Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles
We have used the matrix synthesis protocol of Ryoo et al. for the preparation of highly ordered cubic mesoporous carbon (CMK-1) using mesoporous silica (MCM-48) as a template, in order to prepare palladium-doped CMK-1. The carbon obtained has a high surface area of 1800 m2g-1, a large porous volume...
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Інститут хімії поверхні ім. О.О. Чуйка НАН України
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| Cite this: | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles / V. Gerda, G. Telbiz, N. Kobylinskaya, V. Zaitsev, P. Manoryk, J. Fraissard // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 3. — С. 315-320. — Бібліогр.: 25 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860194992148971520 |
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| author | Gerda, V. Telbiz, G. Kobylinskaya, N. Zaitsev, V. Manoryk, P. Fraissard, J. |
| author_facet | Gerda, V. Telbiz, G. Kobylinskaya, N. Zaitsev, V. Manoryk, P. Fraissard, J. |
| citation_txt | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles / V. Gerda, G. Telbiz, N. Kobylinskaya, V. Zaitsev, P. Manoryk, J. Fraissard // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 3. — С. 315-320. — Бібліогр.: 25 назв. — англ. |
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| container_title | Хімія, фізика та технологія поверхні |
| description | We have used the matrix synthesis protocol of Ryoo et al. for the preparation of highly ordered cubic mesoporous carbon (CMK-1) using mesoporous silica (MCM-48) as a template, in order to prepare palladium-doped CMK-1. The carbon obtained has a high surface area of 1800 m2g-1, a large porous volume of 1.14 cm3g-1 and average pore diameter of 3.03 nm. Step-by-step formation of mesoporous carbon was followed by X-ray diffraction, FTIR, N2 adsorption desorption and TPD mass-spectrometry. The physical data of CMK-1 are hardly changed by Pd incorporation (CMK-1/Pd). Transmission electron microscopy and Raman spectroscopy show that the framework of the highly ordered mesoporous carbon/Pd consists of an aligned carbon phase with a graphite mode region. The potential application of CMK-1 and CMK-1/Pd as sorbents for hydrogen storage is discussed.
Мезопористий вуглець, допований паладієм, був одержаний шляхом матричного синтезу з використанням мезопористого кремнезему як темплату. Отримані зразки високовпорядкованого кубічного мезопористого вуглецю характеризуються питомою площею поверхні до 1800 м2/г, великим об’ємом пор до 1,14 cм3/г і середнім діаметром від 3,03 нм. Стадії одержання мезопористого вуглецю та композитного матеріалу контролювали методами рентгенівської дифракції, ІЧ-спектроскопії з Фур'є-перетворенням, низькотемпературної адсорбції азоту та ТПД мас-спектрометрії. Встановлено, що допування зразків паладієм не приводить до руйнування структури матриці; згідно з даними просвічуючої електронної мікроскопії та спектроскопії комбінаційного розсіювання структура високовпорядкованого мезопористого композиту складається з впорядкованої вуглецевої фази з ділянками графіту і наночастинок паладію, інкорпорованого в мезопорах матриці, а композитні зразки показують підвищену сорбційну ємність по водню.
Мезопористий углерод, допированный палладием, был получен методом матричного синтеза с применением в качестве темплата мезопористого кремнезема. Получены образцы высокоупорядоченного кубического мезопористого угля, которые характеризуются большой удельной площадью поверхности 1800 м2/г, большим объемом пор до 1,14 cм3/г и средним диаметром от 3,03 нм. Стадии получения мезопористого угля и композитного материала контролировали методами рентгеновской дифракции, ИК-спектроскопии с Фурье-преобразованием, низкотемпературной адсорбции азота и ТПД масс-спектрометрии. Установлено, что допирование образцов палладием не приводит к разрушению структуры матрицы; согласно данным просвечивающей электронной микроскопии и спектроскопии комбинационного рассеивания структура высокоупорядоченного мезопористого композита состоит из упорядоченной углеродной фазы с участками графита и наночастиц палладия, инкорпорированного в мезопорах матрицы, а полученные композитные образцы показывают повышенную сорбционную емкость по водороду.
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Хімія, фізика та технологія поверхні. 2010. Т. 1. № 3. С. 315–320
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 3 315
UDC 544.723
ENHANCEMENT OF THE HYDROGEN SORPTION
ON MESOPOROUS CARBON BY DOPING
WITH PALLADIUM NANOPARTICLES
V. Gerda1,2, G. Telbiz3, N. Kobylinskaya2, V. Zaitsev2, P. Manoryk3, J. Fraissard1,4
1Laboratoire de Physique Quantique, Université Pierre and Marie Curie, ESPCI
10 Rue Vauquelin, Paris 75231, France, jacques.fraissard@upmc.fr
2Department of Chemistry, Shevchenko Kyiv National University
62a Volodymyrs’ka Street, Kyiv 01033, Ukraine, nkobilinskaya@rambler.ru
3Pysarzhevskiy Institute of Physical Chemistry of National Academy of Sciences of Ukraine
31 Nauky Ave., Kyiv 03028, Ukraine, g_telbiz@yahoo.com
4University Pierre and Marie Curie, 4 Place Jussieu, Paris 75005, France, jacques.fraissard@upmc.fr
We have used the matrix synthesis protocol of Ryoo et al. for the preparation of highly ordered cubic
mesoporous carbon (CMK-1) using mesoporous silica (MCM-48) as a template, in order to prepare pal-
ladium-doped CMK-1. The carbon obtained has a high surface area of 1800 m2g-1, a large porous volume
of 1.14 cm3g-1 and average pore diameter of 3.03 nm. Step-by-step formation of mesoporous carbon was
followed by X-ray diffraction, FTIR, N2 adsorption desorption and TPD mass-spectrometry. The physical
data of CMK-1 are hardly changed by Pd incorporation (CMK-1/Pd). Transmission electron microscopy
and Raman spectroscopy show that the framework of the highly ordered mesoporous carbon/Pd consists
of an aligned carbon phase with a graphite mode region. The potential application of CMK-1 and
CMK-1/Pd as sorbents for hydrogen storage is discussed.
INTRODUCTION
In recent years, much attention has been given
to the synthesis and the physicochemical properties
of mesoporous [1–6] and microporous [7, 8] materi-
als based on carbon. Carbon nanotubes as well as
carbon mesoporous sieves are characterized by high
values of the specific surface area and pore volume,
a narrow pore diameter distribution, high thermal
stability in an inert environment and high conductiv-
ity. In view of the features these ordered mesopor-
ous carbon (CMK-1) can be used as applied materi-
als. Using mesoporous silica as a template is par-
ticularly attractive due to the possibility of structural
order and diversity in achieving novel carbon nano-
architectures. These materials have aroused consid-
erable interest due to their important fundamental
implications and industrial applications as a potential
element of different electronic nanodevices, sensors,
components of selective catalysts and "containers"
for the storage of hydrogen and methane [4–6].
Controlling and functionalizing carbon nano-
structures are key factors in defining their applica-
tions. For example, various transition and noble
metals can be supported by carbon nanostructures
using the wet impregnation technique [9–14]. In-
deed, carbon with a graphitic structure involves a
unique metal-support interaction resulting in quite
distinct catalytic behavior. For example, carbon-Pd
interactions were discussed in terms of Pd particle
size distribution and geometry which, in turn, are
related to hydrogenation activity/selectivity [15, 16].
Experimental and theoretical investigations reveal
controversies concerning the value of hydrogen sto-
rage capacity and the pore characteristics of carbon
materials as well as metal loading [17–19]. In the
present work ordered mesoporous carbons CMK-1
were synthesized using MCM-48 sieve as matrix
according to ref [2, 5]. CMK-1 formation was fol-
lowed step-by-step. The effects of finely dispersed
metallic palladium on the microstructure and prop-
erties of CMK-1 were also investigated. Potential
applications of CMK-1 and CMK-1/Pd as sorbents
for hydrogen storage are discussed.
EXPERIMENTAL
MCM-48 silica was prepared following a hy-
drothermal synthesis procedure using sodium sili-
cate as the silica source [20]. The molar composi-
tion of the starting mixture for MCM-48 synthesis
was 1TEOS:0.54 NaOH:0.5 CTABr:110 H2O. After
homogenization of the mixture and hydrothermal
treatment in autoclave, the product was filtered,
carefully washed in water, dried at ambient tem-
V. Gerda, G. Telbiz, N. Kobylinskaya et al.
_____________________________________________________________________________________________
316 ХФТП 2010. Т. 1. № 3
perature and finally calcined in air at 823 K. After
template removal, the silica was impregnated with
an aqueous solution of sucrose and sulphuric acid
[2, 5]. 5 mg of MCM-48 was mixed with an aque-
ous solution prepared from 6.25 g of sucrose, 0.7 g
of H2SO4 and 30 ml of H2O. The resultant mixture
was dried for 5 h at 373 K and then at 443 K. After
this partial carbonization, the sample was blended
with a solution containing 3.75 g of sucrose, 0.4 g of
H2SO4 and 30 ml of H2O. The resultant mixture
was dried again for 6 h successively at 373 and
443 K. The resultant powder was calcined and car-
bonized under vacuum in a quartz reactor at various
temperatures (973, 1173 and 1373 K). The blackish
composite was obtained in 50% ethanol. The sam-
ple was filtered, washed in ethanol and dried at
373 K. For Pd loading, 0.1 g of mesoporous carbon
was mixed with H2[PdCl4] in acetone solution,
(CPd2+=1.0009 mg/ml). The volume of solution was
varied depending on the degree of Pd loading re-
quired (1 and 5%). The mixture was stirred for 3 h
and dried until the acetone had evaporated. XRD
patterns were obtained with a CuKα source
(DRON-3 M diffractometer).The hydrogen adsorp-
tion capacity was measured with a volumetric device.
100 mg of carbon sample were put in a cell immersed
in a Dewar vessel with liquid nitrogen (77 K) and
pure hydrogen was passed at atmospheric pressure.
After 45 min the solid-hydrogen equilibrium was
reached and the sample cell was isolated. The hydro-
gen adsorption capacity was computed from the
amount of gas desorbed from the material at 313 K.
This experimental procedure avoids any error related
to temperature gradients between the different parts
of the apparatus. The specific surface area and pore
size distribution of the mesoporous materials were
calculated from nitrogen isotherms at 77 K using
DFT model (Micromeritics ASAP 2000) [21]. Be-
fore starting this adsorption, the samples were out-
gassed under vacuum at 423 K during18 hours.
FTIR spectra were obtained on a BRUKER IFS 66
spectrometer. For TEM measurements, powders
were deposited on a grid with a holey carbon film
and transferred to a JEOL 2000 electron microscope
operating at 80 kV. Changes in the amount of gas-
phase products during sucrose carbonization were
recorded by temperature programmed desorption
monitored by a MX-7304 mass-spectrometer.
RESULTS AND DISCUSSION
Fig. 1 shows the X-ray diffraction patterns of
as-synthesized and calcined MCM-48 and sys-
tematic transformation of structure during the
removal of silica framework after carbonization
of sucrose impregnated in the pores of MCM-48.
2 4 6 8 10
In
te
n
si
ty
, a
.u
.
2 theta, degree
3
4
1
5
2
Fig. 1. XRD patterns for MCM-48 and ordered mesopor-
ous carbon synthesized with sucrose and MCM-48
silica: 1 – MCM-48 as synthesis. 2 – MCM-48,
calcined, 823 K; 3 – МСМ-48, С12Н22О11+Н2SO4
at 433 K; 4 – МСМ-48 after vacuum carbonization
at 1173K; 5 – ordered mesoporous carbon
The sharp diffraction peaks (curve 1, 2) show a
good correspondence to cubic Ia3d symmetry im-
plying that the matrix is mesoporous MCM-48. The
product maintained the cubic structure without col-
lapse after calcination at 823 K demonstrating a
good thermal stability. The intensity change in the
XRD pattern (lattice contraction and intencity loss)
illustrated that channel systems separated by the
silica walls were statistically equally filled with car-
bon (curve 3, 4). Structure formed in these porous
systems is obviously disconnected and capable to
change their position with respect to one another
when the matrix is removed. When the silica walls
were destructed, produced CMK-1, a new reflection
corresponding of the (110) carbon networks forbid-
den for cubic Ia3d appears. This result shows
change of symmetry from cubic Ia3d to another
cubic structure 14132 (curve 5), systematic trans-
formation to new ordered mesoporous structure.
The XRD of carbon material showed no patterns in
the region 2θ greater than 10° indicating that the
carbon framework was atomically disordered.
FTIR spectra confirmed XRD data of the sys-
tematic structural changes and show the possibility
of the checking feature of the forming CMK-1
structure and illustrate all reactions and processes
which pass in structure MCM-48 step by step
(Fig. 2). Calcination of mesostructured matrix at
823 K (curve 2) results in complete releasing of
porous structure of MCM-48 from template, disap-
pearance of the absorption band (VC-H) characteris-
tic for the template molecules at 2800–3000 cm-1.
Enhancement of the Hydrogen Sorption on Mesoporous Carbon
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 3 317
Fig 2. Infrared spectra registered after various stages
of MCM-48 treatment and CMK-1 formation:
1 – as synthesized MCM-48; 2 – calcined at
823 K; 3 – after sucrose+H2SO4, 423 K treat-
ment; 4 – reloaded sucrose, 433 K; 5 – carboni-
zation in vacuum, 1173 K; 6 – final composite,
after dissolved silica matrix
When the template was removed, (VC-H) vibra-
tion bands disappeared and absorption bands cor-
responding to oscillation of physically adsorbed
water at 3420 and 1630 cm-1 were observed.
Сarbonization result in the complete destruc-
tion of structure of MCM-48 (curve 5) and band at
1590 cm-1 which characterizes the unsaturated car-
bon structures appeared in the spectra. After disso-
lution of the silicate matrix (curve 6) only absorp-
tion bands with at 1590 and 1720 cm-1 detected in
a spectrum that can testify to the completeness of
carbonization and formation of the carbon silica
matrix resulted in appearance and increased of the
band at 1590 cm-1 which characterizes the unsatu-
rated carbon structures. After removed of silica
frameworks remain only the absorption bands at
1590 and 1720 cm-1 that characterized formation of
the mesoporous carbon remain in the spectrum.
After dissolution of the silicate matrix
(curve 6) only absorption bands with at 1590 and
1720 cm-1 detected in a spectrum that can testify to
the completeness of carbonization and formation of
carbon. The synthesis information concerning to
effect of the sucrose/sulfuric acid, calcination tem-
perature and optimum amounts of sucrose can be
used for control to obtain highly ordered mesopor-
ous carbon. With this purpose, we continuously
detected r changes in the gas phase by mass spec-
trometer. Special attention has been paid to the
formation of the volatile products which appeared
at heating and carbonization sucrose in a vacuum
with speed of heating 9.7 K/min in 303–1023 K.
As evidently from Fig. 3, in this temperature
range the basic volatile products of thermolysis of
sucrose are H2O, CO and CO2.
3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0 9 0 0 1 0 0 0 1 1 0 0
0
2
4
6
8
In
te
g
ra
l i
n
te
n
si
ty
, a
.u
.
T , K
1
2
3
4
5
6
7
8
9
Fig. 3. Changes in the amount of gas phase products
(calculated from MS data) during the reaction
the sucrose carbonization for the ions with m/z:
1 – 15 (CH3
+); 2 – 17 (OH+); 3 – 18 (H2O
+);
4 – 27 (C2H3
+); 5 – 28(CO+); 6 – 41(C3H5+);
7 – 44 (CO2
+); 8 – 48 (SO+); 9 – 64 (SO2
+)
Their liberation observed at all time heating,
especially it noticeably for H2O, CO. In case of
CO2, we observed intensive take off at 473–773 K
with the maximum about 603 K. The basic proc-
ess of thermodestruction of sucrose from TPDMS
data begins at a temperature 450 K. Thus, at the
low temperature main process of thermolysis are
dehydratation and insignificant release of the CO.
When the temperature increased, we detected
complex process which is linked with splitting of
the heterocyclic group and their destruction (CO
release). Character of curves from m/z=48 and 64,
corresponding SO and SO2, at 323–613 K testify
to destruction of the sulfonate group.
Interestingly, that according to TPDMS data
thermolysis not completed at 1023 K, such as we
detected noticeable release of H2O and CO. Thus,
we can state that for successfully completion of a
process of sucrose carbonization and formation of
the ordered porous carbon structure, additional
treatment at a high temperature is necessary. A
periodic nature of mesoporous carbon was also
confirmed using Raman spectroscopy. In the visi-
ble Raman spectrum vibrational "graphite" mode
appeared at 1582 and 1355 cm-1 bands due to
highly oriented pyrolytic graphite.
Concerning the porosity, for all materials ni-
trogen adsorption exhibits type IV isotherms (not
shown here) presenting a sharp step at a relative
pressure of 0.3–0.4 attributed to capillary conden-
sation in the ordered mesoporous structure. The
results of calculations are given in Table. Pore
size analysis shows that both MCM-48 and
CMK-1 are structurally microporous and meso-
porous but the microporosity is much less impor-
tant for CMK-1. The average pore size and the
6
V. Gerda, G. Telbiz, N. Kobylinskaya et al.
_____________________________________________________________________________________________
318 ХФТП 2010. Т. 1. № 3
total surface area increase from 2.12 nm to
3.03 nm and from 1310 m2/g to 1801 m2/g for
MCM-48 and for CMK-1, respectively. For the
CMK-1/Pd samples, reduction of Pd with hydro-
gen does not change the textural/structural pa-
rameters significantly as compared with those of
CMK-1 (Table). The low angle XRD patterns of
CMK-1 with or without Pd are identical. The spe-
cific surface areas and volumes corresponding to
the different type of pores are roughly the same.
The average pore diameter has the same value
(3.11 nm) but this latter corresponds in fact to a
broader distribution of pore size which could re-
sult from a modification due to the influence of
the solution used for Pd loading.
Analysis of TEM images reveals that the size
distribution of palladium particles is quite narrow
(average size 2~7 nm) and that these latter are
partly dispersed within the matrix. Unfortunately,
TEM shows also some large particles; especially
for CMK-1/Pd 5%.These can be detected also
with high-angle XRD, with a reflection character-
istic of metallic palladium at 39.7 degrees. Of
course, these large particles are located outside
the mesopores of carbon network.
Hydrogen adsorption measurement. First we
compared the results of the effective hydrogen
storage by CMK-1 prepared at different tempera-
tures and sucrose carbonization times. Hydrogen
adsorption on these ordered carbon materials in-
creases noticeably with the carbonization tem-
perature up to 1173 K (Fig. 4).
At higher temperature, further increase up to
1373 K has the reverse effect leading to a de-
crease in hydrogen adsorption. These results show
that the conditions of CMK-1 synthesis have a
great influence on the quantity of hydrogen ad-
sorbed by this material. The experimental data for
the hydrogen capacities of MCM-48 and CMK-1
at 77 K and atmospheric pressure are presented in
Table. The lowest value is obtained with MCM-48
(0.51 wt. %) while the maximum hydrogen sorp-
tion on CMK-1 is 1.80±0.04 wt. % at a carboniza-
tion temperature of 1173 K for 3 hours. Similar
data were observed Gadiou et al. [17] in the case
of ordered nanostructure carbons samples. The
amounts of adsorbed hydrogen, related to the
same amount of corresponding CMK-1, are 2.07
and 2.17 wt % for samples CMK-1 – 1% and 5%,
respectively. The corresponding increases of hy-
drogen adsorption due to this doping are ap-
proximately 15% and 20% (Table).
Fig. 4. Correlation between temperature/time car-
bonization of sucrose and storage capacity dif-
ferent CMK-1 at 77 K and ambient pressure
Table. Surface areas, volumes and H2 capacity of the
samples
Sample
MCM-48 CMK-1 Pd CMK-1
(wt. 1%)
Pd CMK-1
(wt. 5%)
Stot,
m2/g 1308 1800 1794 1720
Smicro,
m2/g 401 156 151 133
Smeso,
m2/g 901 1577 1576 1522
Smacro,
m2/g 6 67 67 65
Vtot,
cm3/g
1.16 1.15 1.12 1.09
Vmicro,
sm3/g 0.10 0.10 0.10 0.09
Vmeso,
sm3/g 0.92 1.00 0.97 0.96
Vmacro,
sm3/g
0.14 0.05 0.05 0.04
D, nm
±0.05 2.12 3.03 3.11 3.11
H2 capac-
ity, wt, % 0.51±0.02 1.80±0.04 2.07±0.05* 2.17±0.06*
*related to the same amount of CMK-1.
Of course, during hydrogen adsorption there is
the formation of β-Pd hydride of approximate for-
mula is Pd-H0.65. However, expressed in wt %, this
corresponding amount is negligible. This phe-
nomenon can be attributed to the spillover effect,
as was proposed in [22]. It was shown in [23] that
there is always equilibrium between H2 gas, H2
adsorbed on the Pd surface and H2 of β-Pd hydride,
this latter form being at its maximum value when
the surface of the particle is saturated
He ⇔ (H) adsorbed ⇔ (H2) gas.
Consequently, there is always exchange and de-
sorption of H species to re-form (H2) gas or to diffuse
throughout the carbon structure as was shown for the
case of Pt supported on silica and zeolites [24, 25].
Enhancement of the Hydrogen Sorption on Mesoporous Carbon
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 3 319
CONCLUSION
Matrix synthesis and transform during the for-
mation of three-dimensional structure of ordered me-
soporous carbon were described. The formation
CMK-1 was checked by X-ray diffraction, FTIR, and
TPD mass spectrometry. It was shown that for suc-
cessfully completion of a process of sucrose carboni-
zation the additional ageing at high temperature
treatment is the necessary criterion. Functionalization
of the ordered carbon by Pd nanoparticles resulted in
increasing of adsorption of hydrogen but more sur-
prisingly that sorptive capacity of H2 does not depend
on Pd concentration (1–5%). In addition the charac-
terization of this volume of narrow micropores can
be a good parameter for the evaluation of the hydro-
gen adsorption capacity of these new Pd doped and
native carbon material.
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Received 24.06.2010, accepted 17.08.2010
Підвищення сорбції водню допуванням мезопористого вуглецю
наночастинками паладію
В.І. Герда, Г.М. Тельбиз, Н.Г. Кобилінська, В.М. Зайцев, П. Манорик, Ж. Фрайсард
Лабораторія квантової фізики, Університет П’єра та Марії Кюрі,
вул. Вакулин10, Париж 75231, Франція, jacques.fraissard@upmc.fr
Хімічний факультет, Київський національний університет ім. Т. Шевченка
вул. Володимирська 62а, Київ 01033, Україна, nkobilinskaya@rambler.ru
Інститут фізичної хімії ім. Л.В. Писаржевського Національної академії наук України
пр. Науки 31, Київ 03028, Україна, g_telbiz@yahoo.com
Університет П’єра та Марії Кюрі, пл. Жюссьє 4, Париж 75005, Франція, jacques.fraissard@upmc.fr
Мезопористий вуглець, допований паладієм, був одержаний шляхом матричного синтезу з використан-
ням мезопористого кремнезему як темплату. Отримані зразки високовпорядкованого кубічного мезопорис-
того вуглецю характеризуються питомою площею поверхні до 1800 м2/г, великим об’ємом пор до 1,14 cм3/г і
середнім діаметром від 3,03 нм. Стадії одержання мезопористого вуглецю та композитного матеріалу
контролювали методами рентгенівської дифракції, ІЧ-спектроскопії з Фур'є-перетворенням, низькотемпе-
ратурної адсорбції азоту та ТПД мас-спектрометрії. Встановлено, що допування зразків паладієм не при-
водить до руйнування структури матриці; згідно з даними просвічуючої електронної мікроскопії та спект-
роскопії комбінаційного розсіювання структура високовпорядкованого мезопористого композиту склада-
ється з впорядкованої вуглецевої фази з ділянками графіту і наночастинок паладію, інкорпорованого в мезо-
порах матриці, а композитні зразки показують підвищену сорбційну ємність по водню.
Повышение сорбции водорода допированием мезопористого угля
наночастицами палладия
В.И. Герда, Г.М. Тельбиз, Н.Г. Кобылинская, В.Н. Зайцев, П. Манорик, Ж. Фрайсард
Лаборатория квантовой физики, Университет Пьера и Марии Кюри,
ул. Вакулин,10, Париж 75231, Франция jacques.fraissard@upmc.fr
Химический факультет, Киевский национальный университет им. Т. Шевченко
ул. Владимирская 62а, Киев 01033, Украина, nkobilinskaya@rambler.ru
Институт физической химии им. Л.В. Писаржевского Национальной академии наук Украины
пр. Науки 31, Киев 03028, Украина, g_telbiz@yahoo.com
Университет Пьера и Марии Кюри, пл. Жюссье 4, Париж 75005, Франция, jacques.fraissard@upmc.fr
Мезопористий углерод, допированный палладием, был получен методом матричного синтеза с приме-
нением в качестве темплата мезопористого кремнезема. Получены образцы высокоупорядоченного кубиче-
ского мезопористого угля, которые характеризуются большой удельной площадью поверхности 1800 м2/г,
большим объемом пор до 1,14 cм3/г и средним диаметром от 3,03 нм. Стадии получения мезопористого
угля и композитного материала контролировали методами рентгеновской дифракции, ИК-спектроскопии с
Фурье-преобразованием, низкотемпературной адсорбции азота и ТПД масс-спектрометрии. Установлено,
что допирование образцов палладием не приводит к разрушению структуры матрицы; согласно данным
просвечивающей электронной микроскопии и спектроскопии комбинационного рассеивания структура вы-
сокоупорядоченного мезопористого композита состоит из упорядоченной углеродной фазы с участками
графита и наночастиц палладия, инкорпорированного в мезопорах матрицы, а полученные композитные
образцы показывают повышенную сорбционную емкость по водороду.
|
| id | nasplib_isofts_kiev_ua-123456789-29000 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 2079-1704 |
| language | English |
| last_indexed | 2025-12-07T18:08:18Z |
| publishDate | 2010 |
| publisher | Інститут хімії поверхні ім. О.О. Чуйка НАН України |
| record_format | dspace |
| spelling | Gerda, V. Telbiz, G. Kobylinskaya, N. Zaitsev, V. Manoryk, P. Fraissard, J. 2011-11-27T17:41:45Z 2011-11-27T17:41:45Z 2010 Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles / V. Gerda, G. Telbiz, N. Kobylinskaya, V. Zaitsev, P. Manoryk, J. Fraissard // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 3. — С. 315-320. — Бібліогр.: 25 назв. — англ. 2079-1704 https://nasplib.isofts.kiev.ua/handle/123456789/29000 544.723 We have used the matrix synthesis protocol of Ryoo et al. for the preparation of highly ordered cubic mesoporous carbon (CMK-1) using mesoporous silica (MCM-48) as a template, in order to prepare palladium-doped CMK-1. The carbon obtained has a high surface area of 1800 m2g-1, a large porous volume of 1.14 cm3g-1 and average pore diameter of 3.03 nm. Step-by-step formation of mesoporous carbon was followed by X-ray diffraction, FTIR, N2 adsorption desorption and TPD mass-spectrometry. The physical data of CMK-1 are hardly changed by Pd incorporation (CMK-1/Pd). Transmission electron microscopy and Raman spectroscopy show that the framework of the highly ordered mesoporous carbon/Pd consists of an aligned carbon phase with a graphite mode region. The potential application of CMK-1 and CMK-1/Pd as sorbents for hydrogen storage is discussed. Мезопористий вуглець, допований паладієм, був одержаний шляхом матричного синтезу з використанням мезопористого кремнезему як темплату. Отримані зразки високовпорядкованого кубічного мезопористого вуглецю характеризуються питомою площею поверхні до 1800 м2/г, великим об’ємом пор до 1,14 cм3/г і середнім діаметром від 3,03 нм. Стадії одержання мезопористого вуглецю та композитного матеріалу контролювали методами рентгенівської дифракції, ІЧ-спектроскопії з Фур'є-перетворенням, низькотемпературної адсорбції азоту та ТПД мас-спектрометрії. Встановлено, що допування зразків паладієм не приводить до руйнування структури матриці; згідно з даними просвічуючої електронної мікроскопії та спектроскопії комбінаційного розсіювання структура високовпорядкованого мезопористого композиту складається з впорядкованої вуглецевої фази з ділянками графіту і наночастинок паладію, інкорпорованого в мезопорах матриці, а композитні зразки показують підвищену сорбційну ємність по водню. Мезопористий углерод, допированный палладием, был получен методом матричного синтеза с применением в качестве темплата мезопористого кремнезема. Получены образцы высокоупорядоченного кубического мезопористого угля, которые характеризуются большой удельной площадью поверхности 1800 м2/г, большим объемом пор до 1,14 cм3/г и средним диаметром от 3,03 нм. Стадии получения мезопористого угля и композитного материала контролировали методами рентгеновской дифракции, ИК-спектроскопии с Фурье-преобразованием, низкотемпературной адсорбции азота и ТПД масс-спектрометрии. Установлено, что допирование образцов палладием не приводит к разрушению структуры матрицы; согласно данным просвечивающей электронной микроскопии и спектроскопии комбинационного рассеивания структура высокоупорядоченного мезопористого композита состоит из упорядоченной углеродной фазы с участками графита и наночастиц палладия, инкорпорированного в мезопорах матрицы, а полученные композитные образцы показывают повышенную сорбционную емкость по водороду. en Інститут хімії поверхні ім. О.О. Чуйка НАН України Хімія, фізика та технологія поверхні Неорганічні та вуглецеві наноматеріали і наносистеми Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles Підвищення сорбції водню допуванням мезопористого вуглецю наночастинками паладію Повышение сорбции водорода допированием мезопористого угля наночастицами палладия Article published earlier |
| spellingShingle | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles Gerda, V. Telbiz, G. Kobylinskaya, N. Zaitsev, V. Manoryk, P. Fraissard, J. Неорганічні та вуглецеві наноматеріали і наносистеми |
| title | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles |
| title_alt | Підвищення сорбції водню допуванням мезопористого вуглецю наночастинками паладію Повышение сорбции водорода допированием мезопористого угля наночастицами палладия |
| title_full | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles |
| title_fullStr | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles |
| title_full_unstemmed | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles |
| title_short | Enhancement of the Hydrogen Sorption on Mesoporous Carbon by Doping with Palladium Nanoparticles |
| title_sort | enhancement of the hydrogen sorption on mesoporous carbon by doping with palladium nanoparticles |
| topic | Неорганічні та вуглецеві наноматеріали і наносистеми |
| topic_facet | Неорганічні та вуглецеві наноматеріали і наносистеми |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/29000 |
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