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Qumica Verde

Enlaces al artculo Dinmicos

Artculo de visin DOI
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Lnea: 10.1039/C3GC40911B

de 11 Qumica Verde

Citan esto: DOI: www.rsc.org/xxxxxx 10.1039/c0xx00000x

Biocomposite de la degradacin nanostructured

MnO
de Fique para el tinte eficiente
2 y las fibras

un
Martha L. Chacn-Patio, un
Cristian Blanco-Tirado, Juan
P. Hinestroza

y Marianny Y. Combariza

un *

Recibido (en XXX, XXX) Xth XXXXXXXXX 20XX, Xth Aceptado XXXXXXXXX 20XX DOI
: EXTRACTO de 10.1039/b000000x

: informamos el
en situ de nanostructured MnO
2 en fibras de Fique naturales. La
eran MnO
superficie fue dado positivo por exposicin a condiciones alcalinas y aniones del permanganatofibra)
(la4-sntesis
10 introducido en la celulosa de lcali consiguiente va interacciones coulombic. Un procedimiento asistido por el ultrasonido
era usado para reducir MnO
4 y MnO
2 nanoparticles de la produccin (NPs). UV-Vis se difunden reflectance estuvo acostumbrado a
tase la influencia de concentracin del precursor, carga y tiempos de reduccin en la sntesis de
nanostructured MnO2. FESEM proporcion la prueba directa que MnO
2 NPs y los conjuntos podran ser formados
en la superficie de la fibra. La actividad cataltica de nuevo bionanocomposite fue probada del retiro de
15 tinte carmn color ail en muestras acuticas. La 2
fibra
-Fique
MnO
bionanocomposite era capaz de quitar hasta el
98%, en menos de 5 minutos, del color presente en muestras acuticas contaminadas. La espectrometra de masas era

20

usado para determinar la ruta de degradacin del tinte. Adems, encontramos que el bionanocomposite
puede ser reutilizado sin el efecto en la eficacia de degradacin del tinte. El procedimiento relatado abre un
nuevo camino para el desarrollo del biodegradable y los fciles para sintetizar materiales compuestos
capaces de eficazmente degradan contaminadores de aguas residuales industriales. La Introduccin

Qumica Verde Manuscrito Aceptado

Publicado el 19 de agosto de 2013. Descargado por Universidad de Cornell durante 26/08/2013 23:41:46. Los

ARTCULO DE INVESTIGAC

nanorods. MnO
2 NPs solo, dispersado en el agua,
slo caus una pequea decoloracin aproximadamente del 10% despus de 20 m
Tintes de industrias textiles es contaminadores acuticos
Capacidad
et al.
de17El
Polzer
relataron que el uso de MnO
x nanoparticles apoy
principales con trastornar impactos1 ambientales.
A causa de su toxicidad y
50 en el polielectrlito esfrico cepilla para la oxidacin de
de reducir el consumo de luz; los tintes interfieren con la
flavonoid tintes en la presencia de H2 O.2 Segn los autores para la
25 fotosntesis de plantas acuticas que de ah tienen un impacto
aplicacin eficiente de estos materiales bastante colloidal
2
directo
en de oxgeno de fuentes acuticas. Los materiales
el contenido
estabilizacin debe ser conseguido primero para guardar el catalizador activo.
Nanostructured pueden ofrecer eficiente e innovacin
Recientemente, Chandra
et al. 18 relat la degradacin photolytic de
soluciones de problemas ambientales. 3,4
Los
Expresamente,
xidos
manganeso tintes orgnicos por graphene cubierto del Milln
55
2 O3 nanoparticles.
son del gran inters y han demostrado la adsorcin y
observaron la degradacin del tinte despus H 2 O2 adicin e irradiacin
30 nueva mediacin
Numerosospara
procedimientos
usan en los
sintticos
xidos ambientales
con luz UV. El
5
cataltica. Las
propiedades
convenientes
de del manganeso
Nuestro inters a bionanocomposites proviene del hecho que
6
tienen incluso sido
el cual
relat
laser ablation de lser,
ofrecen un local sostenible e inventivo para crear materiales
7
8
sonochemical mtodos, mtodos hidrotermales y sntesis
funcionales nuevos. 19 En la sntesis situ de nanomaterials en 60
9
utilizacin de polielectrlitos.
xidos
Milln
e hidrxidos de Milln 3 + y complejos
superficies
de bionanocomposites
la fibra naturales genuino, tiene en cuenta la mejor
, para crear
4+
35
fcilmente oxidan contaminantes organometallic como Co (II) estabilizacin, el control de la talla y la dispersin de NPs en
10,11
as como contaminantes orgnicos como 12,13,14
contraste con compuestos nanofilled. 20 Non-traditional natural
phenols, tintes, amines aromtico, explosivos y pesticidas.
fibras difciles, como el henequen, sisal y fique, puede ser usado como
substituidos Por ejemplo, Chowdhury
Azul 15
etprob
al. la actividad cataltica de (MB)
65 natural no tradicional matrices para sntesis bionanocomposite
Milln
3O 4NPs hacia la degradacin oxidative de Metileno
debido a su estructura compleja, rea de superficie alta inherente,
40 y Rojo prusiano en el agua, mostrando que despus de un perodo de reaccin
fuerza, durabilidad, elasticidad y resistencia de ropa. La
de 24 horas las propiedades de absorcin UV-Vis del tinte
combinacin de complejo cellulosic fibras con xidos de metal de
las soluciones se hicieron insignificantes. Por otra parte, director
et al. 16
administrativo
transicin de la talla del nanmetro podra proporcionar materiales
biodegradables eficientes convenientes a aplicaciones ambientales.
relat un mtodo hidrotermal para la sntesis de /-MnO
2
70
Los
nanorods y evalu su eficacia en la degradacin de
Fique fibras provienen de las hojas de Frucraea
spp, una planta
45 Rhodamine B y MB. La degradacin cataltica, hasta el 95%, era
indgena a las regiones de Andean de Colombia donde son el
conseguido en 90 minutos despus de la adicin
la mezcla
H
de reaccin
del tinte-MnO
2O 2a de
2
el material de la opcin para fabricar de bramante, cuerda y la Pgina 1
Este diario son la Sociedad Real The de Qumica [ao]

[volumen]
[diario] , [ao],
, 0000 |1

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de 11 Qumica

materiales de embalaje para aplicaciones agrcolas como sacos de

instrumento, con lmparas del halgeno del Tungsteno y
caf. 21 son principalmente formados de la celulosa,
55 Deuterio, fue usado para el anlisis reflectance difuso.
Biocomposite
hemicellulose y lignin con porcentajes del peso que hacen un
Los
anlisis deXRD
XPS yfueron realizados, respectivamente, en una
22 17.5 y 14.5, respectivamente.
promedio 63.0,
geometra del modelo D8 ADVANCE with DaVinci de Bruker
Este papel informa sobre la sntesis de un
diffractometer y radiacin CuK1 y en un JEOL JPS-9000MX
5 material bionanocomposite hecho de MnO 2
espectrmetro
y su aplicacin en la degradacin de carmn color ail. Estas fibras de Fique
y NPs usando la radiacin de MgK como la fuente de
energa.
Los anlisis de la espectroscopia de absorcin atmica
bionanocomposite synergically combinan la superficie alta a la
60
(AAS), en un espectrmetro del Electrn de S4 Thermo equipado
proporcin del volumen de NPs inorgnico con la fuerza y
con una lmpara del ctodo del hueco de manganeso y una llama
biodegradability de una fibra difcil. Demostramos que estos
de aire del acetileno, fueron usados para el Milln quantitation en
10 materiales pueden degradar rpidamente y con eficacia
fibras de Fique despus de procedimiento por NEPC para el
25
carmn color ail a travs de caminos diferentes.
Finalmente,Pruebas
nuestrode
trabajo
El anlisis
de XRF fue realizado
quantitation de metales en matrices
orgnico.
inmovilizado
en
en
una
longitud
de
onda
del
tigre
BRUKER
S8 fluorescencia del rayo X dispersiva
que el uso de nanostructured MnOtambin provee
65
2
Fique fibras tienen una separacin franca en cuenta del
el espectrmetro equip con una alta intensidad el tubo de Rh (4
biocomposite del agua tratada y sus usos subsecuentes y mltiples.
kws), el contador del centelleo (SC) para elementos pesados, el
contador proporcional (PC) del flujo para elementos ligeros y una
15
precisin alta gonimetro mecnico para y 2 medidas. El
anlisis cuantitativo fue realizado usando la calibracin multiuso
70
Quant-ExpressTM
paquete.
Materiales
Pruebas de degradacin del tinte

Experimentales
fibras de Fique Crudas fue proporcionado por la Asociacin de
Productores Fique,
Mogotes, Santander, Colombia. Potasio de
(ail de KMnO
), hidrxido de sodio (NaOH), etanol,
4
cido clorhdrico, carmn y cido actico (CH
3COOH)
fue comprado de Sigma-Aldrich (San Luis, Misuri). Todos los
reactivo fueron usados sin la purificacin adicional. Todas las
soluciones
acuosas estuvieron preparadas usando el agua
25 pretratamiento
de la Fibra
desionizada (18.2 M ).
20 permanganato

Qumica Verde Manuscrito Aceptado

Publicado el 19 de agosto de 2013. Descargado por Universidad de Cornell durante 26/08/2013 23:41:46.

Artculo de Visin DOI

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translation.
Lnea: 10.1039/C3GC40911B

Las pruebas de degradacin carmn color ail fueron realizadas

colocando 1.0
g de MnO
de Fique bionanocomposite en contacto con 50 mL
2- Fibra
75 de la solucin del tinte (20 ppm) durante 5 minutos bajo incentivo
constante. El pH de la solucin del tinte fue variado por la adicin
de
El retiro
Color de por la espectroscopia UV-Vis y
CHCOOH.
fue de
supervisado
3
la identificacin de productos de degradacin fue realizada por la
Espectrometra de masas (MS) usando un Amazonas X,
espectrmetro de la masa de la Trampa del ESI-in de Bruker Daltonics que funcion
80

modo del in negativo con un voltaje capilar de 4.5 kV. Los

espectros de la masa de exploracin llenos fueron adquiridos, por
Un ultrasonido asisti el proceso fue realizado en las fibras crudas
la infusin directa de la muestra, que explora de 80 a 500 m/z. Lan
para eliminar carbonatos, lignin, clorofila, saponins y cualquier
CID experimentos fue realizada para identificar productos de degradacin del tinte. Los Resultados de
23
espectrometra de masas de tndem (MS^)
material sobrante del proceso de retting.
Bransonic
30 bao ultrasnico (Branson Ultrasonics, Danbury, Connecticut, 22 kilohercios,
85
130
W) estuvo acostumbrado sonicate las fibras en el agua
desionizada durante una hora en la temperatura ambiente. Despus
sonication fibras limpias fueron secados y almacenados para el
y la discusin
uso adicional. La Fibra de
cationization
la Fig. 1a representan Frucraea
sppque crecen en 1000 m.a.s.l. en hasta 7 m
35 celulosa de lcali estuvo preparada segn el mtodo descrito
pequea ciudad de Mogotes, Santander-Colombia. Las plantas de Fique cultivan pla
por Wang y compaeros 24
delas
trabajo.
fibras Fique Limpias fueron
90 que produce hojas de hasta 3 m de largo, de las cuales las fibras son
sumergidas en una solucin acuosa de HCl del 5% durante 3 horas
extrado a travs de un proceso de retting mecnico. Despus de
en la temperatura ambiente y se lavaron en el agua destilada.
la extraccin, la longitud de la fibra se extiende de 0.8 a 1 m. La
Posteriormente, las fibras fueron sumergidas en una solucin
fig. 1b ilustra el aspecto de fibras de Fique crudas despus de un
acuosa
de
NaOH
del
6%
durante
3
horas
en
60C
y
secaron
en
80C.
La
sntesis
paso
que limpia el ultrasonido. A fin de sintetizar
con eficacia la
40
2 NPs en cellulosic
matriz
de
MnO
95 era necesario modificar el ambiente electrosttico
Nanoparticle
de la superficie de la fibra donde, debido a la repulsin de
- Iones
precursor de
Cationic Fique fibras fue sumergida en KMnO
Coulomb, la celulosa hydroxyl grupos previene 4la
de24 de la Superficie
4 (2,
. vinculacin
Ladel
modificacin
MnO
5, 10, 30 y 100 mm), y la mezcla fue irradiada con la solucin
es fundamental y lleva a la formacin de O Na
ondas del ultrasonido (22 kilohercios, 130 W) durante 45 minutos.
CH2 - + , a travs de los cuales los iones4-MnO
pueden con eficacia
24
Las
fibras
modificadas
fueron
separadas
de
la
solucin
del
45
100 atan. Agua
seguimos
desionizada
un procedimiento sinttico modificado, basado en grupos
precursor,
lavado
y secado en
60Ccon
durante la noche. La caracterizacin de la Fibra de el que relatado por Shihabudheen
et al. 5Los
en cual solucin del precursor cationi
fique fibras fueron colocados en una mezcla de reaccin que contiene
MnO
4
FESEM anlisis fue llevada en un instrumento de FESEM de
1550 LEO equipado con un detector en la lente. Los microgrficos
50 fueron tomados en 5 kV y las fibras fueron cubiertas del grafito
antes
del anlisis.
El anlisis
elemental, usando una espectroscopia
dispersiva pordel
la energa
rayo X de
(EDX) que el accesorio at al microscopio, fue realizado en 20
kV. Un UV-Vis Shimadzu UV 2401PC
2| Ttulo del Diario
[volumen]
, [el ao],
, 0000

105

con concentraciones variables como visto en la Fig. 1c (el encarte superior). La mezcla de reaccin
fue irradiada posteriormente con la energa del ultrasonido. cavitation acstico produce a radicales
reactivos en el agua y otras soluciones acuosas, que exponen precios muy alto refrescantes y
pueden reducir con eficacia iones metlicos a NPs metlico u xidos metlicos NPs. Por consiguiente para la reduccin sonoc

7+

4+
a milln
, La fig. 1c, no usamos la Pgina 2

Este diario es la Sociedad Real The de Qumica [ao]

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Page 3 of 11

Green Chemistry
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DOI: 10.1039/C3GC40911B

Published on 19 August 2013. Downloaded by Cornell University on 26/08/2013 23:41:46.

10

25

30

35

40

45

50

55

60

Fig. 1 a) Frucraea spp plant, b) clean raw Fique fibers, c) solution pH variation and UV-Vis monitoring of MnO4- (abs 528 nm, 10 mM)
conversion to MnO2 (abs 320 nm) using ultrasonic energy: 1 g of Fique fibers immersed in 10 mM KMnO4 solution (top right insert:
initial appearance of the reaction mixture; bottom right insert: reaction mixture after 45 minutes of sonication).
pH evolution over the reaction span (Fig 1c), shows an steady
increase in solution basicity from 7.2 units at the beginningof the
reaction up to 9.6 units after 45 min. Equation 1 shows hydroxyl
ions as a reaction product of MnO 2 sonochemical assisted
synthesis, hence an increase in reaction solution pH was expected
and indeed observed. Though the change in the reaction mixture
UV-Vis absorptive properties and pH indicates MnO 2 formation
in solution, we also observed that MnO 2 deposition on the fiber
surface always resulted in a substantial change in fiber color from
off-white to various shades of brown (Fig 2a). MnO 2 NPs have
characteristic dark-brown color in solution29 as well as supported
onto surfaces, such as reported by Shihabudheen et al. 5 The
This journal is The Royal Society of Chemistry [year]

65

70

observed change in fiber coloration indicates MnO

2 NPs
formation on the fiber surface.
Fig 2a shows the UV-Vis diffuse reflectance analysis of MnO2
NPs modified fique fibers using raw fibers as reference. Diffuse
reflectance spectra exhibit characteristic MnO2 absorption bands
from 300 to 400 nm,27 which correspond to Mn4+O2- charge
transfer transitions. 30 Decreasing reflectance percentages from
28% to 10% in the spectral range of 300 to 400 nm
correlate directly with initial
MnO concentration. As the MnO44 precursor
concentration increases more MnO NPs are formed on the
2
fibers surface. In fact Mn quantitation
by AAS shows a
maximum of 35% w of Mn on the biocomposite when a precursor
[vol], 0000 |
3
Journal Name, [year],

Green Chemistry Accepted Manuscript

additional reducing agents.26,27

minutes, leads to a decrease in the absorption maximum for
colloidal MnO2 NPs. This is due to the further reduction of Mn4+,
Fig 1c shows the reaction course for the ultrasound-assisted
reduction of the MnO4 anion to MnO2 on Fique fibers, using UVin MnO2, to Mn2+ caused by excessive sonication, as has
28
Vis spectroscopy analysis of the liquid phase. We followed the previously reported.been
In our
experiments optimal irradiation
15
reduction process by monitoring absorbance of the characteristic time
for the ultrasound assisted synthesis of MnO2 NPs is 45 minutes.
UV-Vis wavelengths of 528 and 320 nm for MnO4- and MnO2. It
Further support for MnO 2 formation came from monitoring
is clear from Fig 1c that MnO2 forms at the expense of a decrease
reaction solution pH (Fig 1c). MnO 4- sonochemical reduction
in MnO4 concentration. Complete transformation of MnO4 to
proceeds according with the following reaction:27
MnO2 is achieved after 45 minutes of reaction. Results (Fig 1c 20
and Fig S1 Electronic Supporting Information) indicate that
2MnO4- + 3H2 + 6H+ 2MnO2 + 2OH- + 2H2O (Eq1)
excessive irradiation with ultrasound waves, for more than 45

Green Chemistry

Page 4 of 11
View Article Online

DOI: 10.1039/C3GC40911B

solution of 100 mM MnO4- was used (Fig 2). On the other

5 0,5 mM and 100 mM, respectively. This behavior can be related
hand, the diffuse reflectance UV-Vis spectra also shows considerable
to either an increase in the average size of synthesized
nanostructures or an aggregation process, as reported elsewhere31.
band broadening and a noticeable red shift in the absorption
maximum, from 390 to 460 nm for MnO 4 , for concentrations of

15

20

*Amount of Mn on biocomposite

25

30

35

40

45

50

55

Fig. 2 a) UV-Vis diffuse reflectance spectrum of Fique fibers coated with MnO2 NPs using different MnO4- precursor concentrations; b)
Optical image of the MnO2 modified fibers showing characteristic color and appearance due to MnO2 deposition; Insert below shows Mn
amounts, as percentage weight from AAS analysis, present in the biocomposite after in situ synthesis using various precursor
concentrations.
The XRD patterns of raw Fique fibers and MnO 2-Fique
composites are shown in Fig 3a. The XRD pattern of raw Fique
fibers shows characteristic signals for crystalline cellulose at
21.2 and 15.5. The XRD patterns before and after MnO2 NPs

60

synthesis show that the FWHM of the 21.2 signal, corresponding

to the (0 0 2) plane of cellulose, did not change appreciably
indicating no alteration in cellulose structure during the synthetic
process. Additionally, no signals corresponding to MnO2 were
observed by DRX. This may be due to a small MnO 2 crystallite 65
size or to the presence of an amorphous phase of the MnO 2
deposited on Fique fibers, as has been previously reported.32,33
Albeit UV-Vis and Diffuse Reflectance analysis suggest
successful deposition of MnO2 NPs on the fibers surface, we
relied on XPS measurements to determine the interactions of 70
manganese oxides with the cellulosic matrix at the surface level.
XPS spectrum of the MnO2 bionanocomposite, Fig 3b, shows two
characteristic bands corresponding to the 2p1/2 (659.1 eV) and
2p3/2 (647.3 eV) electrons of manganese.
The measured
separation gap corresponds to 11.8 eV; a gap value that has been 75
previously reported for Mn(IV) in MnO 2.34 However, even
though the 11.8 eV band gap between 2p 1/2 and 2p 3/2 states
confirms the presence of Mn(IV), the actual binding energy states
exhibit a shift of 5.3 eV towards higher binding energies
when compared with binding energies reported in the literature for the
80
same states of Mn(IV) on free MnO2.31 A shift towards higher
binding energies does not necessarily imply an increase in the
oxidation state of manganese, this shift could also indicate
stabilization of Mn(IV) due to coordination with oxygen
atoms from the cellulosic matrix. It has been reported that this 85
coordination phenomenon might be responsible for nanoparticles
4 |Journal Name, [year],
[vol], 0000

anchoring and stabilization in electron-rich surfaces such as

cellulosic supports.35,36 We also observed a broadening of the
XPS bands that could be attributed to the presence of Mn 3+ ions.
IR data (not shown) confirmed the presence of Mn3+ ions in the
synthesized MnO2, which could indeed contribute to the observed
37
XPS band broadening.
At a microscopic level the surface of the fiber displays a
heterogeneous morphology (Fig 4a). Fique fibers, similarly to
other hard fibers, are highly complex structures consisting of
microfibril bundles bonded by lignin, hemicellulose and waxes.
Additionally we observed the presence of helical microfibers,
intertwined with straight fibers along the macrostructure,
characteristic of Fique fibers and responsible for their high
mechanical resistance. This irregular structure provides plenty of
channels, micropores and cavities where nanoparticle
synthesis reactions can occur (Fig 4b). Prior to the fibers in
situ modification, it was possible to identify in the
micrographs discrete units closely joined together to create a
continuous, yet irregular fiber surface (Figs
4a,b). upon fiber
However,
modification there is an evident disruption of the fiber continuous
surface (Fig 4c). Under the synthetic conditions used, the fibers
endure harsh conditions due to an initial base/acid reaction
to form alkali cellulose, followed by immersion on a strong
oxidizing solution of MnO -, which is further subjected to
4

reduction by ultrasound energy. These reaction conditions not

only promote MnO2 deposition, but also the removal of
lignin and hemicellulose whose function is to confer mechanical
strength to cell walls and to the fiber.
Once the nanostructured MnO 2 is deposited on the fiber,
FESEM analyses show that the surface no longer exhibits a
This journal is The Royal Society of Chemistry [year]

Green Chemistry Accepted Manuscript

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10

Page 5 of 11

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10

15

continuous structure. Upon modification it is possible to identify

biocomposite. EDX analysis shows characteristic signals for Mn
single strands of microfibers possibly due to the removal of lignin
electrons at 0.58 and 5.92 eV. 40 We also observe the presence
and hemicellulose (Fig 4c). Our group has noticed a similar effect of signals at 0.19 and 0.58 eV attributed to C and O
41
in Fique fibers modified with gold NPs, where deposition
originated from the cellulosic
matrix.hand, Figs 4e and 4f
On the other
20
conditions are even harsher and include the use of strong alkaline clearly
illustrate the effect of increasing MnO 4- precursor concentration
solutions.38 However, instead of compromising the fiber
on MnO2 deposition and morphological characteristics. Low
precursor concentration (2 mM, Fig 4e) results in an even layer of
structural integrity, surface modification with gold NPs generate
a significant improvement in fiber mechanical properties.
nanostructured MnO 2 deposited on the fiber surface. In the
Some authors hypothesize that bionanocomposites from hard 25 image, discrete amorphous MnO2NPs, with sizes ranging from
fibers improved mechanical strength, when compared to the raw fibers,20 to 80 nm, are easily distinguishable. When a higher
precursor concentration is used (100 mM, Fig 4f) we observe
due to a vulcanization-like effect in which the NPs replace
an intricate network of aggregates instead of discrete
lignin and hemicellulose and act as glue between
39
particles. These aggregates could be responsible for the red
individual strands of microfibers.
Currently, we are working on
MnO
the mechanical measuring properties
of the MnO2-Fique fiber 30 shift of the characteristic
2 absorption band at 400 nm observed in the
nanocomposites.
diffuse reflectance measurements, as discussed above.
Fig 4d shows EDX analysis of a MnO
2-Fique fiber

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Fig. 3 a) DRX patterns of raw Fique fibers and Fique-MnO2 bionanocomposites. b) XPS spectrum of MnO2 bionanocomposites obtained
by sonochemical synthesis.

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Manganese oxides, either as free or supported nanostructures,

depends upon the solutions pH, and literature reports a pH 4-5 as
have been widely used as active materials for organic pollutant75 the point of zero-charge (pH ) for this oxide. At solution values
degradation.42-44 We tested the activity of the MnO2-Fique fiber
below pHpzc the MnO2 oxidepzc
surface is positively charged due to
biocomposite towards degradation of a standard dye in aqueous
formation of Mn-OH2+ groups, while at above pHpzc the MnO2
solution. Indigo carmine, a sulfonated derivative of indigo,
surface is negatively charged due to the presence of Mn-O was used because it has the basic molecular make of indigo-basedgroups.45 Organic pollutant degradation by active metal oxide
textile dyes with the advantage of being water-soluble. Indigo 80 surfaces strongly depends on pollutant approximation to the
carmine is an anionic dye widely used in food, pharmaceutical surface by either direct link or by the presence of the target
molecule in the electric double layer. 46 In a solution with pH 7.0,
and cosmetic applications, which in aqueous solution exhibits
a characteristic indigo blue color and possess a strong
indigo carmine exists as an anion while the MnO2 surface is
absorption band in the UV-Vis region at 600 nm (Fig 5a, b).
negatively charged; consequently interaction dye-active surface is
Initial degradation attempts carried out using 1.0 g of the
85 neither expected nor observed.
biocomposite in contact with a 20 ppm (50 mL) solution of
After adjusting the pH from 7.0 to 2.5, by addition of
indigo carmine at pH 7.0 prove to be unsuccessful. Even after one
CH3 COOH, of a 20 ppm (50 mL) indigo carmine solution
hour of contact no change in the UV-Vis absorbance at 600 of the
placing it in contact with 1.0 g of the MnO and2 -Fique fiber
dye solution was observed. We hypothesize that due to the
biocomposite under continuous stirring, complete color removal
anionic nature of the indigo carmine and the effective surface 90 after a short period of time was observed (Fig 5a). We followed
solution color change by UV-Vis spectroscopy, Fig 5b, and
charge of the MnO2 at pH 7.0, there was no efficient interaction
noticed that the characteristic absorption band of the dye in
of the dye molecule with the nanostructured MnO
2 layer of the
the visible region ( ) almost disappears after five minutes
biocomposite. In fact, the surface charge of MnO 2 strongly
of 600 nm
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contact with the biocomposite (blue trace in Fig 5b). We used the
percentage ratio between the characteristic UV-Vis absorption
band of indigo carmine in solution at 600
nm before and after
contact with the biocomposite (Color Removal (CR) % at 600 nm
= [Absorbance at 600 nm after/ Absorbance at 600 nm before] *
5
100)
as a measure of efficiency in color removal.
Fig 5 shows the dynamics of CR% at 600 nm depending upon
the material of choice (raw, cationized and surface modified fique
fibers) for the reaction. Raw and cationized fique fibers were used
as reference materials. Raw fique fibers showed low dye

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adsorption properties (15%), even after one hour of contact with

the dye solution. On the other hand cationized fique fibers
exhibit, as expected and due to Coulombic interactions, a relative
high interaction with the anionic dye and were able to retain upto
30% of the compound from solution. However, the retained
amount of dye on the cationized fiber does not change with time,
as illustrated by UV-Vis measurements. Additionally, contact
with cationized fibers do not alter solution composition as shown
by ESI(-)-MS analysis of the remnant solution, where only
a signal due to indigo carmine was observed (data not shown).

25

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Fig. 4 a), b) FESEM images of the Raw Fique fiber surface. c) FESEM image of the MnO2-Fique fibers biocomposite. d) EDS analysis
of the biocomposite surface. e) and f) FESEM images of fique fibers with MnO2 NPs showing the effect of different precursor
concentrations on NPs distribution, shape and density, e) 2 mM and f) 100 mM.
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From these observations we conclude that, even though

the cationic cellulosic matrix can adsorb some of the dye in
solution, it cannot degrade it. We also believe that after
cationic fiber impregnation
with MnO
anions,
most of the available

removal, UV-Vis measurements show a maximum CR% at 600 nm

of 98.80% after just 5 minutes of contact. Even though other

groups have achieved similar color removal percentages using
nanostructured MnO 2 dispersed in solution, to the extent of our
positive
4 are linked to MnO4- anions 15 knowledge in these literature reports successful dye degradation
charged sites in the fiber
surface
leaving a very small, or probably none, residual positive charges
is always attained by addition of H2O2 to the reaction mixture. 4750
in the final MnO2-Fique biocomposite, hence any
In all our experiments color removal was achieved without
discoloration effect can be attributed to the presence of the nanostructured
using any additional oxygen source in the solution other than the
one provided by the air and the stirring process.
oxide. When using the MnO2-Fique fiber biocomposite for color

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Fig. 5 a) Dye solution appearance before and after contact with the MnOremoval
2 -Fique fiber biocomposite. b) UV-Vis monitoring of color
from an indigo carmine solution before and after contact with th
e MnO
2 -Fique fiber biocomposite. Insert below shows color
removal percentage (CR% at 600 nm) according to the type of material tested.
We also tested the color removal ability of the MnO
2-Fique
fiber biocomposite over a series of eight usage cycles (Electronic
Supporting Information. Fig S2, Table S1). Results show an
average CR% at 600 nm of 98.020.09 over eight continuous
usage cycles with a maximum CR% of 98.15 and a minimum of
97.92 from the same biocomposite sample. No evidence of
manganese in the remnant solution was observed (AAS limitof
detection for Mn was 0.55 ppm). Data in Fig 5 also indicates a
slightly decrease in CR% when increasing MnO 4- concentration.
For instance, using a precursor concentration of 2 mM results in a
98.80% CR% at 600
nm , while for a precursor concentration
of decreases to 96.05%. This effect,
100 mM, CR % at 600 nm
statistically significant, is related to an increase in the size of the
MnO2 particles, and even to aggregate formation at the fiber
surface, as MnO4- concentration increases (Fig 4f). As the particle
size increases, and aggregates are formed, the surface area of
MnO2 available for interaction with the dye decreases and so does
the color removal efficiency.
However since the above-mentioned reactions were carried out
under a molar excess of MnO2, the catalytic nature of the process
was not evident. To test whether or not the colour removal
reaction was catalytic, we performed a degradation experiment in
which the molar ratio indigo carmine:Mn was 2:1. Using always
the same biocomposite sample (0.0619 g with a Mn content
of 0.36%
w for a total of 4.1x10-06 mol of Mn) and eight different
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samples of indigo carmine solution (200 mL, 8.2x10 -06 mol) we

followed the reaction until complete color removal, which in this
particular case took 10 minutesper cycle. UV-vis results show
and average CR% at 600 nm of 92.444.45 over eight continuous
usage cycles using the same MnO 2-Fique fiber biocomposite
sample (Electronic Supporting Information. Fig S2, Table S1).
As in the previous experiments no evidence of Mn in the remnant
solution was observed. In this particular case, and in order to
determine the effect of repeated usage on the catalytically active
nanostructured MnO layer, we performed quantitative X-Ray
Fluorescence (XRF) 2analyses to determine Mn contents on
the biocomposite sample before and after reaction. Quantitative
XRF analyses show a small decrease in Mn in the biocomposite sample

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20

of 4.5% per cycle, in average. The biocomposite sample tested

had an initial Mn amount of 0.36% w and a final Mn content of
0.23%w, after eight continuous cycles. Even though there is some
loss of Mn from the biocomposite sample, due probably to
nanostructured MnO2 detachment from the fiber surface
because of continuous use, stirring and acidic reaction conditions, these
results strongly indicate a catalytic degradation process.
So far UV-Vis data showed it is possible to remove indigo
carmine by using the MnO2-Fique fiber biocomposite. However,
to fully identify and to establish the existence of indigo carmine
degradation products we recurred to ESI(-) MS analysis. Fig
6 shows ESI(-) mass spectra of indigo carmine before and after
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for ions at m/z 244 and m/z 200 respectively. CID of m/z 244
resulted in two fragment ions at m/z 226 [244-H2O]and
m/z 200
[244-CO2] . We selected m/z 200 and performed a MS^ 3
experiment which in turn produced fragment ions at m/z 172
[200-CO]-and m/z 120 [200-SO3]-. In this fashion, reconstruction
of m/z 244 structure was possible. Recurrent losses of 44 mass
units, observed throughout all MS^nexperiments of the degraded
dye samples indicate abundance of carboxylic acids, which in
turn suggest extensive oxidation of the dye molecule and its
degradation products. By performing successive MS^n
experiments on every signal from the original mass spectrum of
the dye solution, after five minutes of contact with the
biocomposite, we were able to establish degradation product
identification.
Based on MS analysis we propose two main degradation routes
for indigo carmine. Degradation route 1, Fig 7a, starts with
an oxidative cleavage mechanism in which indigo carmine is
oxidized and split in two, to give Product 1. From this initial step

30

follows loss of water and further oxidation reactions, resulting on

Products 2, 3 and 4. On the other hand degradation route 2, Fig
7b, goes through a specific cleavage of the aromatic rings,
51
resulting on Products 5 and 6.
Products 1, 2, 3 and 4 do not
have an extensive conjugated electronic system; consequently
they do not absorb visible light. 52 Products 1 and 2 (Fig 7a), have
been reported elsewhere as result of the photocatalytic
degradation of indigo carmine bynanostructured SnO2. 53

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Combining data from MS^nCID experiments and the proposed

degradation pathways wewere able to account for all of the ions
observed in the full scan ESI (-) MS spectrum of the dye solution
after five-minute contact with biocomposite (Fig 6). In summary,
MS signals from ions below m/z 300 correspond to single anionic
species while signals above m/z 300 correspond to ion clusters.
For example while the singly charged ion at m/z 297 corresponds
to the deprotonated Product 5 (Fig 7 b); the signal atm/z 390
corresponds to a cluster ion formed by a deprotonated Product 6,
plus an Mn 2+ ion and two acetate ions for a net charge of -1. The
same is true for ion at m/z 405, which corresponds to a cluster ion
formed by the deprotonated Product 3 plus an Mn2+ ion and two
acetate ionsfor a net charge of -1. Cluster ion identification
was achieved by CID analysis and experimental isotopic
pattern comparison with theoretical patterns. The Electronic
Supporting Information section (Figs S3-S7 and Table S2-S3) includes CID
MS data for each degradation product and cluster ions and
^2
a summary of observed MS
ion fragments.

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Fig. 6 ESI (-) Mass spectra of an indigo carmine solution before (top left) and after (top right) contact with the MnO
2-Fique fiber
biocomposite. MS^2CID tandem mass spectrum of degradation product at m/z 244 (bottom right), and MS^3CID tandem mass spectrum
8 |Journal Name, [year],
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reaction with the biocomposite, respectively. Before reaction,

ESI(-) MS shows a base peak at m/z 421 corresponding to a
single charged anion of indigo carmine. After a 5 minutes
reaction no signal for indigo carmine m/z
( 421) was registered,
and instead a wide variety of degradation products at lowm/z
values were observed. Collision-induced dissociation (CID)
tandem mass spectrometry allowed identification of each product
observed. Fig 6 also shows MS^ 2 and MS^ 3tandem mass spectra

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of m/z 200 (bottom left), originated from the fragmentation of ion m/z 244.

Conclusions

10

We demonstrated that Fique fibers could be successfully used as

support for the in situ synthesis of nanostructured MnO 2 to
produce a genuine bionanocomposite. The high electron density
on the surface of Fique fibers enabled the deposition and
stabilization of manganese dioxide nanostructures. In addition the
biocomposite was successfully used for indigo carmine
degradation, with a maximum efficiency of 98.80% after just 5

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minutes of contact, by means of oxidative and ring cleavage

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Fig. 7 Proposed degradation routes for indigo carmine: a) Route 1: Oxidative cleavage mechanism. b) Route 2: Specific aromatic ring
cleavage.
a

Escuela de
Qumica, Universidad Industrial de Santander,
Bucaramanga, Santander 680002, Colombia.
b
Department of Fiber Science and Apparel Design, Cornell University, 65
Ithaca, New York 14853, USA.
*Escuela de Qumica, Universidad Industrial de Santander,
Bucaramanga,
Santander
680002,
Colombia.
E-mail:
marianny@uis.edu.co

Acknowledgments
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This work was supported by COLCIENCIAS (Grant RC No. 3732012) and Universidad Industrial de Santander Research ViceThe authors also acknowledge technical chancellors office.
support from the Central Research Laboratory Facility at
Guatiguars Tech Park, Universidad Industrial de Santander,
Piedecuesta-Santander.

Notes and references

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Electronic Supplementary Information (ESI) available: Fig S1

shows UV-Vis spectra of
MnO after 45 minutes of irradiation with
4 solution
ultrasound waves. Fig S2 and Table S1 show data about CR% in
eigth continuous usage cycles using the same biocomposite sample. Figs
S3 to S7 and Table S2 show CID mass spectra of degradation products. Table
S3 lists MS^2 fragments for all signals observed in the full scan MS of the
degradation products of indigo carmine.
See DOI: 10.1039/b000000x/

[vol], 0000 |
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pathways.
We
conclude
that
MnO2-Fique
fibers
bionanocomposite is a promising, environmentally friendly and
easy to synthesize, material for use in contaminated water
treatment.54 Additionally, all of our dye degradation
experiments were carried out without the addition ofoxidizing
agents. To the extent of our knowledge this is the first
report in which a biocomposite of a transition metal
oxide is able to degrade organic pollutants without
supplementary oxygen sources added to the reaction mixture.

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