Magnetically separable chicken feathers: A biopolymer based heterogeneous catalyst for the oxidation of organic substrates

Article abstract of DOI:10.1039/c6ra03978b

Magnetically separable poultry chicken feathers were found to be an efficient, green and heterogeneous catalyst for the oxidation of alcohols and sulfides to the corresponding carbonyl compounds and sulfoxides, respectively using t-butyl hydroperoxide (TBHP) as oxidant with complete selectivity and high conversions. The developed catalyst exhibited higher stability, activity and better recycling ability than the bare magnetic nanoparticles. The designed catalyst could readily be recovered using an external magnet without showing any significant leaching during the reaction.

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Magnetically separable chicken feather: a biopolymer based
heterogeneous catalyst for oxidation of organic substrates
Padma L. Patnam,a Mukesh Bhatt,a Raghuvir Singh,b Sandeep Saranb and Suman L. Jaina*
Received 00th January 20xx,
Accepted 00th January 20xx
Magnetically separable poultry chicken feathers were found to be efficient, green and heterogeneous catalyst for
oxidation of alcohols and sulfides to the corresponding carbonyl compounds and sulfoxides, respectively using t-butyl
hydroperoxide (TBHP) as oxidant with complete selectivity and higher conversions. The developed catalyst exhibited
higher stability, activity and better recycling ability than the bare magnetic nanoparticles. The designed catalyst could
readily be recovered by external magnet without showing any significant leaching during the reaction.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Recently, the use of magnetic nanoparticles (MNPs) as Chicken feather is made up of polypeptide chains which are
heterogeneous catalyst in organic transformations is receiving environmentally green, abundantly available, inexpensive and
considerable interest. The main advantage of these catalysts renewable. It holds the potential to act as a support and also
lies in the fact that the magnetic nanoparticles can be as source of various functional groups like -COOH, -NH2, -SH
efficiently isolated from the reaction mixture through a simple and –OH for various important chemical reactions. However
magnetic separation using external magnet. However, the the use of chicken feathers in catalytic applications is rarely
main problem1-3 associated with MNPs is their agglomeration known in the literature.19
and oxidation by air, which can adversely affect their catalytic
Selective oxidation of alcohols and sulphides to
activity. These problems can be overcome by coating of corresponding aldehydes/ketones and sulfoxides is one of the
magnetic nanoparticles with an organic or inorganic core. most significant transformations in organic chemistry.3,20-21
These coatings not only prevent agglomeration but also Traditionally, a number of stoichiometric oxidants such as
provide a barrier to prevent oxidation of MNPs. So far several chromium(VI) reagents, permanganates, metallic salts and N-
natural and synthetic polymers have been used in the chlorosuccinimide (NCS) are known; however, these reagents
preparation of coated MNP.4
Chicken feather, a waste material is a cheapest, biodegradable environmental problems.22-23 Subsequently
generate a huge amount of undesirable wastes which causes
number of
a
and natural biopolymer produced in large amounts from noble24 and non-noble metal25 based catalysts in combination
poultry industries. It is mainly (> 90%) composed of the protein with greener oxidants such as molecular oxygen, hydrogen
keratin, bio polymer with a high degree of cysteine cross- peroxide and t-butyl hydroperoxide (TBHP) have been
linkings.5-6 In the recent decades, increasing environmental reported. However, limited efficiency, requirement of basic
concerns have led interest towards the potential uses of additives, difficult separation of catalysts and poor product
renewable resources.7-9 Their limited applicability and tedious yields are certain drawbacks.26 Thus, considering the economy
disposal procedures are becoming a major concern in the and environmental friendliness, it is highly desirable to
recent decades.10 Chicken feather has been found to be a high develop less expensive, easily separable, reusable non-noble
performance material in various fields; for instance, in making heterogeneous catalysts, particularly, based on bio-derived
plastics, as a sorbents, feather meal and other products.11-13 materials under base-free conditions using green oxidants and
Recently researchers have found potential applications of green media (e.g., water) as the solvent. In this context,
waste feathers by converting them into biodegradable several biodegradable supports such as chitosan27, wool,28
polymers for expending the industrial applications.14-16 In cellulose,29 and starch30 have been reported. In addition, the
addition to these applications, feather keratin has widely been presence of magnetic element in heterogeneous catalysts is
used for developing water-resistant thermoplastic materials additionally desirable owing to their facile and efficient
for various applications.17-18
magnetic separation after reactions.31
In the present paper we report the successful synthesis of
magnetically separable chicken feather (Fe3O4@CF) and its
application as heterogeneous catalyst for oxidation of various
alcohols and sulfides using TBHP as oxidant (Scheme 1).
aChemical Sciences Division, CSIR-Indian Institute of Petroleum, Mohkampur
Dehradun-248005; Email: suman@iip.res.in; Tel: 91-135-2525788
bAnalytical Sciences Division, CSIR-Indian Institute of Petroleum, Mohkampur
Dehradun-248005
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concluded that the Fe3O4@CF nanoparticles were successfully
obtained along with a strong interaction between amine
groups of the supported CF with Fe3O4 nanoparticles.
R
H
R
H
OH
O
CH2OH
CHO
Fe3O4@CF
H2O, 60 oC, TBHP
R''
R''
O
S
S
R'
R'
R'
R'
Scheme 1: Fe3O4@CF catalyzed oxidation reactions
Result and Discussion
Synthesis and characterization of the catalyst
The required chicken feather coated magnetic (Fe3O4)
nanoparticles were prepared by a hydrothermal method as
proposed by Zhang et al32 with the little modifications (Scheme
2). The obtained heterogeneous chicken feather coated MNPs
denoted as Fe3O4@CF were found to be quite stable without
their agglomeration and could easily be recovered by external
magnet without any detectable leaching.
Fig. 1 FTIR spectra of: a) bare MNP; b) bare CF; c) Fe3O4@CF
Afterwards, the crystalline structure of Fe3O4@CF was
determined by XRD. As shown in Fig. 2a, CF has amorphous
structure, however, in Fe3O4@CF (Fig. 2b) the characteristic
diffraction peaks (2θ = 30.21o, 35.61o, 43.31o, 53.8o, 57.31o and
63.01o) corresponding to the (220), (311), (400), (422), (511)
and (440) reflections of cubic spinel structure with Fe3O4 phase
confirmed the successful formation of CF coated MNPs.33
Scheme 2: Synthesis of Fe3O4@CF nanoparticles
The structural changes after the modification of magnetic
nanoparticles with CF (Fe3O4@CF) were determined by FTIR as
shown in Fig. 1. Fig. 1a, shows the FTIR spectrum of bare
MNPs. The observed band at 579 cm-1 is associated with the
stretching vibration of Fe-O. Further two bands around 3426
and 1635 cm-1 ascribed to the stretching and bending
vibrations of surface hydroxyl groups, respectively. Fig. 1b
represents the FTIR spectrum of bare chicken feather. The
absorption peaks at 1647, 1536 and 3423 cm−1 are attributed
to the characteristic absorption bands of the amide I and
amide II and (-NH, -OH) stretching, respectively. However, in
the FTIR spectrum of Fe3O4@CF (Fig. 1c), an additional peak at
around 579 cm−1, corresponding to the Fe-O vibrations
confirmed the presence of iron NPs (Fig. 1c). The peak shifting
of bending vibration of amide I and amide II from 1647 and
Fig. 2 XRD patterns of: a) bare CF; b) Fe3O4@CF
The morphology of the synthesized Fe3O4@CF catalyst was
initially determined by transmission electron microscopy
(TEM). However, the TEM image (Fig. 3a) did not provide
appropriate information; hence we analyzed the sample by
HR-TEM as shown in Fig. 4. Fig. 4a-c, clearly indicates the
homogeneous distribution of black coloured CF coated MNPs
with a narrow size distribution in the range of 3-15 nm. The
SAED pattern in Fig. 3b exhibited a number of rings which
1536 cm-1 to 1641 and 1515 cm-1 respectively was most likely
,
due to the interaction of amide groups of feather with metal
nanoparticles (Fig. 1c). Furthermore, the peak at 1072 cm-1
corresponding to C-O stretching vibration of –OH of chicken
feather is disappeared in modified feather due to the
interaction with MNPs (Fig. 1c). Based on these results, it was
clearly indicates
a highly polycrystalline nature of the
magnetite without the presence of any other crystalline
phases. Furthermore, the elemental composition as
determined by EDX analysis (Fig. 3c, 5d) indicates the presence
2 | J. Name., 2012, 00, 1-3
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of C, O and Fe elements in the synthesized Fe3O4@CF. Images
of elemental mapping of C, Fe and the combined composition
(Fig. 5a-c) clearly reveal the presence of iron oxide
nanoparticles bounded with CF.
Fig. 5 Elemental mapping of Fe3O4@CF for (a) C ; (b) Fe; (C) mixture of C, Fe; d) EDX
image of Fe3O4@CF.
The surface textural properties of the synthesized material
Fe3O4@CF was determined by N2 adsorption/desorption as
shown in Fig. 6. The N2 adsorption/desorption isotherms of the
core–shell magnetic Fe3O4@CF nanoparticles showed a curve,
and the BET surface area, BJH pore volume and pore size was
found to be 59.71 m2/g, 0.16 cm3 g-1 and 3-15 nm, respectively.
The loading of iron in the synthesized catalyst was found to be
27 wt % (1.6 mmol/g) as determined by ICP-AES analysis.
Fig. 3 a) TEM image; b) SAED pattern; c) EDX of Fe3O4@CF
Fig. 4 HR-TEM images of Fe3O4@CF; a, c) of fresh catalyst; b) particle size distribution
in fresh catalyst; d) recovered catalyst after 10 run.
Fig. 6 N2 adsorption/desorption isotherms of Fe3O4@CF and the Insert is the
corresponding pore size distribution
Catalytic activity
After the successful synthesis of Fe3O4@CF, we intended to
explore the catalytic activity of the catalyst for oxidation of
alcohols using aqueous TBHP as oxidant. 4-methoxy benzyl
alcohol was chosen as a model substrate to perform the
optimization experiments by varying the reaction parameters.
The results of these experiments are summarized in Table 1.
Initially the reaction was carried out in different solvents such
as acetonitrile, dichloromethane n-hexane, chloroform and
water as shown in Fig. 7. Among the various solvents studied,
water was found to be
a promising solvent for this
transformation which further makes the developed protocol
more attractive from environmental and economical
viewpoints. The enhanced activity of the CF coated MNPs in
water is most likely due to the possible strong hydrogen
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bonding between water molecules and amino acid chains.
Owing to this bonding the amino acid chain may get stretched
and provide more accessibility of active iron sites to the
substrate molecules. However the organic solvents such as
chloroform, dichloromethane, owing to their inability to form
hydrogen bonding with functionalities of CF showed poor
efficiency of this transformation.
substituted with electron-donating groups (Table 2, entries 4-
5) were found to be more reactive and required lesser reaction
time in completion of the reaction as compared to those
having electron withdrawing substituents (Table 2, entries 7-
9). Furthermore, chicken feather coating enhances the stability
as well as catalytic efficiency of the MNPs, resulted to nearly
two times higher activity than the bare MNPs for oxidation of
4-methoxy benzyl alcohol under identical reaction conditions
(Table 2, entry 5). This enhancement is probably due to the
interaction of functional groups of CF with substrate molecule
through hydrogen bonding, which probably helps in
abstracting the proton from alcohol molecule. Bare chicken
feather (CF) without magnetic core did not show any activity
for the oxidation of alcohol under otherwise similar reaction
conditions (entry 5). This finding suggests that iron is the main
active catalytic site for this transformation. Furthermore, we
investigated the oxidation of secondary alcohols such as
benzhydrol, cyclohexanol and cyclopentanol under the
optimized reaction conditions (Table 2, entries 10-12).
Secondary alcohols were selectively converted to the
corresponding carbonyl compounds without any evidence for
the formation of any by-product.
Fig. 7 Effect of solvent
Further, we checked the effect of catalyst loading by varying
the catalyst amount from 0.2 to 2 mol % (Table 1, entry 1-4)
under otherwise identical experimental conditions. The
conversion was found to be increased with increasing the iron
loading from 02 to 1.0 mol% (Table 1, entry 1-3); however
further increase in loading did not influence the yield to any
significant extent (Table 1, entry 4). A very poor conversion
was obtained in the absence of catalyst under otherwise
identical reaction conditions (Table 1, entry 5). Further, the
effect of reaction temperature was investigated. The reaction
was found to be very slow at room temperature (Table 1, entry
6); however 60 °C was found to be optimum and gave
maximum conversion of 4-methoxy benzyl alcohol to aldehyde
with 97% isolated yield. Further increase in temperature (80
°C) afforded the poor yield (Table 1, entry 7) of 4-methoxy
benzaldehyde along with the formation of benzoic acid as
over-oxidation product.
Table 1: Results of optimization experiments.a
Entry
Cat
(mol %)
0.2
Temp.
oC
Time
(h)
2
Conv.
(%)b
58
1
2
3
4
5
6
7
60
0.5
60
2
67
1.0
60
2
97
2.0
60
2
98
5c
1.0
60
12
10
2
1.0
RT
-
1.0
80
72
aReaction conditions: 4-methoxy benzyl alcohol (1 mmol), TBHP (1.5 eq.), at 60 ᴼC
for 3h.; bdetermined by GC-MS; cblank reaction without catalyst.
Next, the scope of the reaction was explored by performing
the oxidation of a variety of aliphatic and aromatic primary
alcohols under the optimized reaction conditions. The results
are presented in Table 2 (entries 1-10). All the substrates were
efficiently converted to the corresponding carbonyl
compounds in good to excellent yields. Benzyl alcohols
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Table 2: Fe3O4@CF-catalyzed oxidation of alcohols
Table 3: Comparison of Fe3O4@CF with known methods
Entry
Alcohol
Product
Yield
(%)b
Substrate
Catalyst/
Oxidant
O2
Solvent
PhCH3
PhCH3
Yield
(%)
Ref.
temp. (ᴼC)
O
O
1
2
OH
OH
98
97
Benzyl
alcohol
RuO2.xH2O/
80 ᴼC
16
76
34
34
CH2OH
CH2OH
CHO
CHO
3
93
1ꢀoctanol
5% Ptꢀ
1%BiꢀAl2O3/
60 ᴼC
O2
34
4
91
Benzyl
alcohol
0.5%
Pd/Al2O3/80
ᴼC
O2
scCO2
87
CH3
CH3
97
51c,
20d
CHO
CH2OH
2ꢀheptanol
2ꢀdecanol
Na2WO4/ 90
ᴼC
H2O2
H2O2
H2O2
TBHP
Solvent
free
95
92
95
88
35
35
36
37
5
e
-
OCH3
OCH3
98f
92
Na2WO4/ 90
ᴼC
Solvent
free
OH
6
7
O
CHO
CHO
O
CH2OH
Benzyl
alcohol
Fe2O3/SBAꢀ
H2O
15/95 ᴼ
C
90
92
OH
OH
Benzyl
alcohol
[Cn*RuIII(C
F3CO2)3‚H2
O] (Cn* )
N,N′,N′′ꢀ
trimethylꢀ
1,4,7ꢀ
triazacyclon
onane)/ RT,
12h
CH2Cl2
CHO
CH2OH
8
9
Cl
Cl
CHO
CH2OH
85
94
NO2
NO2
OH
CH
O
C
10
11
Although the exact mechanism of the reaction is not clear
at this stage, in analogy to the existing reports38 a plausible
mechanism of the reaction is shown in Scheme 3. Based on the
experimental results, it is clear that iron is the active catalyst
for the reaction, which converts to oxo-iron intermediate
through reaction with TBHP. In the next step, oxo-iron
intermediate abstracts hydrogen from alcohol molecule and
transforms it into corresponding carbonyl compound with the
regeneration of the original catalyst as shown in Scheme 3.
Water and t-butanol are formed as by-products during the
reaction.
OH
O
90
93
OH
O
12
aReaction conditions: substrate (1 mmol), catalyst (1.0 mol %), tBuOOH (1.5
eq), at 60 ᴼC for 3h; bIsolated yields; cusing bare MNPs as catalyst; drecycling
experiment u sing recovered bare MNPs; eusing bare chicken feather powder
as catalyst; fyield of corresponding acid while using 3 mmol TBHP, 100 ᴼC
temp. and 6h reaction time. .
tꢀBuꢀOꢀOH
tꢀBuOH
Furthermore, we compared the catalytic activity of developed
protocol with the literature known methods for oxidation of
alcohols using molecular oxygen, hydrogen peroxide and TBHP
as oxidant (Table 3). As shown in Table 3, the reported
methods either use expensive, toxic metallic catalysts or
require tedious synthetic procedures and afforded poor
product yield in comparatively longer reaction time. However,
the present methodology uses a waste material chicken
feather based magnetic nanoparticles which are readily
synthesized, low cost, easily accessible, easily recoverable with
the effect of external magnet, exhibited excellent catalytic
activity and afforded excellent conversions/ yields under
comparatively mild conditions. These benefits make the
developed methodology a facile and promising tool from
environmental and economical viewpoints.
O
Fe
O
Fe
O
O
O
O
O
Fe Fe
O
Fe Fe
O
ꢀH2O
O
R
OH
R'
R'
R
Scheme 3: possible mechanism of the reaction
Oxidation of Sulfides to Sulfoxides
Furthermore, we investigated the oxidation of a variety of
substituted aromatic and aliphatic sulfides under optimized
experimental conditions. The results are summarized in Table
4. We used several sulfides as substrates for oxidation and
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obtained corresponding sulfoxides without by-products such syntheszied catalyst is quite stable. Furthermore, we
as sulfones.
determined the iron content in the recovered catalyst after 10
runs. The loading of iron in the recovered catalyst was found
to be 27 wt % (1.6 mmol/g) as determined by ICP-AES analysis,
which is similar to the fresh catalyst.
Table 4: Fe3O4@CF catalyzed oxidation of sulfides to sulfoxides using aq TBHP as
oxidant.a
O
Fe3O4@CF (1 mol %)
R
S
R'
S
R'
H2O, 60 o
TBHP
C
R
Entry
R
R1
Yield (%)b
1
2
3
4
5
6
7
8
9
n-C3H7
n-C4H9
i-C3H7
C6H5
n-C3H7
n-C4H9
i-C3H7
C6H5
98
97
98
96
97
98
96
94
92
C6H5CH2
C6H5
C6H5
CH3
C6H5
n-C4H9
C6H5CH2
C6H5CH2
C6H5
Fig. 9: FTIR spectra of Fe3O4@CF: a) fresh catalyst; b) recovered catalyst after 10 run
C6H4 (OCH3-p)
aReaction conditions: substrate (1 mmol), catalyst (1.0 mol%), aq. TBHP (1.5
mmol) at 60 ᴼC using water as solvent; reaction time 3 h.; bisolated yield
Experimental Section
Materials
Recycling of the catalyst
Chicken feather was supplied by local poultry farm, the
feathers were cleaned (washed and treated with ethanol),
dried in oven. Feather barbs separated from quill and ground
in a Retsch ball mill to get feather powder. Ferric chloride and
ferrous chloride was purchased from Sigma-Aldrich. All other
chemicals were of the highest available grade and were used
without further purification.
Furthermore, we have tested the recycling of the developed
heterogeneous catalyst by choosing the 4-methoxy benzyl
alcohol as the model substrate. After the completion of the
reaction, the catalyst could be easily recovered by external
magnet and reused for subsequent ten runs. The recovered
catalyst showed an efficient recycling ability without giving any
significant change in the yield of the desired product under
identical reaction conditions (Fig. 8).
Characterization techniques
The synthesized catalyst, bare Fe3O4 and bare CF was
characterized using various analytical techniques. The Fourier
transform infrared (FT-IR) spectra were recorded by the KBr
method with a Perkin Elmer spectrometer between 500 and
4000 cm−1. Samples for XRD analysis was prepared on glass
slide and the diffraction plot of CF, Fe3O4@CF was analyzed
with Bruker D8 Advance diffractometer at 40 kv and 40 mA
with Cu Kα radiation (λ = 0.15418 nm). Scanning electron
microscopy (SEM) was performed by Jeol Model JSM-6340F.
High resolution transmission electron microscopy (HR-TEM) of
the samples was executed using a JEOL JEM 2100 Microscope.
N2 adsorption-desorption using a Micromeritics ASAP2010
instrument of samples evacuated at 200 °C for 4 h was used to
determine specific BET surface area (SBET) and pore volume.
Pore size was calculated from the desorption branch of the
adsorption-desorption isotherms by the Barrett-Joyner-
Halenda (BJH) method. The iron content in catalyst was
analyzed by inductively coupled plasma atomic emission
spectrometer (ICP-AES DRE, PS-3000UV, Leeman Labs Inc,
USA). Sample for ICP-AES was prepared by digesting 0.01 g
catalyst with conc. HNO3 at 70 ᵒC for 30 min to oxidize all
organic materials and leach out iron metal in the oxidized
Fig. 8 results of recycling experiments
In order to check the stability of the catalyst we also
characterized the recovered catalyst after tenth run by FTIR,
HR-TEM and ICP-AES analysis. Fig. 4d, shows the HR-TEM
iamge of recovered catalsyt which seems to be identical with
the fresh one. Furthermore, nearly identical FTIR spectra of
both fresh and recovered catalyst (Fig. 9) indicates that the
6 | J. Name., 2012, 00, 1-3
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Iron oxide nanoparticles were synthesized by co-
precipitation method, in which NaOH solution was slowly
added to the 40 mL solution of ferric chloride (4.86 g, 0.03mol)
and ferrous chloride (2.976g, 0.015mol) and the resulting
mixture was stirred at 60 ᵒC under nitrogen atmosphere.
During this process, magnetite Fe3O4 NPs were precipitated
out which were collected by an external magnet and
subsequently washed with methanol, acetone and deionized
water. The collected MNPs were dried in a vacuum and then
dispersed in deionized water. To this suspension, 3g of feather
powder was added and the mixture was sonicated for
approximately 2h and then stirred for subsequent 5h at room
temperature (30 ᴼC). The obtained Fe3O4@CF material was
separated by external magnet and washed with methanol,
acetone and deionized water to remove impurities. The final
material so obtained was dried at 60 ᴼC under vacuum.
General experimental procedure for oxidation reaction
,
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A 50 mL round bottomed flask was charged with substrate
(1.0 mmol), catalyst (1 mol %), water (5 mL), TBHP (70 wt%
aq.; 1.5 eq) and the resulting mixture was stirred at 60 °C for
3h. The reaction progress was monitored by TLC. After
completion of the reaction, the mixture was cooled to room
temperature and the catalyst was separated by external
magnet. The recovered catalyst was washed with methanol,
dried under vacuum and used for recycling experiments. The
filtrate so obtained was extracted with dichloromethane (20
mL). The organic layer was dried over anhydrous MgSO4 and
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Magnetically separable chicken feather: a biopolymer
based heterogeneous catalyst for oxidation of organic
substrates
Padma L. Patnam, Mukesh Bhatt, Raghuvir Singh, Sandeep Saran
and Suman L. Jain
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