Hydrogenation of naphthalene and anthracene on Pt/C catalysts

Article abstract of DOI:10.1007/s11172-018-2232-2

Hydrogenation of naphthalene and anthracene deposited on Sibunit and active carbon was studied. The reactions were carried out at a temperature of 280 °C and a pressure of 90 atm. The directions for the complete hydrogenation of the investigated substrates were studied. Correlations between the structures of naphthalene and anthracene and their activity in hydrogen absorption are presented. The hydrogenation rates decrease as the substrate is saturated with hydrogen.

Full text of DOI:10.1007/s11172-018-2232-2

Russian Chemical Bulletin, International Edition, Vol. 67, No. 8, pp. 1406—1411, August, 2018
1406
Hydrogenation of naphthalene and anthracene on Pt/С catalysts
А. N. Kalenchuk,а,b A. E. Koklin,b V. I. Bogdan,a,b and L. М. Kustovа,b
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1/3 Leninskie Gory, 119991 Moscow, Russian Federation
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prop., 119991 Moscow, Russian Federation.
Fax: +7 (499) 137 2935. E-mail: akalenchuk@yandex.ru
Hydrogenation of naphthalene and anthracene deposited on Sibunit and active carbon was
studied. The reactions were carried out at a temperature of 280 °C and a pressure of 90 atm.
The directions for the complete hydrogenation of the investigated substrates were studied.
Correlations between the structures of naphthalene and anthracene and their activity in hydro-
gen absorption are presented. The hydrogenation rates decrease as the substrate is saturated
with hydrogen.
Key words: hydrogenation, naphthalene, anthracene, decalin, perhydroanthracene, Pt/C.
Last years, power engineering of hydrogen fuel cells
to reveal and study the features of hydrogenation of
polyaromatic hydrocarbons with different degrees of con-
densation.
(HFCs) has been actively developed world wide. Among
factors that restrain wide use of HFCs is the absence of
compact and safe systems of storage with a high hydrogen
capacity, which are capable of ensuring a completed rapid
charging and hydrogen evolution. It is known that in
chemical compounds hydrogen atoms are packed as close
as possible.1 Among them aromatic hydrocarbons play
a special role, since they have the hydrogen capacity higher
than 7 wt.% and can multiply absorb and evolve chemically
pure hydrogen without impurities of СОx gases in the
course of reversible catalytic reactions of hydrogenation—
dehydrogenation.2,3 The monocyclic systems, such as
benzene/cyclohexane and toluene/methylcyclohexane,
dehydrogenation and hydrogenation processes of which
are widely used in industry, are the most studied hydrogen
storage materials.4—8 However, many problems directly
concerning processes of hydrogen accumulation and gen-
eration remain still unclear. This is especially true for
cyclic compounds with many rings.9,10 For example, dif-
ferent mechanisms of adsorption can be involved in the
hydrogenation of aromatic molecules on the Pt catalysts,
while accessibility of some С—С bonds decreases with
increasing degree of condensation.11—14 In particular, the
hydrogenation rates for a series of linearly conjugated
biphenyl and terphenyl molecules observed on Pt/C cata-
lysts were lower than that for benzene.2,15 Stereoisomers
of terphenyl also showed different characters of hydroge-
nation,15 which also affects the hydrogen charging for
storage systems based on these hydrocarbons.
Experimental
Catalysts. The catalyst 3%Pt/Sibunit on the carbon sup-
port Sibunit (Institute of Problems of Hydrocarbons Proces-
sing, Siberian Branch, Russian Academy of Sciences, Omsk;
 = 0.62 g cm–3) with the granule size d = 1.5—1.8 mm was used
for hydrogenation. Platinum was deposited on the surface by
the impregnation of the support with an aqueous solution of
[H2PtCl6] using the incipient wetness impregnation method
according to a known procedure.2 The catalyst 3%Pt/C (Aldrich,
lot No. 06523VT;  = 0.32 g cm–3) on active carbon (d < 0.1 mm)
was used for comparison. Prior to reactions, the catalysts were
activated for 2 h in a hydrogen flow (30 mL min–1) at 305 С.
The specific surface area (SBET) of the catalysts was determined
by the method of low-temperature nitrogen sorption using the
polymolecular BET model. The particle size (R) and dispersity
of Pt (D) were determined on an ASAP 2020 microanalyzer
(USA) using the method of irreversible chemisorption of CO at
35 С. The morphology of the catalyst surface was studied by
scanning electron microscopy (SEM) with field emission on
a Hitachi SU8000 electron microscope. Images were recorded
in the secondary electron detection mode at an accelerating volt-
age of 2—30 kV and a working distance of 8—10 mm. The mi-
crostructure of the samples was studied by transmission electron
microscopy (TEM) on a Hitachi HT7700 electron microscope.
Images were recorded in the light field mode at an accelerating
voltage of 100 kV.
Substrates. The following chemical reagents without impuri-
ties of sulfur compounds and other chemical poisons of catalysts
were used as substrates: benzene (Acros Organics, 99.5%; m.p.
5—6 С, b.p. 80 С,  = 0.88 g cm–3), naphthalene (Acros
Organics, 99%; m.p. 80—82 С, b.p. 217 С,  = 1.14 g cm–3),
In this work, we compared the liquid-phase hydroge-
nation of naphthalene and anthracene with that of benzene
on the Pt/С catalysts. The purpose of the investigation is
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1406—1411, August, 2018.
1066-5285/18/6708-1406 © 2018 Springer Science+Business Media, Inc.

Hydrogenation of naphthalene and anthracene
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 8, August, 2018
1407
and anthracene (Aldrich, 97%; m.p. 218 С, b.p. 340 С,
 = 1.25 g cm–3).
N (%)
a
60
Kinetic experiment. One volume of the catalyst and 10 volumes
of substrate (10 cm3 : 100 cm3) were charged in a PARR-5500
high-pressure autoclave (USA) with a volume of 600 mL. The
liquid-phase hydrogenation of naphthalene and anthracene with
mechanical stirring (600 rpm) was conducted at 280 С and
90 atm, and benzene was hydrogenated at 180 С and 70 atm.
At certain intervals. the reaction was stopped and the samples
were taken for the analysis. The composition of the reaction
products was analyzed on a KristalLyuks-4000M chromatograph
(Khromatek, Russia) with the ZB-5 (Zebron, USA) and TR-FFAP
(Thermo Scientific, USA) capillary columns with a flame-ion-
ization detector and on a FOCUS DSQ II mass spectrometer
coupled with chromatograph (MS/GC) (Thermo Fisher Scien-
tific, USA) with the TR-5MS capillary column (Thermo, USA).
The conversion (Х) and selectivity (S) of the hydrogenation
products were calculated by the equations
50
40
30
20
10
2
4
6
8
d/nm
N (%)
40
b
Х = [(c0 – c)/c0]•100%,
S = [c(i)/c(k)]•100%,
30
20
10
where c0 and с are the initial and final concentrations of the
starting substrate, respectively; and c(i) and c(k) are the sums
of concentrations of individual products and all reaction products,
respectively.
Results and Discussion
According to the SEM data, the catalyst surface on the
active carbon 3%Pt/C (Aldrich) consists of aggregates
formed by particles of varying shape larger than 2 m in
size.16 The 3%Pt/Sibunit catalyst has a more ordered
surface formed of numerous particles less than 1 m. The
uniform distribution of Pt is observed on the TEM images
of both studied catalysts. The histograms of the particle
size distribution of both catalysts were calculated from
their TEM images. It is seen that fine clusters (to 2 nm)
mainly located on the external surface of the Sibunit glob-
ules prevail in the Sibunit-based catalysts. The catalyst on
active carbon has a broader particle size distribution
(dav = 7 nm). The porous structure of active carbons is
characterized by the presence of all types of pores with the
following pore sizes and specific volumes: submicro- and
micropores (to 2 nm, 0.2—0.6 cm3 g–1), mesopores
(2—50 nm, 0.15—0.2 cm3 g–1), and macropores (>50 nm,
0.02—0.10 cm3 g–1).17 Sibunit is a predominantly meso-
porous material. According to the data of CO chemisorp-
tion, the average pore size in Sibunit used as a support in
the catalyst studied is 6 nm.18
2
4
6
8
10
12
d/nm
Fig. 1. Histograms of the Pt particle size distribution for the
catalysts 3%Pt/Sibunit (a) and 3%Pt/C (Aldrich) (b).
of the platinum clusters, and a substantially lower specific
surface area. However, the times of complete benzene
hydrogenation for both catalysts do not differ within the
experimental error. The 95% conversion of benzene on
the both catalysts is achieved approximately 20 min after
the reaction onset, whereas the complete hydrogena-
tion is attained in 24 min. Similar catalytic activities
of both samples can be related to blocking of some Pt
atoms in the active carbon-based catalyst micropores,
which decreases the fraction of the accessible surface of
active metal.19
Table 1. Texture characteristics of the Pt/C catalysts
a
Catalyst
Bulk density SBET
Db (%) Rc/nm
/g cm–3
/m2 g–1
The texture characteristics of the catalysts 3%Pt/
Sibunit and 3%Pt/C (Aldrich) are presented in Table 1.
A comparison with the data in Fig. 1 shows that the sizes
of platinum clusters determined by the chemisorption
method and electron microscopy are comparable. The
catalyst on Sibunit has a higher dispersity, smaller sizes
3%Pt/Sibunit
0.65
0.32
300
760
49
22
2.5
5.5
3%Pt/C (Aldrich)
a Surface area.
b Dispersity of Pt.
c Particle size of Pt.

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Russ. Chem. Bull., Int. Ed., Vol. 67, No. 8, August, 2018
Kalenchuk et al.
ring in tetralin improves,21 but the cyclohexane "chair"
violates complanarity of the molecule to induce steric
hindrances for the interaction with the catalyst. It is seen
from Fig. 2 that the maximum on the curve of tetralin
formation is achieved within 15 min, and the curve of
decalin formation reaches a plateau already within 35 min.
Fifty minutes are required for the complete saturation of
naphthalene on the catalyst at 99.5% conversion. Figure 2
also shows that about 15 min are needed to achieve 95%
conversion for naphthalene hydrogenation, less time than
required to convert 95% of benzene. The final hydrogena-
tion product, decalin, consists of a mixture of trans-
(60 wt.%) and cis-isomer (40 wt.%). The overall selectiv-
ity of two isomers exceeds 99.5%. For the complete satu-
ration of naphthalene with hydrogen on the 3%Pt/Sibunit
catalyst 60 min are needed, and the shape of the curves
and the ratio of formed isomers remain unchanged.
The experimental curves showing a change in the
concentrations of the hydrogenation products of anthra-
cene (С14Н10) on the 3%Pt/C (Aldrich) catalyst in time
are presented in Fig. 3. Perhydroanthracene (С14Н24) is
the product of the complete hydrogenation of anthracene.
The induction period on curve 5 (see Fig. 3) also indicates
the formation of perhydroanthracene via intermediates.
The chromatographic and MS/GC analyses showed that
9,10-dihydroanthracene (С14Н12), 1,2,3,4-tetrahydroan-
thracene (С14Н14), and isomers of octahydroanthracene
(С14Н18) with different arrangements of the last unsatu-
rated ring are formed as intermediate products of the reac-
tion. No compounds with incompletely saturated benzene
rings, such as hexahydroanthracene (С14Н16), decahydro-
anthracene (С14Н20), and dodecahydroanthracene (С14Н22),
were found among the reaction products. According to the
stoichiometry of formation of the observed reaction prod-
ucts, the hydrogenation of anthracene can be presented as
general Scheme 2.
C (%)
100
80
60
40
20
0
2
3 (trans)
1
3 (cis)
10
Fig. 2. Concentration of the products of naphthalene hydrogena-
tion as a function of the reaction time: 1, C10H8; 2, C10H12
and 3, C10H18
20
30
40
50 t/min
;
.
The experimental time dependences of the concentra-
tion of the hydrogenation products of naphthalene (С10Н8)
on the 3%Pt/C catalyst (Aldrich) are shown in Fig. 2.
Curve 3 in Fig. 2 describes the kinetics of tetralin forma-
tion and has a characteristic "induction period" indicat-
ing that decalin (decahydronaphthalene, С10Н18) is not
formed directly but via the intermediate product tetralin
(1,2,3,4-tetrahydronaphthalene, С10Н12). The concentration
of tetralin increases from zero, passes through a maximum,
and again decreases to zero (see Fig. 2, curve 2). The
dependence of the naphthalene consumption on time (see
Fig. 2, curve 1) is described by an S-like curve, according
to which the concentration decreases rapidly to the mo-
ment of formation of a maximum on the curve of tetralin
and then decreases slowly to zero. The hydrogenation of
naphthalene can be presented as general Scheme 1.
C (%)
100
Scheme 1
I
II
III
80
60
40
20
0
4
5
2
1
C14H10
C14H12 (I)
C
C
14H14 (I)
14H18 (II)
C14H24 (III)
3
In a naphthalene molecule, four С(1)—С(2) bonds are
shorter than those in benzene (1.365 Å) and two С(2)—С(3)
bonds (1.404 Å), four С(4)—С(10) bonds (1.420 Å), and
the distance between the С(9)—С(10) nodal atoms (1.420
Å) are longer, which leads to a distortion of symmetry of
two fused benzene rings.13,20 The symmetry of the benzene
10
20
30
40 t/h
Fig. 3. Concentration of the products of anthracene hydrogena-
tion as a function of the reaction time (see clarifications in
the text).

Hydrogenation of naphthalene and anthracene
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 8, August, 2018
1409
Scheme 2
In Fig. 3, all compounds obtained are graphically
combined into three groups according to the degree of
saturation of aromatic rings. Group I of compounds with
one cyclohexane ring contains 9,10-dihydroanthracene
and 1,2,3,4-tetrahydroanthracene. Octahydroanthracene
isomers form group III of compounds with two saturated
rings. Group III includes conformers of perhydroanthra-
cene. The total concentrations taking into account all
found isomeric compounds for groups II and III are shown
in Fig. 3 (curves 4 and 5, respectively).
of molecules of both compounds favor the enhancement
of steric hindrances for the interaction with the catalyst.
The conversion for both intermediates as high as 95% is
achieved in approximately 10 h after the reaction onset
under the experimental conditions used.
The major product of a deeper hydrogenation of
9,10-dihydroanthracene and 1,2,3,4-tetrahydroanthracene
is 1,2,3,4,5,6,7,8-octahydroanthracene (Fig. 4, a, curve 3)
with the central (sym-) benzene ring and two stereoisomers
of octahydroanthracene with the terminal benzene ring:
The symmetry of benzene rings in an anthracene mol-
ecule is also violated compared to the symmetry of
a benzene molecule. The central ring with four С(9)—С(11)
distances of 1.400 Å is distorted to a lesser extent than both
terminal rings with four С(1)—С(2) distances of 1.370 Å,
two С(2)—С(3) distances of 1.410 Å, and four С(1)—С(11)
distances of 1.463 Å. Both bonds between the nodal atoms
lengthen compared to those in naphthalene and are equal
to 1.450 Å each.13,20 The curve of changing the anthracene
concentration in time on the 3%Pt/C catalyst (Aldrich)
(see Fig. 3, curve 1) resemble in shape the curve for naph-
thalene. However, about 60 min are required to achieve
95% conversion of anthracene, which exceeds the time
found for naphthalene. The same conversion of anthracene
on the 3%Pt/Sibunit catalyst is achieved approximately
10 min later.
C (%)
70
a
1,2,3,4,4aa,9aa,10-C14H18
1,2,3,4,4aaa,9,10,10aa-C14H18
1,2,3,4,5,6,7,8-C14H18
1
2
3
60
50
40
30
20
10
3
1
2
5
10 15
20 25 30
35
40 t/h
The presence of two terminal benzene rings on the
central ring favors an increase in the reactivity of anthra-
cene in positions С(9) and С(10) Å.13,20 It is seen from
Fig. 3 that the amount of 9,10-dihydroanthracene found
in analysis of the samples (see Fig. 3, curve 2) exceeds the
amount of 1,2,3,4-tetrahydroanthracene (see Fig. 3, curve 3)
approximately threefold. A 9,10-dihydroanthracene mol-
ecule can structurally be characterized as tetralin shielded
by the benzene ring, and 1,2,3,4-tetrahydroanthracene can
be presented as naphthalene shielded by the cyclohexane ring.
According to this representation and results of naphthalene
hydrogenation, a lower concentration of 1,2,3,4-tetra-
hydroanthracene in the products (see Fig. 3, curve 3) is
possibly attributed to a higher rate of its conversion to
octahydroanthracene compared to 9,10-dihydroanthra-
cene. It is seen that additional violations of complanarity
C (%)
60
b
50
40
30
20
10
0
1
2
3
5
4
5
10
15
20
25
30
35
40 t/h
Fig. 4. Concentration of isomers of octahydroanthracene (1—3)
(a) and perhydroanthracene (1—5) (b) formed during anthracene
hydrogenation as a function of the reaction time.

1410
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 8, August, 2018
Kalenchuk et al.
1,2,3,4,4aa,9,9aa,10- and 1,2,3,4,4aa,9,10,10aa-octa-
hydroanthracene (see Fig. 4, a, curves 1, 2). Molecules of
each octahedroanthracene isomer can be presented as
tetralin-like structures shielded by the cyclohexane "chair"
in different manners. Two stereoisomers with the terminal
benzene ring are formed in approximately equal amounts
(see Fig. 4, a, curves 1, 2) but in appreciably smaller
amounts than the sym-isomer with the central benzene
ring. A similar ratio can also be related to a higher reactiv-
ity of the terminal rings of octahydroanthracene compared
to the central ring. On the one hand, an increase in non-
complanarity of the octahydroanthracene isomers stronger
impeded hydrogenation but, on the other hand, increases
the possible number of hydrogenation routes.
Chromatographic and MS/GC analyses showed that
the samples of the reaction products contain five com-
pounds of the general stoichiometric composition С14Н24
corresponding to perhydroanthracene conformers (see Fig. 4, b,
curves 1—5). The overall selectivity to five conformers
exceeded 99%, and the complete saturation with hydrogen
of the initial anthracene to final perhydroanthracene,
under the conditions of certain experiment, was achieved
within 38 h after the start of hydrogenation.22 It is seen
from Fig. 3 that the slope of experimental curve III that
characterizes the rate of formation of a conventional group
of compounds with three saturated rings is smaller than
the slope of curves II and I describing the rate of formation
of the compounds with two and one saturated rings, re-
spectively.
The obtained experimental data show that the hydro-
genation of the studied compounds with fused structures
can be presented as a combination of hydrogenation reac-
tions of each benzene ring in naphthalene and anthracene
molecules, and optimum conditions differ for each reac-
tion. Based on the time needed to achieve 95% conversion
of hydrogenation and ignoring different reaction condi-
tions of hydrogenation of benzene, naphthalene, and
anthracene, a series of decreasing activity for these sub-
strates is naphthalene  benzene < anthracene. The time
required to achieve complete hydrogenation increases in
the order benzene < naphthalene << anthracene. A simi-
lar decrease in activity correlates with the results obtained
earlier for linearly conjugated biphenyl and terphenyl
molecules.2 However, hydrogenation is impeded for fused
naphthalene and anthracene molecules because of the
enhancement of steric hindrances in the initial molecules
and intermediate reaction products, especially at the nodal
carbon atoms.
was observed to be –0.63 eV per one Pt atom.23—25 For
naphthalene with two fused benzene rings, the adsorption
energy in the dibridge conformation (Nph2) is also higher
than that in the conformation Nph1: –0.67 and –0.5 eV
per one Pt atom, respectively.23,25
The adsorption energy of the anthracene molecule
in the tribridge configuration (Аnt2) was found to be
–0.71 eV per one Pt atom.25 It is seen from comparison
that the calculated adsorption energies per one Pt atom
for the studied substrates in the bridge conformation in-
crease in the series naphthalene  benzene < anthracene.
Taking into account the total number of Pt atoms necessary
for the accomplishment of the corresponding bridge con-
formations, the order of increasing adsorption energy
per molecule is benzene < naphthalene << anthracene.
A comparison of the experimental and theoretical data
shows a correlation between the time needed to achieve
complete hydrogenation of benzene, naphthalene, and
anthracene and calculated adsorption energies of the cor-
responding molecules on the Pt(111) surface.
To conclude, similar parameters of hydrogenation were
obtained on the Pt/C catalysts with different morphologies:
on active carbon and carbon support Sibunit. Comparing
the experimental data on the hydrogenation of benzene,
naphthalene, and anthracene in a direct way and ignoring
more stringent reaction conditions, it can be inferred that
the times needed to achieve 95% conversion are compa-
rable at the step of hydrogenation of the first benzene ring
in planar naphthalene and benzene molecules. Nearly
twice as much time was needed to achieve 95% conversion
of anthracene as the size of the molecule increased to three
rings. As the saturation with hydrogen increases, the cyclo
hexane ring impart non-complanarity to molecules of
the formed intermediates, which favors an increase in
steric hindrances and inhibition of the hydrogenation
reaction. Under these conditions, nodal C atoms become
significant, different hydrogenation conditions of which
favor different quantitative ratio of isomers in the final
products. In particular, the formation of cis- and trans-
isomers of decalin depends on the orientation of the
H atom (to the face or to the side from the surface) in
position 10 in the intermediate product octahydronaph-
thalne (1,9-octalin).22,26,27 Analyzed samples contained
no cracking products in all experiments.
The quantum chemical (DFT) modeling of benzene
adsorption on the Pt(111) surface showed that with allow-
ance for the optimization of geometric parameters a stron-
ger interaction (Еads = –0.69 eV per Pt atom) occurs in
the bridge position (Вz2) when the bond is formed with
four metal atoms. In Вz1, when the benzene molecule
forms a bond with three Pt atoms, the adsorption energy
The authors are grateful to the Department of Structure
Studies of the N. D. Zelinsky Institute of Organic Chem-
istry (Russian Academy of Sciences) for investigations of
the samples by electron microscopy.

Hydrogenation of naphthalene and anthracene
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 8, August, 2018
1411
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Science Foundation (Project No. 14-50-00126).
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Received June 4, 2018;
accepted June 15, 2018