Platinum nanoparticles supported on reduced graphite oxide are produced by reduction of a slurry including graphite oxide and H2PtCl6·xH2O, and pyridine as modifying agent. Four compounds as a formation formateion decene-1 and nitrobenzene hydrogenation at hydrogen atmospheric pressure and 45°C. 
In the result of reduction Pt4+ is converted to Pt metal and graphite oxide loses of oxygen. The symbasis 
Pt loading with C/O ratio is observed. Compositions Pt - reduced graphite oxide catalyze the hudrogenation of decene-1 and nitrobenzene in a solution. The greatest activity is shown composition reduced by sodium borohydride with the particle size of 2.0 nm, however it is substantially lower than it for Pt/fullerene 
black catalyst. Some inhibiton of hydrogenation by incompletely reduced graphite oxide is shown.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3505

Dremova, N.N.

Korshunova, L.A.

Kushch, S.D.

Kuyunko, N.S.

Muradyan, V.E.

Tarasov, B.P.

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 1 No 1, 01NDLCN06(3pp) (2012)   2304-1862/2012/1(1)01NDLCN06(3) 01NDLCN06-1  2012 Sumy State University Platinum Nanoparticles Supported on Reduced Graphite Oxide as Hydrogenation Catalyst   S.D. Kushch *, N.S. Kuyunko †, V.E. Muradyan, L.A. Korshunova, N.N. Dremova, B.P. Tarasov  The Institute of Problems of Chemical Physics of the Russian Academy of Sciences (IPCP RAS),  Academician Semenov Av. 1, Chernogolovka, Moscow region, 142432 Russian Federation  (Received 13 June 2012; published online 21 August 2012)  Platinum nanoparticles supported on reduced graphite oxide are produced by reduction of a slurry in-cluding graphite oxide and H2PtCl6·xH2O, and pyridine as modifying agent. Four compounds as a formate-ion or ethylene glycol or hydrazine or sodium borohydride as reducing agents were used. Both initial graphite oxide and Pt-containing compositions reduced were investigated by elemental analysis, thermo-gravimetric analysis, IR- and Raman spectroscopies. Reduced compositions are tested as catalysts of de-cene-1 and nitrobenzene hydrogenation at hydrogen atmospheric pressure and 45°C.  In the result of reduction Pt4+ is converted to Pt metal and graphite oxide loses of oxygen. The symbasis Pt loading with C/O ratio is observed.  Compositions Pt - reduced graphite oxide catalyze the hydrogena-tion of decene-1 and nitrobenzene in a solution. The greatest activity is shown composition reduced by so-dium borohydride with the particle size of 2.0 nm, however it is substantially lower than it for Pt/fullerene black catalyst. Some inhibiton of  hydrogenation by incompletely reduced graphite oxide is shown.  Keywords: Graphite oxide, Platinum nanoparticles, Catalyst, Hydrogenation.    PACS number: 81.05.Uw   ______________ * ksd@icp.ac.ru † arbuzovartem@yandex.ru 1. INTRODUCTION  Carbon nanomaterials with graphene structure at-tract attention as potential catalysts or electrocatalysts supports in recent years. A dominant causes of this interest to nanomaterials with graphene structure are associated with substrate possibility to coordination with aromatic fragments of their structure and availa-bility of the conjugate bonds system, and the abnormal wide two-sided surface and high (comparable with graphite) conduction that is necessary for catalysts of the reactions proceeding with electron transfer from metal to a substrate [1]. The perspective support for catalysts for reactions with electron transfer from these points of view may be the graphene, i.e. the graphite inclucive one layer and being, thus, a two-dimensional conductor. At the same time, an effective catalyst support in-cludes anchor functional groups, suitable for covalent bonds formation with metal ions. In a structure of car-bon nanomaterials with aromatic conjugation system as recently noted [2-4] it is difficult to introduce func-tional groups into carbon nanomaterials to the extent sufficient for the formation of covalent bonds with plat-inum. In fact, substitution reactions involving aromatic ring protons are impossible in this case because of the absence of protons and extremely small (of the order 10–4 g–1) amount of dangling bonds. Widely used for graphite functionalization methods of oxidation by various agents allows to introduction carbonyl-, carboxyl-, epoxy- and hydroxyl (phenolic) groups, but leads to destruction of conjugation system and conduction degradation. One of products of graph-ite deep oxidation as  graphite oxide may be reduced to graphene and this method is discussed as graphene preparation methods in the appreciable quantities [5, 6].  It seemed tempting to produce platinum particles supported on graphene since appears possible to fix of platinum by means of functional groups graphite oxide and to combine of platinum reduction with graphite oxide reduction to graphene.  2. RESULTS AND DISCUSSION  The graphite oxide produced by oxidation of graph-ite by sulfuric or nitric acids or their mixture, includes, except carbon, significant amounts of oxygen and char-acterised by С/О ratio equal of 2.544 (Tab. 1).   Table 1 – Properties of graphite oxide and Pt-containing compositions based on it  A sample Content of , % wt. Gross formula C/O ratio ID/IG C H N O GO 49.31 2.42 0.03 45.02 C8H4.68O5.48 1.459 0.964 Pt/RGOF 49.48 2.85 0.44 40.92 1.81 % Pt/C8H5.49O4.97N0.06 1.610 1.008 Pt/RGOEG 70.77 1.53 0.73 17.96 3.70 % Pt/C8H2.06O1.52N0.07 5.263 1.037 Pt/RGOH 79.64 0.94 2.82 6.02 8,82 % Pt/C8H1.125O0.45N0.24 17.622 1.106 Pt/RGOB 71.14 1.91 1.52 12.41 8,22 % Pt/C8H2.56O1.05N0.148 7.636 1.034  As per a conventional nonstoichiometric models by Lerf and Klinovski, graphite oxide includes mainly hy-droxylic and epoxy- (1,2-ethers) functional groups. Car-boxyl groups are present along the edges graphene  S.D. KUSHCH, N.S. KUYUNKO, V.E. MURADYAN, ET AL.  PROC. NAP 1, 01NDLCN06 (2012)   01NDLCN06-2 sheets. Besides, oxygen is present as 5 and 6-membered lactols. The presence of such functional groups agrees with the thermogravimetric analysis of graphite oxide in Ar (Fig. 1) according to which the basic products of decomposition are carbon oxide with m/e 28, water (m/e 18) and carbon dioxide (m/e 44), escaping with ekzo-effect mainly to 200°С.   200 400 600 800-6-4-202468020406080143DSC, mW/mgTemperature, oC2Ion Current, pA   Fig. 1 - Thermogram in Ar of (1) graphite oxide combined with the mass spectrometric analysis of gas products with mass numbers, m/e: (2) 28, (3) 18, (4) 44  The presence of these functional groups in а graphite oxide structure proves to be true also by IR- data wherein the absorbtion peaks can be assigned to the O–H stretch-ing vibrations at 3430 cm-1, C–O stretching at 1070 cm-1, the C  O carbonyl stretching at 1727 cm-1, the C  C ring stretching at1624 cm-1, the phenol O–H deformation vi-bration at 1407 cm-1 and С-ОН at 1226 cm-1). The introduction of hydroxyl and epoxy-groups into graphene structure with sp2- hybridization of carbon at-oms causes reorganisation of planar conjugate system into spacial system with sp3- hybrid carbon atoms. As a result of it in Raman-spectra graphite oxide (Fig. 3) both G - and D-mode in the ID/IG ratio of 0.964 are observed. Compositions platinum - reduced graphite prepared by platinum addition to graphite oxide by covalent bonds and the subsequent reduction. The presence of hydroxyl and epoxy (1,2-ether) groups in graphite oxide structure as-sumes some possibility of Pt4+ addition to graphite oxide. Replacement of chloride acido ligand onto oxyl-fragment of hydroxyl group demands a presence of platinum in cati-on part of its compound that is reached by introduction of amine, in particular pyridine, to reaction system. Recently [2-4] pyridine role in platinum fixation with use of carbox-yl groups of support was discussed., one of which aspects is rearrangement of a complex of platinum to cationic complex formation. On the other hand, pyridine disacidi-fies of acid formed by proton replacement of hydroxyl group on platinum-containing cation. The hydroxyl group of graphite oxide as opposed to carboxyl is monodentate ligand that is a little suitable for platinum bonding. Addi-tional use of epoxy (1,2-ether) group of graphite oxide as ligand is unproductively as platinum-containing anion reacts with epoxide by trans-addition, i.e. add to reverse side with regard to hydroxyl group. A reducing agent able to both Pt4+, and graphite oxide reduction is required for preparation of compositions on the base of graphite oxide (GO). Four compounds as a formate-ion or ethylene glycol or hydrazine or sodium borohydride as a reducing agents were used. The re-duced bases of these compositions after reduction in the depending on reductant is called as RGOF, RGOEG, RGOH, and RGOB respectively. A composition bases after its reduction lose of oxy-gen (Tabl. 1). In result of this the amounts of decompo-sition products are decrease (Fig. 2).  200 400 600 8004050607080901005432Mass relative, %Temperature, оС1  Fig. 2 - Thermograms in Ar of (1) GO and compositions (2) Pt/ RGOF, (3) Pt/RGOEG, (4) Pt/RGOB, and (5) Pt/RGOH  The observed after reduction increases in compari-son with GO of C/O ratio (Tabl. 1) and ID/IG ratio (Fig. 3), and the temperatures of decomposition (Fig. 2) and oxidation (Fig. 4) point out to a change of non-conjugating sp3-hybridised graphite oxide in ordered sp3-hybridised system.    Fig. 3 – Raman spectra of (1) GO, (2) Pt/RGOH, (3) Pt/RGOB, (4) Pt/ RGOF and (5) Pt/RGOEG  Moreover, in Raman spectra of platinum-reduced graphite oxide compositions against to graphite pris-tine D-mode are present and 2G-mode about of 2700 cm-1 are absent (Fig. 3) i.e. product of reduction of graphite oxide is not graphene and right call as re-duced graphite oxide. Thus, hydrazine react with carbonyl compounds (Wolff–Kishner reaction) with deoxygenation and car-bohydrates formation. Epoxides ineract with hydrazine yielded aminoalcohols (Wharton reaction). High nitro-gen content observed for Pt/RGOH (Tabl. 1) very likely is associated with aminoalcohols formation and/or the transient formation of hydrazones in these reactions [7]. Interactions of both carbonyl- and epoxy- com-pounds with formate-ion or ethylene glycol with oxygen loss not associate.   PLATINUM NANOPARTICLES SUPPORTED ON REDUCED GRAPHITE… PROC. NAP 1, 01NDLCN06 (2012)   01NDLCN06-3 200 400 600 8000204060801005431Mass relative, %Temperature, оС2  Fig. 4 - Oxidative thermograms of (1) GO and compositions (2) Pt/RGOB, (3) Pt/RGOH, (4) Pt/RGOF, and (5) Pt/RGOB  The reduced compositions contained platinum (0) were produced, but only at the use of hydrazine or NaBH4 as a reducing agent in contrast to a formate-ion or ethylene glycol its Pt loading correspond to calculat-ed value (Tabl. 1). The symbatic change of Pt loading with C/O ratio (Tabl. 1), i.e. slope opposition of Pt load-ing with oxygen content is observed.     Fig. 5 - Pt/RGOB TEM image  Thus, platinum fixation by means covalent bonds formation and its reduction to metal are carried out within one process and platinum is supported on the surface of graphite oxide subjected to interaction with reductant. Platinum particles in Pt - reduced graphite oxide compositions prepared by reduction by formate-ion or ethylene glycol or hydrazine are distributed non-uniformly. The reduction of composition by sodium borohydride produces platinum particles with average particle size ≈2.0 nm (Fig. 5). Nitrogen atomic content is in 2-4 times higher than platinum atomic content (Tabl. 1) that asso-ciated with our reasons on pyridine role [2-4, 8].  Pt - reduced graphite oxide compositions catalyze the hydrogenation of decene-1 in solution (Fig. 6). The hydrogenation rate in all instances is sufficiently low therefore in one of cases reaction has not been finished. Specific activity of the most preferable catalyst Pt/RGOB during reaction time 30 min decreases from 24 H2 mole·(Pt mole·min)-1 five times. Pt - reduced graphite oxide compositions catalyze the nitrobenzene hydrogenation in solution too. The greatest catalytic activity is shown for the com-position reduced by sodium borohydride with the parti-cle size of 2.0 nm, however it is substantially lower than it for catalyst based on fullerene black (Fig. 6)[8].  10 20 30 40 50 6005101520255H2, mmoleReaction time, min43 2 1  Fig. 6 - H2 consumption profiles in decene-1 hydrogenation over (1) Pt/RGOF, (2) Pt/RGOH, (3) Pt/RGOEG, (4) Pt/RGOB, and (5) Pt/fullerene black  Decene-1 hydrogenation rate converted by the first reaction order, decreases disproportionately to decene-1 concentration loss (Fig. 1). These observations point to catalyst poisoning by reaction product as decane or to some inhibition of hydrogenation in presence incom-pletely reduced graphite oxide.  AKNOWLEDGEMENTS  This work was supported by the Russian Founda-tion for Basic Research (No 11-03-01190-а).   REFERENCES  1. E.G. Chepaikin, M.L. Khidekel'. Conjugation as a stimu-lating factor in the processes of electron transfer with the participation of coordination compounds. (Institute of Chemical Physics of USSR Academy of Sciences. Preprint. Chernogolovkap: 1979). 2. N.S. Kuyunko, S.D. Kushch, V.E. Muradyan, A.A. Volodin, V.I. Torbov, B.P. Tarasov, Hydrogen Materials Science and Chemistry of Carbon Nanomaterials. NATO Security through Science. Series A. Chemistry and Biology (Spring-er Science + Business Media BV: 2006). 3. S.D. Kushch, N.S. Kuyunko, B.P. Tarasov, Russ. J. Gen. Chem. 79, 706 (2009).  4. S.D. Kushch, N.S. Kuyunko, B.P. Tarasov, Zhurn. Obshch. Khim. 79, 542 (2009). 5. S.D. Kushch, N.S. Kuyunko, B.P. Tarasov, Kinetics and Catalysis 50, 860 (2009); Kinetika i kataliz 50, 895 (2009). 6. V. Singh, D. Joung, L. Zhai, S. Das, S.I. Khondaker, S. Seal, Prog. Mat. Sci. 56, 1178 (2011). 7. C. Soldano, A. Mahmood, E. Dujardin, Carbon, 48, 2127 (2010). 8. S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Yue Wu, SonBinh T. Nguyen, R.S. Ruoff, Carbon 45, 1558 (2007). 9. S.D. Kushch, N.S. Kuyunko, B.P. Tarasov, Russ. J. Gen. Chem. 79, 1106 (2009); Zhurn. Obshch. Khim. 79, 934 (2009). 

Platinum Nanoparticles Supported on Reduced Graphite Oxide as Hydrogenation Catalyst

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 1 No 1, 01NDLCN06(3pp) (2012) 
 
 
2304-1862/2012/1(1)01NDLCN06(3) 01NDLCN06-1  2012 Sumy State University 
Platinum Nanoparticles Supported on Reduced Graphite Oxide as Hydrogenation Catalyst 
  
S.D. Kushch *, N.S. Kuyunko †, V.E. Muradyan, L.A. Korshunova, N.N. Dremova, B.P. Tarasov 
 
The Institute of Problems of Chemical Physics of the Russian Academy of Sciences (IPCP RAS),  
Academician Semenov Av. 1, Chernogolovka, Moscow region, 142432 Russian Federation 
 
(Received 13 June 2012; published online 21 August 2012) 
 
Platinum nanoparticles supported on reduced graphite oxide are produced by reduction of a slurry in-
cluding graphite oxide and H2PtCl6·xH2O, and pyridine as modifying agent. Four compounds as a formate-
ion or ethylene glycol or hydrazine or sodium borohydride as reducing agents were used. Both initial 
graphite oxide and Pt-containing compositions reduced were investigated by elemental analysis, thermo-
gravimetric analysis, IR- and Raman spectroscopies. Reduced compositions are tested as catalysts of de-
cene-1 and nitrobenzene hydrogenation at hydrogen atmospheric pressure and 45°C.  
In the result of reduction Pt4+ is converted to Pt metal and graphite oxide loses of oxygen. The symbasis 
Pt loading with C/O ratio is observed.  Compositions Pt - reduced graphite oxide catalyze the hydrogena-
tion of decene-1 and nitrobenzene in a solution. The greatest activity is shown composition reduced by so-
dium borohydride with the particle size of 2.0 nm, however it is substantially lower than it for Pt/fullerene 
black catalyst. Some inhibiton of  hydrogenation by incompletely reduced graphite oxide is shown. 
 
Keywords: Graphite oxide, Platinum nanoparticles, Catalyst, Hydrogenation. 
 
  PACS number: 81.05.Uw 
 
 
______________ 
* ksd@icp.ac.ru 
† arbuzovartem@yandex.ru 
1. INTRODUCTION 
 
Carbon nanomaterials with graphene structure at-
tract attention as potential catalysts or electrocatalysts 
supports in recent years. A dominant causes of this 
interest to nanomaterials with graphene structure are 
associated with substrate possibility to coordination 
with aromatic fragments of their structure and availa-
bility of the conjugate bonds system, and the abnormal 
wide two-sided surface and high (comparable with 
graphite) conduction that is necessary for catalysts of 
the reactions proceeding with electron transfer from 
metal to a substrate [1]. 
The perspective support for catalysts for reactions 
with electron transfer from these points of view may be 
the graphene, i.e. the graphite inclucive one layer and 
being, thus, a two-dimensional conductor. 
At the same time, an effective catalyst support in-
cludes anchor functional groups, suitable for covalent 
bonds formation with metal ions. In a structure of car-
bon nanomaterials with aromatic conjugation system 
as recently noted [2-4] it is difficult to introduce func-
tional groups into carbon nanomaterials to the extent 
sufficient for the formation of covalent bonds with plat-
inum. In fact, substitution reactions involving aromatic 
ring protons are impossible in this case because of the 
absence of protons and extremely small (of the order 
10–4 g–1) amount of dangling bonds. 
Widely used for graphite functionalization methods 
of oxidation by various agents allows to introduction 
carbonyl-, carboxyl-, epoxy- and hydroxyl (phenolic) 
groups, but leads to destruction of conjugation system 
and conduction degradation. One of products of graph-
ite deep oxidation as  graphite oxide may be reduced to 
graphene and this method is discussed as graphene 
preparation methods in the appreciable quantities 
[5, 6].  
It seemed tempting to produce platinum particles 
supported on graphene since appears possible to fix of 
platinum by means of functional groups graphite oxide 
and to combine of platinum reduction with graphite 
oxide reduction to graphene. 
 
2. RESULTS AND DISCUSSION 
 
The graphite oxide produced by oxidation of graph-
ite by sulfuric or nitric acids or their mixture, includes, 
except carbon, significant amounts of oxygen and char-
acterised by С/О ratio equal of 2.544 (Tab. 1). 
 
 
Table 1 – Properties of graphite oxide and Pt-containing compositions based on it 
 
A sample 
Content of , % wt. 
Gross formula C/O ratio ID/IG 
C H N O 
GO 49.31 2.42 0.03 45.02 C8H4.68O5.48 1.459 0.964 
Pt/RGOF 49.48 2.85 0.44 40.92 1.81 % Pt/C8H5.49O4.97N0.06 1.610 1.008 
Pt/RGOEG 70.77 1.53 0.73 17.96 3.70 % Pt/C8H2.06O1.52N0.07 5.263 1.037 
Pt/RGOH 79.64 0.94 2.82 6.02 8,82 % Pt/C8H1.125O0.45N0.24 17.622 1.106 
Pt/RGOB 71.14 1.91 1.52 12.41 8,22 % Pt/C8H2.56O1.05N0.148 7.636 1.034 
 
As per a conventional nonstoichiometric models by 
Lerf and Klinovski, graphite oxide includes mainly hy-
droxylic and epoxy- (1,2-ethers) functional groups. Car-
boxyl groups are present along the edges graphene 
 
S.D. KUSHCH, N.S. KUYUNKO, V.E. MURADYAN, ET AL.  PROC. NAP 1, 01NDLCN06 (2012) 
 
 
01NDLCN06-2 
sheets. Besides, oxygen is present as 5 and 6-
membered lactols. The presence of such functional 
groups agrees with the thermogravimetric analysis of 
graphite oxide in Ar (Fig. 1) according to which the 
basic products of decomposition are carbon oxide with 
m/e 28, water (m/e 18) and carbon dioxide (m/e 44), 
escaping with ekzo-effect mainly to 200°С.  
 
200 400 600 800
-6
-4
-2
0
2
4
6
8
0
20
40
60
80
1
4
3
D
S
C
, 
m
W
/m
g
Temperature, 
o
C
2
Io
n
 C
u
rr
en
t,
 p
A
 
 
 
Fig. 1 - Thermogram in Ar of (1) graphite oxide combined 
with the mass spectrometric analysis of gas products with 
mass numbers, m/e: (2) 28, (3) 18, (4) 44 
 
The presence of these functional groups in а graphite 
oxide structure proves to be true also by IR- data wherein 
the absorbtion peaks can be assigned to the O–H stretch-
ing vibrations at 3430 cm-1, C–O stretching at 1070 cm-1, 
the C  O carbonyl stretching at 1727 cm-1, the C  C ring 
stretching at1624 cm-1, the phenol O–H deformation vi-
bration at 1407 cm-1 and С-ОН at 1226 cm-1). 
The introduction of hydroxyl and epoxy-groups into 
graphene structure with sp2- hybridization of carbon at-
oms causes reorganisation of planar conjugate system 
into spacial system with sp3- hybrid carbon atoms. As a 
result of it in Raman-spectra graphite oxide (Fig. 3) both 
G - and D-mode in the ID/IG ratio of 0.964 are observed. 
Compositions platinum - reduced graphite prepared by 
platinum addition to graphite oxide by covalent bonds and 
the subsequent reduction. The presence of hydroxyl and 
epoxy (1,2-ether) groups in graphite oxide structure as-
sumes some possibility of Pt4+ addition to graphite oxide. 
Replacement of chloride acido ligand onto oxyl-fragment 
of hydroxyl group demands a presence of platinum in cati-
on part of its compound that is reached by introduction of 
amine, in particular pyridine, to reaction system. Recently 
[2-4] pyridine role in platinum fixation with use of carbox-
yl groups of support was discussed., one of which aspects 
is rearrangement of a complex of platinum to cationic 
complex formation. On the other hand, pyridine disacidi-
fies of acid formed by proton replacement of hydroxyl 
group on platinum-containing cation. The hydroxyl group 
of graphite oxide as opposed to carboxyl is monodentate 
ligand that is a little suitable for platinum bonding. Addi-
tional use of epoxy (1,2-ether) group of graphite oxide as 
ligand is unproductively as platinum-containing anion 
reacts with epoxide by trans-addition, i.e. add to reverse 
side with regard to hydroxyl group. 
A reducing agent able to both Pt4+, and graphite oxide 
reduction is required for preparation of compositions on 
the base of graphite oxide (GO). Four compounds as a 
formate-ion or ethylene glycol or hydrazine or sodium 
borohydride as a reducing agents were used. The re-
duced bases of these compositions after reduction in the 
depending on reductant is called as RGOF, RGOEG, 
RGOH, and RGOB respectively. 
A composition bases after its reduction lose of oxy-
gen (Tabl. 1). In result of this the amounts of decompo-
sition products are decrease (Fig. 2). 
 
200 400 600 800
40
50
60
70
80
90
100
5
4
3
2
M
as
s 
re
la
ti
v
e
, 
%
Temperature, 
о
С
1
 
 
Fig. 2 - Thermograms in Ar of (1) GO and compositions 
(2) Pt/ RGOF, (3) Pt/RGOEG, (4) Pt/RGOB, and 
(5) Pt/RGOH 
 
The observed after reduction increases in compari-
son with GO of C/O ratio (Tabl. 1) and ID/IG ratio 
(Fig. 3), and the temperatures of decomposition (Fig. 2) 
and oxidation (Fig. 4) point out to a change of non-
conjugating sp3-hybridised graphite oxide in ordered 
sp3-hybridised system. 
 
 
 
Fig. 3 – Raman spectra of (1) GO, (2) Pt/RGOH, 
(3) Pt/RGOB, (4) Pt/ RGOF and (5) Pt/RGOEG 
 
Moreover, in Raman spectra of platinum-reduced 
graphite oxide compositions against to graphite pris-
tine D-mode are present and 2G-mode about of 2700 
cm-1 are absent (Fig. 3) i.e. product of reduction of 
graphite oxide is not graphene and right call as re-
duced graphite oxide. 
Thus, hydrazine react with carbonyl compounds 
(Wolff–Kishner reaction) with deoxygenation and car-
bohydrates formation. Epoxides ineract with hydrazine 
yielded aminoalcohols (Wharton reaction). High nitro-
gen content observed for Pt/RGOH (Tabl. 1) very likely 
is associated with aminoalcohols formation and/or the 
transient formation of hydrazones in these reactions 
[7]. Interactions of both carbonyl- and epoxy- com-
pounds with formate-ion or ethylene glycol with oxygen 
loss not associate. 
 
 PLATINUM NANOPARTICLES SUPPORTED ON REDUCED GRAPHITE… PROC. NAP 1, 01NDLCN06 (2012) 
 
 
01NDLCN06-3 
200 400 600 800
0
20
40
60
80
100
5
4
3
1
M
as
s 
re
la
ti
v
e,
 %
Temperature, 
о
С
2
 
 
Fig. 4 - Oxidative thermograms of (1) GO and compositions 
(2) Pt/RGOB, (3) Pt/RGOH, (4) Pt/RGOF, and (5) Pt/RGOB 
 
The reduced compositions contained platinum (0) 
were produced, but only at the use of hydrazine or 
NaBH4 as a reducing agent in contrast to a formate-ion 
or ethylene glycol its Pt loading correspond to calculat-
ed value (Tabl. 1). The symbatic change of Pt loading 
with C/O ratio (Tabl. 1), i.e. slope opposition of Pt load-
ing with oxygen content is observed.  
 
 
 
Fig. 5 - Pt/RGOB TEM image 
 
Thus, platinum fixation by means covalent bonds 
formation and its reduction to metal are carried out 
within one process and platinum is supported on the 
surface of graphite oxide subjected to interaction with 
reductant. Platinum particles in Pt - reduced graphite 
oxide compositions prepared by reduction by formate-
ion or ethylene glycol or hydrazine are distributed non-
uniformly. 
The reduction of composition by sodium borohydride 
produces platinum particles with average particle size 
≈2.0 nm (Fig. 5). Nitrogen atomic content is in 2-4 times 
higher than platinum atomic content (Tabl. 1) that asso-
ciated with our reasons on pyridine role [2-4, 8].  
Pt - reduced graphite oxide compositions catalyze 
the hydrogenation of decene-1 in solution (Fig. 6). The 
hydrogenation rate in all instances is sufficiently low 
therefore in one of cases reaction has not been finished. 
Specific activity of the most preferable catalyst 
Pt/RGOB during reaction time 30 min decreases from 
24 H2 mole·(Pt mole·min)-1 five times. Pt - reduced 
graphite oxide compositions catalyze the nitrobenzene 
hydrogenation in solution too. 
The greatest catalytic activity is shown for the com-
position reduced by sodium borohydride with the parti-
cle size of 2.0 nm, however it is substantially lower 
than it for catalyst based on fullerene black (Fig. 6)[8]. 
 
10 20 30 40 50 60
0
5
10
15
20
25
5
H
2
, 
m
m
o
le
Reaction time, min
4
3 2 1
 
 
Fig. 6 - H2 consumption profiles in decene-1 hydrogenation 
over (1) Pt/RGOF, (2) Pt/RGOH, (3) Pt/RGOEG, 
(4) Pt/RGOB, and (5) Pt/fullerene black 
 
Decene-1 hydrogenation rate converted by the first 
reaction order, decreases disproportionately to decene-1 
concentration loss (Fig. 1). These observations point to 
catalyst poisoning by reaction product as decane or to 
some inhibition of hydrogenation in presence incom-
pletely reduced graphite oxide. 
 
AKNOWLEDGEMENTS 
 
This work was supported by the Russian Founda-
tion for Basic Research (No 11-03-01190-а). 
 
 
REFERENCES 
 
1. E.G. Chepaikin, M.L. Khidekel'. Conjugation as a stimu-
lating factor in the processes of electron transfer with the 
participation of coordination compounds. (Institute of 
Chemical Physics of USSR Academy of Sciences. Preprint. 
Chernogolovkap: 1979). 
2. N.S. Kuyunko, S.D. Kushch, V.E. Muradyan, A.A. Volodin, 
V.I. Torbov, B.P. Tarasov, Hydrogen Materials Science and 
Chemistry of Carbon Nanomaterials. NATO Security 
through Science. Series A. Chemistry and Biology (Spring-
er Science + Business Media BV: 2006). 
3. S.D. Kushch, N.S. Kuyunko, B.P. Tarasov, Russ. J. Gen. 
Chem. 79, 706 (2009).  
4. S.D. Kushch, N.S. Kuyunko, B.P. Tarasov, Zhurn. Obshch. 
Khim. 79, 542 (2009). 
5. S.D. Kushch, N.S. Kuyunko, B.P. Tarasov, Kinetics and 
Catalysis 50, 860 (2009); Kinetika i kataliz 50, 895 (2009). 
6. V. Singh, D. Joung, L. Zhai, S. Das, S.I. Khondaker, 
S. Seal, Prog. Mat. Sci. 56, 1178 (2011). 
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https://essuir.sumdu.edu.ua/bitstream/123456789/35054/1/princon_2012_1_1_55.pdf

Platinum Nanoparticles Supported on Reduced Graphite Oxide as Hydrogenation Catalyst

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