Академический Документы
Профессиональный Документы
Культура Документы
http://web.icf.ro/rrch/
Oxidic compounds of NiFe2O4 type were synthesized by sol-gel autocombustion method. Reaction in solid phase was monitored by
infrared spectroscopy. The structure of synthesized compounds was investigated by IR, XRD and SEM. It was found that these are
structure of cubic spinel-type, and the particle size it is of nanometer order, ranging between 22 50 nm. Characterized samples were
catalytic tested for the reaction of hydrogen peroxide decomposition. It was found that catalytic activity of oxidic compounds is
influenced by chelating/fuel agent and thermal treatment.
*
Corresponding autor: alexandra.iordan@uaic.ro
844 Anca Mihaela Dumitrescu et al.
Thermal treatment at
Obtaining the solution Obtaining Drying 250oC (1 h), 300oC (1 h), Characterization
Combustion Catalytic behavior
of metal precursors the gel the gel 350oC (1 h), 500oC (5 h), (IR, SEM, XRD)
700oC (7 h), 900oC (9 h)
Solution of metallic precursor was obtained by mixing, in Scanning electron microscopy (SEM) images were obtained in
stoichiometric ratio, of Fe(NO3)3 9H2O, Ni(NO3)2 6H2O a Quanta 200 apparatus with EDAX system of elemental
and a chelating/fuel agent: citric acid (C8H12O7), cellulose analysis.
((C6H10O5)n) and mixing cellulose-citric acid. Molar ratio Characterized samples were catalytic tested in the reaction
between Ni2+ and Fe3+ cations was 1:2, and between metallic of hydrogen peroxide decomposition. Release oxygen
cations in solution and chelating/fuel agent was 1:3. volume/time dependence was monitored at 60 s intervals for
Chelating/fuel agents used for synthesis of oxidic compounds all analyzed samples. The chemical process took place at
with ordered structure have the ability to decrease the sintering ambient temperature and pressure and at pH = 13.4, using for
temperature compared with the ceramic method. Homogenate testing a quantity of 0.2 g catalyst and hydrogen peroxide 3 %.
mixing obtained was stirred until the formation of gel. The gel
was subjected to thermal treatment at different temperature, as
can be seen from the protocol synthesis (Fig. 1).
Solid phase reaction was followed by IR spectroscopy.
RESULTS AND DISCUSSION
Thus, IR spectra were recorded at different stages of synthesis.
The spectra give information about the disappearance of
organic phase and nitrate ion from reaction medium and the
Characterization
position of metal ions in the crystal structure. This information
is useful to determine how the synthesis process should be IR spectra. The IR spectra recorded for oxidic
directed. IR spectra were recorded in the mid infrared range compounds synthesized show that after thermal
(4000 300 cm-1) with Fourier transform (FTIR) using a treatment at 500C, there are no absorption bands
Bruker spectrophotometer TENSORTM 27-type with an anvil
ATR cell and a resolution of 2 cm-1.
characteristic of nitrate or carbonate groups. So, it
Synthesized samples were characterized by XRD and was in discussion wavelength range between 1000
SEM. X-ray diffraction (XRD) patterns were recorded with a 300 cm-1.
Shimadzu LabX 6000 instrument equipped with a graphite
monochromator using a Cu K radiation (=0.15406 nm).
CL-CA CL-CA
1,2
1,2
CL
CL
1,0
1,0
Transmitance (a.u.)
Transmitance (a.u.)
465
CA CA
457
0,8
478
0,8
467
472
542
532
476
0,6 0,6
364
366
474
357 0,4
392
0,4
545
530
368
391 370
357
360
0,2 0,2
548
375
544
376
365
359 351 357
0,0 0,0
1000 900 800 700 600 500 400 300 1000 900 800 700 600 500 400 300
a b
Fig. 2 IR spectra from NiFe2O4 treated at 500C (a) and 700C (b).
Catalytic effect of oxidic compounds 845
311
100
311
* - Fe2O3
440
100
440
* - Fe2O3
80
400
511
400
511
80
220
220
Intensity (a.u.)
60
222
Intensity (a.u.)
* *
222
422
60
533
422
533
622
622
620
444
620
531
* *
444
* *
531
* *
40
40 CL-CA CL-CA
CL
20 20
CL
CA CA
0 0
20 30 40 50 60 70 80 20 30 40 50 60 70 80
2 (degree) 2 (degree)
a b
Fig. 3 XRD for NiFe2O4 treated at 500C (a) and 700C (b) (* - Fe2O3).
It is also shown absorption bands characteristic higher heat treatment temperature does not cause
spinel-type structure (Fig. 2). So, for the samples the disappearance of secondary phase. It is possible
thermal treated at 500C are present broad that this disappeared at temperature above 700C,
absorption bands at 548 cm-1, 545 cm-1 and 532 but such treatment has as result a better ordering of
cm-1 respectively, assigned to the stretching () spinelic network. It does not favor the catalytic
vibrations corresponding to Fe O bonds of properties of synthesized compounds.
tetrahedral sites.5 The same broad absorption bands, From XRD crystallite size and lattice parameter
wavelengths moved slightly larger or smaller, a were calculated (Table 1) using Scherrer
544 cm-1, 530 cm-1 and 542 cm-1 respectively, are 0.94
formula:7 D p = where = 1.5405 ;
presented in the case of ferrites treated at 700C. 1 cos
These shifts are due to metal cations ordering in 2
spinel network, which occurs with increasing of 1 width line diffraction measured at half
2
heat temperature. In the wavelengths range of
375 350 cm-1 are observed absorption bands of maximum intensity; and relation:8
small amplitude, assigned to the stretching () a = d hkl (h 2
+ k2 +l2
where a is the lattice )
vibrations corresponding to Fe O bonds of parameter of the unit cell, dhkl is the distance
octahedral sites. This difference between absorption between two equivalent planes and it was
bands in tetrahedral and octahedral sites of the oxidic
calculated from Bragg relation d hkl = n 2 sin
compounds synthesized is due to different distance
between Fe3+ and O2- ions in the tetrahedral and with n = 1 for cubic system; hkl the reflector plan
octahedral sites.5, 6 Absorption bands in the 480 of crystal.
450 cm-1 are assigned to asymmetrical stretching () From Table 1 it can be observed that using the
vibrations of Ni O bonds. sol-gel autocombustion method for synthesis of
X-ray diffraction. Results obtained by X-ray NiFe2O4 ferrite type allowed the obtaining of the
diffraction of synthesized ferrite are showed in Fig. 3. compounds with nanometer size particles ranging
It can be observed that both for samples treated between 22 35 nm. Increase of heat treatment
at 500C and those at 700C were obtained temperature produced an agglomeration of
compounds with cubic spinel structure but there is crystallites, such as their size increases, but
also a secondary phase identified as iron oxide. It remains in the tens order of nanometers. A larger
was observed also that with increasing of heat agglomeration is observed in the case of
treatment temperature, in NiFe2O4/CA the NiFe2O4/CA samples compared with other samples
secondary phase disappears, obtaining the pure analyzed. This is observed from electronic
compound. For the other two compounds, micrographs showed in Fig. 4.
NiFe2O4/CL and NiFe2O4/CL-CA respectively,
846 Anca Mihaela Dumitrescu et al.
Table 1
Crystallographic data for oxidic compounds of NiFe2O4 type
Sample thermal treated at 500C Sample thermal treated at 700C
Sample Dp Lattice parameter a Dp Lattice parameter a
(nm) () (nm) ()
NiFe2O4/CA 22 8.343 51 8.348
NiFe2O4/CL 25 8.346 39 8.346
NiFe2O4/CL-CA 35 8.324 47 8.341
Table 2
Elemental analysis for oxidic compounds of NiFe2O4 type
Compound NiFe2O4/CA NiFe2O4/CL NiFe2O4/CL-CA
Element 500C 700C 500C 700C 500C 700C
Ni 4.78 4.30 4.37 4.35 4.59 4.48
Fe 13.30 9.25 12.89 12.05 13.93 12.13
O 67.28 60.95 68.02 65.01 68.10 62.35
The lattice parameter calculated from XRD is electrostatic forces between the crystallites of
8.34 , value which is in agreement with literature nanometer sizes and surface tensions from the
data published so far.9, 10 microfiber crystallite interface.11
Electron microscopy. From SEM micrographs Micrographs obtained for samples treated at
obtained for samples treated at 500C could be 700C (Fig. 4) confirm the structure of
observed that NiFe2O4/CA ferrite has porous agglomerate cubic particles for NiFe2O4/CA and
particles of cubic form of different sizes. rod-shapes for NiFe2O4/CL and NiFe2O4/CL-CA.
NiFe2O4/CL and NiFe2O4/CL-CA ferrites have In Table 2 the results obtained by EDAX
rod-shapes of different sizes. This structure is elemental analysis were summarized. It can be
favored by the chelating/fuel agent used cellulose considered that the ratio of 1:2 between metallic
for which SEM micrograph is showed in Fig. 5. cations Ni2+ and Fe3+ is respected. The differences
In practice, the ferrite crystallites grow on the which appear in the case of iron are due to iron
cellulose microfibers. This type of aggregation oxide present as secondary phase.
prevents agglomeration and may be favored by
Catalytic effect of oxidic compounds 847
a b
Fig. 6 Catalytic behavior of oxidic compounds synthesized:
a samples thermal treated at 500C; b samples thermal treated at 700C.
Fig. 7 Catalytic behavior of Fe2O3. Fig. 8 Influence of heat treatment temperature on the catalytic
activity of NiFe2O4/CL.
848 Anca Mihaela Dumitrescu et al.
HOO + HO
. . O2 + H2O
Fe 2+ + HO OH Fe 3+ + HO - + HO
.
. . OH
. HO + 1/2 O 2 + H2O
Fe 3+ + HO OH Fe 2+ + H + + HOO
+ -
H + HO H 2O