general. Furthermore, such compounds are recognized as potential carcinogens [1,3,5].
Due to these concerns a variety of research has been performed
in recent years to degrade MO and MB from waste waters. Some
physical methods have been tested without adding any material
but using solar irradiation, ultrasonication or generation of radio
frequency plasma in water solution [6]. But traditionally, functionalized and nanosized materials such as Na2SO3, MgO, ZnO, copper, silver doped ZnO, ferric tungsten or nanoscale zero-valent iron
particles [3,711] etc. are added for degradation or decolorization
of these dyes. The most popular catalyst for MO and MB degradation is TiO2 nanomaterial, which are used solely or with
some additives like H2O2, under solar irradiation [1,2,1216]. But
the disadvantage of TiO2 is that that the material is costly and
being a large band-gap material, its photosensitivity is limited to
the wavelengths below 400 nm, i.e. to the ultraviolet region only,
which comprises less than 5% of the overall solar energy spectrum
[17].
Therefore, attention has shifted to nd new and cost-effective
low-bandgap catalysts which function in the visible-light-driven
region, thus expanding the solar photocatalysis into the visible
portion of the solar radiation. In this respect, manganese oxide
(MnO2) and its composites are considered to be highly promising
catalysts for dye degradation, due to their low bandgap (direct
bandgap 2 eV or less [18]). MnO2 which are well known as a
strong adsorbents of metal ions, is naturally found in soils, aquifers
T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
51
3. Results
2. Experiments
3.1. Catalyst characterization
2.1. Synthesis of the catalyst
The catalyst was synthesized using the following steps. At rst,
a solution of 0.1 M potassium permanganate (Sigma-Aldrich, 99%),
was prepared using distilled water. A separate solution of 6.0 M
hydrochloric acid (Sigma-Aldrich) was also prepared. Secondly, 1 g
of diatomite (Sigma-Aldrich, used as received), was mixed in
10 mL potassium permanganate solution. Then 2 ml of 6.0 M HCl is
added to this mixture drop-wise. After the mixture has been
stirred at room temperature for 4 h, amorphous manganese oxide
(MnO2) is formed on the diatomite, which is then separated, washed ve times with DI water and then dried at room temperature
for 48 h. The approximate weight ratio of coating material (MnO2)
on the surface of diatomite was 1.6. A separate set of process steps
were carried out without adding any diatomite. In this case
amorphous MnO2 was precipitated from the solution. This is referred to as control MnO2, and was used to compare the performance of manganese oxide coated diatomite (MOCD). The detail of the synthesis process is furnished elsewhere [44].
2.2. Characterization
The control MnO2, uncoated- and MnO2- coated diatomite are
characterized by x-ray powder diffraction (XRD) using a D8
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T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
Fig. 1. SEM images of diatomite (a); MOCD under permanganate-to-diatomite weight ratio () of 1.6 (b, c) and the elemental mapping (d: Si mapping, e: Mn mapping, f: O
mapping). Inset of (b) represents the magnied image of a single diatomite pore covered with MnO2.
T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
53
Fig. 2. TEM images of diatomite (a); and MOCD under permanganate-to-diatomite weight ratio () of 1.6 (b). HRTEM images and SAED pattern of the hairy parts of MOCD at
two different magnications (c, d).
adye
% d = 1 0 100
adye
(1)
0
adye
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T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
Fig. 3. (a) XRD patterns of diatomite; control MnO2; and MOCD; EDX patterns of diatomite (b) and MOCD (c).
control MnO2 with similar Mn 4 concentration. The average difference of the catalytic performance between MOCD and control
MnO2 is 20% higher for the former. An obvious reason for this is
the porous morphology of the host diatomite matrix, which offers
much higher reactive surfaces for hydroxyl radical formation, as
clearly depicted by the BET surface area measurements furnished
above, and therefore, better degradation of the dye solution.
In this study, the catalytic ability for organic dye degradation of
MOCD is not only tested with Methylene Blue (MB) - a thiazine
class color dye but also with Methyl Orange (MO) - an azo class
color dye. The decolorization of MO by the MOCD composite is
shown in the digital images given in the upper half of Fig. 5(a),
whereas the degradation measurements in terms of UVvis absorption curves are furnished in the lower half of Fig. 5(a). For
comparison, MO solution is degraded with control MnO2 too, with
similar Mn 4 concentrations as MOCD composites.
In a similar way, the analysis of the catalytic performances of
control MnO2 and MOCD, as a function of different added amounts
of catalysts into MO solutions, was performed using Eq. 1, and the
data are furnished in Fig. 5(b), which shows better catalytic performance of MOCD composites over control MnO2, apparently
because of the higher reactive surfaces of the porous diatomite
T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
Fig. 4. (a) The digital photographs of Methylene Blue dye solution at different
amount of catalysts to show color change due to catalytic degradation of MB and
UVvis adsorption spectra of catalytically degraded MB solution treated with
MOCD. Inset shows the molecular structure of MB. (b) Material inuence on catalytic degradation of MB dye using control MnO2 and MOCD.
4. Discussions
The catalytic activity of uncoated diatomite is also tested in a
similar way, but the previous data revealed that bare diatomite
had insignicant efciency in the degradation of color dyes [44].
This is because, under the operating experimental conditions, the
natural pH of the diatomite solution is around 5 (mild acidic) and
the surface charge of diatomite is approximately zero, and hence,
there is no considerable attraction between the diatomite surface
and color dyes [41,48]. Generally, the ionic dyes are removed via a
surface adsorption mechanism, under very high (411) or very low
(o 3) pH values, through electrostatic interaction between surface
charge of the diatomite and ionized dye molecules [41,48].
Therefore, unless the diatomite solution is extremely acidic or alkaline, the dye removal would be insignicant. That is the reason
the diatomite surface is coated with MnO2 nanoparticles to produce strong oxidizing radicals within the dye solution, which
55
Fig. 5. (a) The digital photographs of Methyl Orange dye solution at different
amount of catalysts to show color change due to catalytic degradation of MO and
UVvis adsorption spectra of catalytically degraded MO solution treated with
MOCD. Inset shows the molecular structure of MO. (b) Material inuence on catalytic degradation of MO dye using control MnO2 and MOCD.
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T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
(3)
MnIV , 2HOH
(4)
B) Transfer of electron
) (
(5)
(6)
( MnII,
(7)
(8)
n
Ct
dye
ln i = a t
Cdye
(9)
t
i
where Cdye
is the initial dye concentration and Cdye
is the same at a
degradation time t. a is the pseudo rst order rate constant. A plot
t
Cdye
of ln i vs. t will be a straight line with the slope as a. The
C
dye
above plots for the highest catalyst amount (0.0125 g) for MOCD
(which is having highest degradation rate), and for both MB and
MO degradations are given in Fig. S3 (Supporting data). The graph
is tted with a straight line with the value of a around 0.14 to
0.15 min 1. For other catalysts amounts, the graphs are similarly
well-tted with pseudo rst order kinetic model. Recently, Zhang
and co-authors [53] reported the catalytic degradation of
Fe2O3@MnO2 hybrid catalyst and showed that the degradation
kinetics follow similar pseudo rst order model with a around
0.16 min 1, which is comparable to our values.
Also to understand the relative inuence of catalysts amount
(both MOCD and MnO2) on the dye degradations of both MB and
MO, a relative %-degradation rate is obtained by considering the
T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
5. Conclusions
This study has presented the rapid degradation of a thiazine
class dye - methylene blue and an azo class dye - methyl orange,
under the presence of MnO2-coated Diatomite. The MOCD composite catalyst is produced via a wet-chemical method under
ambient conditions. Both control MnO2 and MOCD show very
good catalytic activity, and with the assistance of them, the degradation rate of MB and MO was promoted considerably, shortening the degradation time to as low as 30 min or less. With respect to control MnO2, MOCD composite shows much better catalytic activity, mainly because of three simultaneous processes,
such as (a) a chemical process, where hydroxyl radicals are formed
via the reduction of Mn(IV) to Mn(II) which consequently degrade
the dye, (b) a physicochemical process, where dye molecules are
intercalated within the layered structure of birnessite MnO2 to
remove the dye from aqueous solution, and (c) a physical process,
57
where higher active surface sites are provided by the porous matrix of the diatomite support to manifest greater surface reactions.
Thus the material and method have potential applications in the
eld of waste water treatment, water splitting and pollution
degradation.
Acknowledgments
This work is funded by Vietnam's National Foundation for
Science and Technology Development (NAFOSTED) (Project Nr.
103.02-2013.76). We thank for the supporting from British Council
and Newton Fund-Researcher Links Travel Grant (ID 172711746).
We also thank Professor S.W. Joo of School of Mechanical Engineering, Yeungnam University and Professor M. A. Cheney of
University of Maryland for insightful discussions.
References
[1] L. Yu, J. Xi, M.D. Li, H.T. Chan, T. Su, D.L. Phillips, W.K. Chan, Phys. Chem. Chem.
Phys. 14 (2012) 3589.
[2] M. Salehi, H. Hashemipour, M. Mirzaee, Am. J. Environ. Eng. 2 (2012) 1.
[3] Y.H. Shih, C.P. Tso, L.Y. Tung, J. Environ. Eng. Manag. 20 (2010) 137.
[4] L. Zhang, Y. Nie, C. Hu, X. Hu, J. Hazard. Mater. 190 (2011) 780.
[5] S.D. Gakakakar, A.V. Salker, Indian J. Chem. Technol. 16 (2009) 492.
[6] I. Miyamoto, T. Maehara, H. Miyaoka, S. Onishi, S. Mukasa, H. Toyota,
M. Kuramoto, S. Nomura, A. Kawashima, J. Plasma Fusions Res. Ser. 8 (2009)
627.
[7] M.A. Tabbara, M.M. El Jamal, J. Univ. Chem. Technol. Metall. 47 (2012) 275.
[8] Ch Girginov, P. Stefchev, P. Vitanov, Hr Dikov, J. Eng. Sci. Tech. Rev. 5 (2012) 14.
[9] S.B. Gajbhiye, Inter. J. Mod. Eng. Res. 2 (2012) 1204.
[10] R. Rahimi, J. Shokrayian and M. Rabbani, 17th Inter. Electronic Conference on
Synthetic Organic Chemistry Proceeding, DOI: http://dx.doi.org/10.3390/ec
soc-17-b018.
[11] A. Ameta, R. Ameta, M. Ahuja, Sci. Rev. Chem. Commun. 3 (2013) 172.
[12] X.T. Zhou, H.B. Ji, X.J. Huang, Molecules 17 (2012) 1149.
[13] K. Bubacz, J. Choina, D. Dolat, A.W. Morawski, Pol. J. Environ. Stud. 19 (2010)
685.
[14] M.N. Rashed, A.A. El-Amin, Int. J. Phys. Sci. 2 (2007) 73.
[15] A. Houas, H. Lachheb, M. Ksibi, E. Elaloui, C. Guillard, J.M. Herrmann, Appl.
Catal. B Environ. 31 (2001) 145.
[16] S.S. Al-Shamali, Aust. J. Basic Appl. Sci. 7 (2013) 172.
[17] U. Diebold, Surf. Sci. Rep. 48 (2003) 53.
[18] B.A. Pinaud, Z. Chen, A.N. Abram, T.F. Jaramillo, J. Phys. Chem. C 115 (2011)
11830.
[19] D.C. Golden, C.C. Chen, J.B. Dixon, Science 231 (1986) 717.
[20] J. Luo, S.L. Suib, Chem. Commun. 11 (1997) 1031.
[21] J. Moon, M. Awano, H. Takagi, Y. Fujishiro, J. Mater. Res. 14 (1999) 4594.
[22] J. Cai, J. Liu, S.L. Suib, Chem. Mater. 14 (2002) 2071.
[23] M.A. Cheney, S.W. Joo, A.N. Banerjee, B.K. Min, J. Colloid Interface Sci. 379
(2012) 141.
[24] M.A. Cheney, R. Jose, A.N. Banerjee, P.K. Bhowmik, S. Qian, J.M. Okoh, J. Nanomater. 2009 (2009), ID 940462.
[25] M.A. Cheney, P.K. Bhowmik, S. Moriuchi, M. Villalobos, S. Qian, S.W. Joo, J.
Nanomater. 2008 (2008), ID 168716.
[26] M.A. Cheney, P.K. Bhowmik, S. Qian, S.W. Joo, W. Hou, J.M. Okoh, J. Nanomater.
2008 (2008), ID 763706.
[27] K.R. Engh, in: M. Howe-Grant (Ed.), Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8, Wiley, New York, 1993, p. 108.
[28] E.I. El-Shafey, M.L.F. Gameiro, P.F.M. Correia, J.M.R. De Carvalho, Sep. Sci.
Technol. 39 (2004) 3237.
[29] A. Ridha, H. Aderdour, H. Zineddine, M.Z. Benabdallah, M. El Morabit, A. Nadiri,
Ann. Chim. Sci. Mater. 23 (1998) 161.
[30] S. Aytas, S. Akyil, M.A.A. Aslani, U. Aytekin, J. Radioanal. Nucl. Chem. 240
(1999) 973.
[31] K. Agdi, A. Bouaid, A.M. Esteban, P.F. Hernando, A. Azmani, C. Camara, J. Environ. Monit. 2 (2000) 420.
[32] A.N. Christensen, B. Lundtoft, I.C. Madsen, J. Am. Ceram. Soc. 84 (2001) 878.
[33] Z.Q. Wen, M. Li, F. Li, S.J. Zhu, X.Y. Liu, Y.X. Zhang, T. Kumeria, D. Losic, Y. Gao,
58
T.-D. Dang et al. / Journal of Physics and Chemistry of Solids 98 (2016) 5058
[44] T.D. Dang, A.N. Banerjee, M.A. Cheney, S. Qian, S.W. Joo, B.K. Min, Colloids Surf.
B 106 (2013) 151.
[45] A. Khataee, S. Bozorg, B. Vahid, T.D. Dang, Y. Hanihefpour, S.W. Joo, Curr. Nanosci. 11 (2015) 129.
[46] A. Nasser, G. Sposito, M.A. Cheney, Colloids Suf. A 163 (2000) 117.
[47] A.N. Banerjee, S.W. Joo, B.M. Kim, J. Nanomater. 2012 (2012), ID 201492.
[48] Y. Aldegs, M.A.M. Khraisheh, M.F. Tutunji, Water Res. 35 (2001) 3724.
[49] A.T. Stone, Environ. Sci. Technol. 21 (1987) 979.
[50] Y. Su, Y. Yang, H. Zhang, Y. Xia, Z. Wu, Y. Jiang, N. Fukuta, Y. Bando, Z.L. Wang,
Nanotechnology 24 (2013) 295401.
[51] K. Dai, H. Chen, T. Peng, D. Ke, H. Yi, Chemosphere 69 (2007) 1361.
[52] N.A. Laou, D. Tassalit, F. Bentahar, Glob. NEST J 10 (2008) 404.
[53] S. Zhang, Q. Fan, H. Gao, Y. Huang, X. Liu, J. Li, X. Xu, X. Wang, J. Mater. Chem. A
4 (2016) 1414.
[54] H. Benhebal, M. Chaib, T. Salmon, J. Geens, A. Leonard, A.D. Lambert, M. Crine,
B. Heinrichs, Alexandra Eng. J. 52 (2013) 517.
[55] M. Hu, K.S. Hui, K.N. Hui, Chem. Eng. J. 254 (2014) 237.